CN108424551B

CN108424551B - Composite rubber

Info

Publication number: CN108424551B
Application number: CN201810291672.0A
Authority: CN
Inventors: 洪金龙; 李华春
Original assignee: Yunnan Dianyuan Rubber Co ltd
Current assignee: Yunnan Dianyuan Rubber Technology Co.,Ltd.
Priority date: 2018-03-30
Filing date: 2018-03-30
Publication date: 2020-12-01
Anticipated expiration: 2038-03-30
Also published as: CN108424551A

Abstract

The invention provides a composite rubber, which is prepared by processing a solid rubber material by using a composite constant-viscosity agent; the composite rubber has the impurity content of 0.05-0.16%, the ash content of 0.5-1.0%, the nitrogen content of less than or equal to 0.6%, the volatile matter content of less than or equal to 0.8%, the plasticity retention rate of more than or equal to 40%, the Mooney viscosity ML/(1 '+ 4') of 55-72 ℃ at 100 ℃, the copper content of less than or equal to 8mg, the manganese content of less than or equal to 10mg and the water soluble matter content of 0.8-2.4%; according to the invention, the solid rubber material is subjected to constant viscosity treatment by using the composite constant viscosity agent, so that gelation of the prepared composite rubber caused by rising of Mooney viscosity is avoided, and the stability of the Mooney viscosity of the rubber is improved; meanwhile, the composite rubber prepared by the method has better mechanical property and aging resistance.

Description

Composite rubber

Technical Field

The invention relates to the field of natural rubber, in particular to composite rubber and a preparation method thereof.

Background

Currently, natural rubber is widely used in the rubber industry and the tire industry because of its excellent physical properties. Specifically, in the production process of natural rubber, natural rubber latex produced in tropical countries or regions such as thailand, malaysia, indonesia and the like is generally used, the natural rubber latex is subjected to a series of treatments such as purification, coagulation and curing, dehydration and impurity removal, drying and the like to form natural rubber, then the natural rubber is classified according to the variety and the grade, and the natural rubber is subjected to corresponding secondary processing according to the requirements of different application fields to produce corresponding rubber products.

However, since the molecular chain of the natural rubber has active groups such as aldehyde groups, cross-linking in the molecular chain and among the molecular chains is easy to occur during the storage of the natural rubber, and a macromolecular network structure is formed, so that the mooney viscosity value of the natural rubber is increased, and the gelation of the natural rubber is caused. Due to the cross-linking reaction among the active groups on the molecular chain, various physical and mechanical processing properties of the natural rubber are changed, such as poor viscosity stability, reduced mechanical properties, reduced aging resistance and the like of the natural rubber, which has great influence on secondary processing and utilization of the natural rubber. Therefore, in order to avoid crosslinking between reactive groups on the molecular chain of the natural rubber as much as possible, it is generally carried out by adding a tackifier to ensure stability of the Mooney viscosity index of the natural rubber.

However, in the prior art, the process of performing constant viscosity treatment on natural rubber by adding a constant viscosity agent into natural rubber often has the problems of poor stability of the used constant viscosity agent and poor dispersion degree of the constant viscosity agent in the natural rubber caused by unreasonable constant viscosity treatment process, so that the mooney viscosity stability of the produced natural rubber is poor, meanwhile, the consistency of mooney viscosity indexes of different batches of natural rubber is poor, the mechanical property and the aging resistance of the natural rubber are not improved, and the physical property and the aging resistance of a natural rubber product after secondary processing are not improved.

Application document with the application number of CN201310672741.X discloses a constant-viscosity natural rubber and a preparation method thereof, belonging to the technical field of natural rubber processing. The Mooney viscosity of the rubber is 50.00-65.00, the plasticity retention rate is not less than 60, the tensile strength is not less than 14MPa, and the elongation at break is not less than 700%. The constant-viscosity natural rubber is prepared by adding more than or equal to 2.5 percent of hydroxylamine constant-viscosity agent solution and more than or equal to 8.0 percent of hydrazine hydrate solution into fresh latex. In the application, a hydroxylamine constant viscosity agent solution with the concentration of more than or equal to 2.5 percent and a hydrazine hydrate solution with the concentration of more than or equal to 8.0 percent are used as constant viscosity agents, however, hydroxylamine compounds belong to toxic substances and are forbidden to be used in many countries, and the hydroxylamine compounds are easy to decompose, so that the mooney viscosity stability of the natural rubber is not improved; meanwhile, the application does not relate to the dispersion condition of the constant viscosity agent in the natural rubber, which is not only not beneficial to improving the Mooney viscosity stability of the natural rubber, but also not beneficial to ensuring the consistency of Mooney viscosity indexes of different batches of natural rubber, thereby being not beneficial to improving the mechanical property and the aging resistance of the natural rubber and natural rubber products after secondary processing.

Application No. CN01121044.3 discloses a natural rubber latex and a natural rubber containing a viscosity stabilizer and a production method thereof, a method for producing a natural rubber containing a viscosity stabilizer including a step of adding a viscosity stabilizer liquid diluted with a solvent to a natural rubber and a method for producing a natural rubber latex containing a viscosity stabilizer by adding a viscosity stabilizer dissolved in an aliphatic chain compound, and a natural rubber containing a viscosity stabilizer produced by adding a viscosity stabilizer liquid diluted with a solvent thereto after coagulation of a natural rubber. In the application, an aliphatic chain compound, especially an aliphatic polyol, is used as a solvent of a viscosity stabilizer, and most of the aliphatic chain compounds, including all the aliphatic polyols, can release part of protons when being used as the solvent, so that the stability of natural rubber latex is damaged in the production process of natural rubber, the latex is promoted to be solidified prematurely, the viscosity stabilizer is not favorably dispersed in the latex more sufficiently, the dispersion condition of the viscosity stabilizer in the latex is influenced to a certain extent, the Mooney viscosity stability of the natural rubber is not favorably improved, the consistency of Mooney viscosity indexes of different batches of natural rubber cannot be ensured, and the mechanical property and the aging resistance of the natural rubber and natural rubber products subjected to secondary processing are not favorably improved; meanwhile, the process of the natural rubber in the application is simple, so that the natural rubber and the natural rubber product subjected to secondary processing cannot have good mechanical property and aging resistance.

Disclosure of Invention

The invention provides a composite rubber for solving the problems of poor stability of a constant viscosity agent, poor dispersion degree of the constant viscosity agent in natural rubber and the like caused by unreasonable constant viscosity treatment process in the process of constant viscosity treatment of the natural rubber in the prior art, so that Mooney viscosity indexes of different batches of rubber have better consistency, the Mooney viscosity stability, the mechanical property and the aging resistance of the natural rubber are improved, and the mechanical property and the aging resistance of related rubber products prepared by using the natural rubber are ensured.

In order to solve the technical problems, the technical scheme of the invention is as follows:

a composite rubber is prepared by processing a solid rubber material with a composite constant-viscosity agent to obtain a composite rubber; the composite rubber has the impurity content of 0.05-0.16%, the ash content of 0.5-1.0%, the nitrogen content of less than or equal to 0.6%, the volatile matter content of less than or equal to 0.8%, the plasticity retention rate of more than or equal to 40%, the Mooney viscosity ML/(1 '+ 4') of 55-72 at 100 ℃, the copper content of less than or equal to 8mg, the manganese content of less than or equal to 10mg and the water soluble matter content of 0.8-2.4%.

Further, the composite constant viscosity agent comprises an organic constant viscosity agent and/or an inorganic constant viscosity agent; the organic constant viscosity agent comprises an organic amine compound, wherein the organic amine compound comprises at least one compound of hydroxylamines, fatty amines, alcamines, alicyclic amines and aromatic amines; the inorganic constant viscosity agent comprises inorganic ammonium salt, and the inorganic ammonium salt comprises at least one of ammonium chloride, ammonium sulfate and ammonium nitrate.

Further, the composite constant viscosity agent comprises an organic constant viscosity agent and/or an inorganic constant viscosity agent, wherein the organic constant viscosity agent is an organic amine compound solution taking a polar aprotic organic solvent as a solvent; the inorganic constant adhesive is an inorganic ammonium salt solution containing zinc-ammonia complex ions;

the organic amine compound comprises at least one compound of hydroxylamines, fatty amines, alcamines, alicyclic amines and aromatic amines;

the polar aprotic organic solvent comprises one or more of dimethylformamide, dimethylacetamide, hexamethylphosphoramide, and 1, 3-dimethyl-2-imidazolidinone;

the inorganic ammonium salt comprises at least one of ammonium chloride, ammonium sulfate and ammonium nitrate.

Further, the solid rubber material comprises at least one of standard rubber, rubber cup rubber ball, crepe rubber, air-dried rubber sheet and rubber sheet stock.

Further, the composite rubber is prepared by taking a solid rubber material as a raw material, and comprises the following steps:

s1, taking inorganic ammonium salt solution with the concentration of 2.5-6.0mol/L as leachate, leaching zinc ore at 90-102 ℃, filtering the leachate, and cooling the filtrate to room temperature to obtain inorganic ammonium salt solution containing zinc ammine complex ions; dissolving an organic amine compound in a polar aprotic organic solvent to prepare 2.0-3.2mol/L organic amine compound solution; adding an inorganic ammonium salt solution containing zinc-ammonia complex ions into the organic amine compound solution to prepare a composite constant adhesive for later use;

s2, crushing the solid rubber, and carrying out floating washing in water;

s3, extruding the floated rubber material, and floating in water;

s4, judging whether the rubber material meets the first condition, and if not, directly performing the step S5; if so, adding an aqueous solution of organic dibasic acid into a creper, and then performing step S5;

s5, conducting crepe on the extruded rubber material to enable the rubber material to be in a continuous sheet shape, and meanwhile conducting spray washing on the rubber material;

s6, judging whether the rubber material meets the second condition, and if not, directly performing the step S7; if so, adding an aqueous solution of an inorganic base into the granulation tank, and then performing step S7;

s7, putting the rubber material subjected to crepe into a granulation tank, performing granulation treatment, and spraying and washing the rubber material;

s8, spraying or soaking the granulated rubber material by using the composite constant viscosity agent in the step S1;

and S9, sending the rubber material to a drying furnace, dehumidifying, drying at high temperature and low temperature, and cooling to room temperature to obtain the composite rubber.

Preferably, in step S1, the ratio of the mass of the zinc ore to the volume of the inorganic ammonium salt solution is 100-150 g/L; the ratio of the volume of the inorganic ammonium salt solution containing the zinc-ammonia complex ions to the volume of the organic amine compound solution is 1: 1.5-2.0;

the zinc ore comprises at least one of calamine, willemite and hydrozincite.

Further, the first condition comprises at least one of the surface temperature of the rubber material is less than or equal to 10 ℃ or the Shore hardness of the rubber material is more than or equal to 40 HA;

the second condition is that the Shore hardness of the rubber material is less than or equal to 20 HA.

Further, the organic dibasic acid comprises at least one of oxalic acid, succinic acid and malonic acid;

the inorganic base comprises at least one of calcium hydroxide, barium hydroxide and ammonia water.

Further, the drying furnace adopts saturated steam to dry the sizing material, and comprises a dehumidifying part, a high-temperature drying part, a low-temperature drying part and a cooling part, wherein the dehumidifying part is communicated with the high-temperature drying part, the high-temperature drying part is communicated with the low-temperature drying part, and the low-temperature drying part is communicated with the cooling part;

the cooling part is a cooling cabinet, and an air supplementing fan is arranged on the cooling cabinet to enable the whole cooling cabinet to be in a negative pressure state;

the drying furnace also comprises an automatic steam pressure adjusting device, the automatic steam pressure adjusting device is connected with the steam pipeline, and the temperatures of the dehumidification part, the high-temperature drying part, the low-temperature drying part and the cooling part are controlled by adjusting the steam pressure in the steam pipeline; the drying furnace is provided with a rubber vehicle limiting device at an outlet so as to ensure the cooling time of the rubber material in the cooling part.

Further, the preparation method comprises the steps of taking solid rubber as a raw material, cutting the rubber into preset weight according to a proportion, putting the rubber into a dry stirring machine, wherein a constant-viscosity agent spray head is arranged at the inlet of the dry stirring machine, and spraying the composite constant-viscosity agent according to a preset proportion; and (3) fully and uniformly stirring the rubber material and the composite constant binder, extruding the rubber material out of a dry stirring machine under the action of extrusion and shearing, cooling the rubber material in a cooling cabinet by using a blast cooling or negative pressure draft cooling mode after the rubber material enters a cooling hopper through a vibrating screen, and discharging the rubber material after the temperature of the rubber material is lower than 55 ℃ to obtain the composite rubber.

Compared with the prior art, the composite rubber provided by the invention has the advantages that the constant-viscosity agent is compounded, the solid rubber material is subjected to constant-viscosity treatment, the gelation of the prepared composite rubber caused by the increase of the Mooney viscosity can be effectively avoided, and the stability of the Mooney viscosity of the composite rubber is improved.

Meanwhile, by adding the composite constant adhesive containing zinc-ammonia complex ions, the activity of the vulcanization accelerator is improved, the vulcanization speed is accelerated, the vulcanization period is shortened, the consumption of the vulcanization accelerator is reduced, the production cost is reduced, short vulcanization crosslinking bonds are generated in the vulcanization process of the rubber, the crosslinking density is improved, the acting force between the chemical bonds and the stability of the chemical bonds are enhanced, and therefore, after the composite rubber prepared by the invention is processed into a rubber product, the mechanical property of the rubber product is improved, and the heat-resistant aging performance of the rubber product is ensured.

The polar aprotic organic solvent used in the composite constant adhesive not only improves the dispersion performance of the organic amine compound, but also promotes the inorganic ammonium salt solution containing the zinc-ammonia complex ions to be uniformly mixed with the organic amine compound solution, namely, ensures the full and uniform mixing of the organic constant adhesive component and the inorganic constant adhesive component; meanwhile, in the composite constant-viscosity agent, water and a polar aprotic organic solvent are compounded to serve as a solvent of the composite constant-viscosity agent, so that the dispersibility of the constant-viscosity agent in constant-viscosity treatment of solid rubber materials is improved, the uniform contact between the composite constant-viscosity agent and the solid rubber materials is ensured, the reaction uniformity between active groups in rubber and the constant-viscosity agent is improved, the efficiency of constant-viscosity treatment is improved, the stability of the Mooney viscosity of the composite rubber is also ensured, and the Mooney viscosity indexes of different batches of composite rubber have better consistency.

In addition, the invention controls the content index of water-soluble substances and the content index of protein in the rubber and performs corresponding process treatment, so that the prepared composite rubber not only has better mechanical property, but also has excellent aging resistance, and the mechanical property and the aging resistance of related rubber products prepared by using the composite rubber are further improved.

Meanwhile, in the invention, two stages of judging processes of the state of the rubber material are arranged in the production and preparation process, so that the rubber material has better hardness and viscosity all the time in the processing process, the processing performance of the rubber material is ensured, the processing processes of wrinkling, granulating, drying and the like are facilitated, the rubber material can be fully subjected to the wrinkling, granulating and drying processes, the production efficiency is favorably improved, the mechanical performance and the aging resistance of the composite rubber are favorably improved, and the consistency of the composite rubber in different production batches on the product performance is favorably improved.

Drawings

In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a flow chart of the preparation of a compounded rubber in the present invention;

FIG. 2 is a schematic diagram of an apparatus for manufacturing a compounded rubber processing system according to the present invention;

FIG. 3 is a side view of a creper in a processing system for compounded rubber according to the present invention.

Wherein the first crusher 1; a conveyor 2; a second crusher 3; a second conveyor 4; a first flotation tank 5; a second flotation tank 6; a bucket elevator 7; a second bucket elevator 8; a third bucket elevator 9; a third crusher 10; a fourth crusher 11; a twin-roll machine 12; a third flotation tank 13; a fourth flotation tank 14; a fifth flotation tank 15; a single-roll extruder 16; a fourth bucket elevator 17; a second single roll machine 18; a second twin-roll machine 19; a fifth bucket elevator 20; a granulation tank 21; a crepe unit 22; a conveyor 23; a first creper system 24; a transfer device 25; a glue pump 26; a first granulator 27; a second granulator 28; a third granulation tank 29; a third granulator 30; a sixth glue spreader 31; a third creper system 32; a third conveyor system 33; a fourth granulation tank 34; a fourth granulator 35; a second glue pump 36; a first exhaust treatment system 37; a second exhaust treatment system 38; a vibrating screen 39; a glue feeder 40; a dehumidifying fan 41; a drying oven 42; a blower 43; a second blower 44; a cooling fan 45; a parking space brake 46; a bag sawing machine 47; a work table 48; a third conveyor 49; a weighing device 50; a packing machine 51; a fourth conveyor 52; a second weighing device 53; an all metal detector 54; a bagging device 55; a second detection device system 56; a coagulation tank 57; a thinning machine 58; a water tank 59; a second vibrating screen 60; a milk-standard wastewater circulating device 61; a coagulation waste water circulating device 62; a clear water circulating device 63.

Detailed Description

The technical solutions in the embodiments of the present invention are further described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.

It should be noted that, in order to facilitate the understanding of the present invention by those skilled in the art, the percentage of the substance content or the percentage of the substance addition amount referred to in the present invention are mass fractions; meanwhile, the composite rubber in the invention is natural rubber, wherein the composite double-character means the rubber and the auxiliary agent are compounded to prepare the natural rubber, but not the rubber prepared by compounding different kinds of rubber.

The composite rubber has impurity content of 0.05-0.16%, ash content of 0.5-1.0%, nitrogen content not more than 0.6%, volatile matter content not more than 0.8%, plasticity maintaining rate not less than 40%, Mooney viscosity ML/(1 '+ 4') at 100 deg.c of 55-72%, copper content not more than 8mg, manganese content not more than 10mg and water soluble matter content of 0.8-2.4%.

Furthermore, the water-soluble substance content of the composite rubber is 1.0-2.0%, and the protein content is 1.3-1.8%.

Preferably, the water soluble content of the composite rubber is between 1.0% and 2.0%, the protein content is between 1.3% and 1.8%, and the absolute value of the difference between the water soluble content and the protein content of the composite rubber is not more than 0.6%.

The present invention will be described in detail below by way of experimental examples:

it should be noted that the data in the following experimental examples are obtained by a lot of experiments, which are limited by the text, and only a part of the data is shown in the specification, and those skilled in the art can understand and implement the present invention under the data, and the rest of the data have the same trend and can draw the same conclusion as the experimental conclusion described below, and will not be described in detail later.

Experimental example 1

Taking rubber raw materials with different qualities, preparing the natural rubber by adopting the same existing process on the premise of not carrying out any treatment on the content of water-soluble substances in the rubber raw materials, taking intermediate values of other parameters in the process, and detecting the mechanical property and the aging resistance of the natural rubber.

As can be seen from table 1, when the content of the water-soluble substance in the natural rubber is less than 0.8%, the tensile strength, the tear strength and the tensile strength after aging of the natural rubber are all significantly reduced, which not only affects the aging resistance of the natural rubber to a certain extent, but also severely affects the mechanical properties of the natural rubber; when the content of the water soluble substance in the natural rubber is more than 2.4%, the tensile strength, the elongation at break, the tensile strength after aging and the elongation at break after aging of the natural rubber are all obviously reduced, which seriously influences the aging resistance and the mechanical property of the natural rubber. Therefore, the invention adopts the natural rubber with the water soluble substance content of 0.8-2.4%.

TABLE 1 influence of the content of water-soluble substances in natural rubber on its mechanical and ageing resistance properties

Note: detecting the content of the natural rubber water-soluble substance according to a standard NY/T1527-2007; detecting the tensile strength, the tearing strength and the elongation at break of the natural rubber according to the standard GB/T528-2009; after heat aging (aging at 100 ℃ for 72 hours) in a ventilation oven, the tensile strength after aging and the elongation at break after aging of the natural rubber are detected according to the standard GB/T528-2009.

It should be noted that, when the same index is detected in the present invention, the same standard file is used for detection, which is not described in detail below.

Experimental example 2

Taking rubber raw materials with different qualities, preparing the natural rubber by adopting the same existing process on the premise of not carrying out any treatment on the protein content in the rubber raw materials, taking intermediate values of other parameters in the process, and detecting the mechanical property and the aging resistance of the natural rubber.

As can be seen from table 2, when the protein content in the natural rubber is less than 1.0%, the elongation at break, the tensile strength after aging, and the elongation at break after aging of the natural rubber are all significantly reduced, which not only affects the mechanical properties of the natural rubber to a certain extent, but also severely affects the aging resistance of the natural rubber; when the protein content in the natural rubber is more than 2.0 percent, the tensile strength, the tearing strength and the elongation at break of the natural rubber are all obviously reduced, which seriously influences the mechanical property of the natural rubber, and the aging resistance still keeps a good level at the moment. Therefore, the invention adopts the natural rubber with the protein content of 1.0-2.0%.

TABLE 2 influence of the protein content of Natural rubber on its mechanical and ageing resistance Properties

Note: the protein content of natural rubber was determined according to the standard GB/T8088-1999.

Experimental example 3

Taking rubber raw materials with different qualities, preparing natural rubber by adopting the same production processing technology on the premise of not carrying out any treatment on the content of water-soluble substances and the content of protein in the rubber raw materials, taking intermediate values of other parameters in the technology, grouping the natural rubber with the content of the water-soluble substances between 0.8% and 2.4% and the content of the protein between 1.0% and 2.0% to obtain the natural rubber with different numbers, and detecting the mechanical property and the ageing resistance of the natural rubber.

As shown in table 3, when the water soluble content of the natural rubber is 1.0% to 2.0% and the protein content is 1.3% to 1.8%, the tensile strength, the tear strength, the elongation at break, the tensile strength after aging and the elongation at break after aging of the natural rubber all have good levels, i.e., the natural rubber not only has good mechanical properties, but also has excellent aging resistance, and the data thereof has statistical significance (p is less than 0.01).

TABLE 3 influence of the indices of the content of water-soluble substances and of the content of protein in the natural rubber on its mechanical and ageing resistance properties

In addition, according to experimental example 3, in the case where a specific mechanism is not temporarily defined, the researchers of the present application unexpectedly found through a large number of experimental procedures that when the water-soluble substance content of the natural rubber is 1.0% to 2.0% and the protein content is 1.3% to 1.8%, and the absolute value of the difference between the water-soluble substance content and the protein content of the natural rubber is less than or equal to 0.6%, the natural rubber has both excellent mechanical properties and aging resistance, and the data thereof has statistical significance (p < 0.05).

Through the experimental examples 1-3 of the invention, the inventor finds that when the water soluble substance content of the natural rubber is 1.0% -2.0%, the protein content is 1.3% -1.8%, and the absolute value of the difference between the water soluble substance content and the protein content of the natural rubber is less than or equal to 0.6%, the natural rubber has excellent mechanical properties and ageing resistance.

Meanwhile, in order to solve the problems that the stability of the constant viscosity agent is poor, the dispersion degree of the constant viscosity agent in the natural rubber is poor and the like caused by unreasonable constant viscosity treatment process in the process of performing constant viscosity treatment on the natural rubber in the prior art, and simultaneously, the content index of water soluble substances and the content index of protein of the natural rubber are controlled to ensure that the prepared composite rubber has better Mooney viscosity stability, good mechanical property and aging resistance, the inventor provides a method for preparing the composite rubber by treating a solid rubber material by using a composite constant viscosity agent;

wherein the solid rubber material comprises at least one of standard rubber, rubber cup rubber ball, crepe rubber, air-dried rubber sheet and raw rubber sheet. The composite constant viscosity agent comprises an organic constant viscosity agent and/or an inorganic constant viscosity agent, namely the composite constant viscosity agent can be an organic constant viscosity agent, an inorganic constant viscosity agent or a mixture of the organic constant viscosity agent and the inorganic constant viscosity agent.

The organic constant viscosity agent comprises an organic amine compound, wherein the organic amine compound comprises at least one compound of hydroxylamines, fatty amines, alcamines, alicyclic amines and aromatic amines; as a preferred embodiment of the present invention, the organic amine compound includes at least one of hydroxylamine hydrochloride, tripropylamine, diethanolamine, cyclohexylamine, and aniline.

The inorganic constant viscosity agent comprises inorganic ammonium salt, and the inorganic ammonium salt comprises at least one of ammonium chloride, ammonium sulfate and ammonium nitrate.

In a preferred embodiment of the present invention, the organic constant viscosity agent is an organic amine compound solution using a polar aprotic organic solvent as a solvent, and the inorganic constant viscosity agent is an inorganic ammonium salt solution containing a zinc-ammonia complex ion; specifically, the organic amine compound comprises at least one of hydroxylamines, fatty amines, alcamines, alicyclic amines and aromatic amines; the polar aprotic organic solvent comprises one or more of dimethylformamide, dimethylacetamide, hexamethylphosphoramide, and 1, 3-dimethyl-2-imidazolidinone; the inorganic ammonium salt comprises at least one of ammonium chloride, ammonium sulfate and ammonium nitrate.

Specifically, the composite rubber is prepared by taking a solid rubber material as a raw material, and the preparation method comprises the following steps:

in step S1, the organic amine compound includes at least one of hydroxylamines, aliphatic amines, alkanolamines, alicyclic amines, and aromatic amines; as a preferred embodiment of the present invention, the organic amine compound includes at least one of hydroxylamine, tripropylamine, diethanolamine, cyclohexylamine, and aniline.

The polar aprotic organic solvent comprises one or more of dimethylformamide, dimethylacetamide, hexamethylphosphoramide, and 1, 3-dimethyl-2-imidazolidinone; the inorganic ammonium salt comprises at least one of ammonium chloride, ammonium sulfate and ammonium nitrate.

The ratio of the mass of the zinc ore to the volume of the inorganic ammonium salt solution is 100-150 g/L; the ratio of the volume of the inorganic ammonium salt solution containing the zinc-ammonia complex ions to the volume of the organic amine compound solution is 1: 1.5-2.0; the zinc ore comprises at least one of calamine, willemite and hydrozincite.

The inorganic ammonium salt solution used in the invention is nearly neutral, and the zinc ore is leached under a proper temperature condition, so that the dissolution of compounds such as calcium, magnesium, silicon, iron and the like contained in the ore can be effectively inhibited, thereby effectively avoiding the mixing of impurities when the inorganic ammonium salt solution containing zinc-ammonia complex ions is prepared.

The polar aprotic organic solvent has stronger polarity, has good solubility for organic amine compounds, particularly organic amine compounds such as hydroxylamines, aliphatic amines, alcamines, alicyclic amines, aromatic amines and the like, due to the similar intermiscibility of substances, and ensures that the organic amine compounds can be uniformly dispersed in the solvent, and simultaneously can solvate cations due to the polar aprotic organic solvent, and dimethylformamide, dimethylacetamide, hexamethylphosphoramide and 1, 3-dimethyl-2-imidazolidinone which are used as the polar aprotic organic solvent can be mixed and dissolved with water, so that the inorganic ammonium salt solution containing zinc ammino complex ions and the organic amine compound solution can be promoted to be uniformly mixed, namely, the full and uniform mixing between the organic constant binder component and the inorganic constant binder component is ensured; meanwhile, in the composite constant viscosity agent, water and a polar aprotic organic solvent are compounded to serve as a solvent of the composite constant viscosity agent, so that the dispersibility of the constant viscosity agent in constant viscosity treatment of a solid rubber material is improved, the uniform contact between the composite constant viscosity agent and the solid rubber material is ensured, the reaction uniformity between active groups in natural rubber and the constant viscosity agent is improved, the constant viscosity treatment efficiency is improved, the Mooney viscosity stability of the composite rubber is also ensured, and the Mooney viscosity indexes of different batches of the composite rubber have better consistency.

S2, crushing the solid rubber, and carrying out floating washing in water;

putting solid rubber materials into a crusher, simultaneously spraying water for washing, crushing rubber blocks through the combination of a movable cutter and a fixed cutter in a crusher body, filtering out impurities, ash substances and water-soluble substances along with flowing water in the shearing and kneading process, and primarily crushing large rubber materials; then the glue blocks are stirred and mixed evenly in the float water for float washing to further remove the doped impurities and the water-soluble substances in the glue blocks;

the specific crushing process comprises at least two-stage crushing, wherein the rubber material is crushed in one stage to prepare rubber blocks of 10cm multiplied by 4 cm-25 cm multiplied by 15cm multiplied by 10cm, and the rubber blocks are stirred and mixed uniformly in the float water, and the float time is more than or equal to 10 min; and secondly crushing the mixed rubber material to prepare rubber blocks of 5cm multiplied by 2 cm-10 cm multiplied by 5cm, and uniformly stirring and mixing the rubber blocks in the float water, wherein the float time is not less than 10 min.

The solid rubber material comprises at least one of standard rubber, rubber cup rubber ball, crepe rubber, air-dried rubber sheet and raw rubber sheet.

S3, extruding the floated rubber material, and floating in water;

specifically, the rubber material after being subjected to the floating washing in the step S2 is put into an extruder for further kneading and shearing, so that the rubber material is further crushed and mixed, the consistency of the rubber material is improved, the rubber material is favorable for obtaining better hardness, the rubber material is convenient to be pressed into sheets, and favorable conditions are provided for granulation; water spraying washing is carried out during the extrusion process, so that impurities, ash and water-soluble substances in the rubber are further removed; the extruded gum stock is then subjected to a flotation wash in water to further remove contaminating impurities and water soluble materials therein.

Preferably, the rubber compound is extruded in two stages in step S3, that is, the rubber compound after the first extrusion is fed into the second extruder to be extruded for the second time under the condition that the rubber compound is kept washed; specifically, the two-stage extrusion process comprises the steps of firstly carrying out two-roller extrusion on the rubber material to carry out primary extrusion, carrying out flotation washing on the rubber material, then carrying out single-roller extrusion to carry out secondary extrusion, and carrying out flotation washing on the rubber material.

specifically, the first condition comprises at least one of the surface temperature of the rubber material is less than or equal to 10 ℃ or the Shore hardness of the rubber material is more than or equal to 40 HA; after extrusion and flotation, the first condition is set for the state of the rubber material, so that the rubber material has a better physical and chemical state in creping, particularly on the indexes such as viscosity, hardness and the like, the rubber material is ensured to have good processing performance, the rubber material is convenient to be creped and sliced, favorable conditions are provided for granulation, the production efficiency is favorably improved, and the prepared composite rubber has better mechanical performance;

if the sizing material does not meet the first condition, the indexes of the sizing material such as viscosity, hardness and the like are relatively poor, the problems of insufficient kneading, uneven mixing and poor tearing effect of the sizing material, no sheet forming, more broken sizing, uneven mixing, low impurity removal rate, and incapability of ensuring the product quality and consistency can occur in the creping process, and in order to solve the problem, an aqueous solution of organic dibasic acid is added into the creping machine before the sizing material is creped, so that the sizing material is creped in the environment of the organic dibasic acid; the organic dibasic acid comprises at least one of oxalic acid, succinic acid and malonic acid, the rubber material is treated by the organic dibasic acid, the viscosity and the hardness of the rubber material can be reduced to a certain extent, the processing performance of the rubber material is improved, the crepe condition of the rubber material is improved, the consistency of the rubber material is improved, the rubber material after being creped obtains better hardness, favorable conditions are provided for the later granulation, constant viscosity treatment and drying processes, and the product quality of the prepared composite rubber is ensured.

specifically, the extruded rubber materials are mutually kneaded and sheared in a crepe machine, and the blocky rubber materials are pressed into sheets, so that the rubber materials are fully kneaded and mixed in the process; and meanwhile, water spraying washing is carried out in the process of crepe, so that impurities, ash and water-soluble substances in the sizing material are further removed.

Preferably, four stages of crepes are carried out on the rubber material, the roller spacing of each stage of crepe is sequentially from large to small, the effect of the later stage of crepe is obviously improved compared with the effect of the former stage of crepe, the rubber material is gradually made into a continuous sheet, and the roller spacing processed by each stage of crepe is sequentially 7-10 mm, 5-6 mm, 3-4 mm and 1-2 mm. Each creper is provided with a spraying device for spraying and removing impurities from the rubber material in the process of creping; simultaneously, the method is favorable for reducing the hardness of the sizing material and improving the crepe effect.

specifically, the second condition is that the Shore hardness of the rubber material is less than or equal to 20HA, and after crepe, indexes such as hardness and viscosity of the rubber material can be changed correspondingly due to sufficient crushing and kneading of the rubber material; if the rubber material is too soft and too sticky, the particles of the rubber material can be bonded into a mass in the granulation process and even after granulation, so that the constant-viscosity treatment and uniform and thorough drying of the rubber material are not facilitated, and the mechanical property, the aging resistance and the Mooney viscosity stability of the composite rubber are not facilitated to be improved.

Therefore, a second condition is set for the state of the sizing material before granulation, and if the sizing material does not meet the second condition, the sizing material is too soft and too sticky, which is not beneficial to the operation of the subsequent process; in order to solve the problem, before the sizing material is granulated, adding an aqueous solution of inorganic base into a granulating pool to granulate the sizing material in the environment of the inorganic base; the inorganic base comprises at least one of calcium hydroxide, barium hydroxide and ammonia water, the hardness and viscosity index of the rubber material can be improved to a certain extent by treating the rubber material through the inorganic base, so that the condition that the rubber material is bonded and agglomerated in the granulation process or after granulation is avoided, rubber material particles can be uniformly subjected to constant-viscosity treatment and drying, the production efficiency is improved, and the mechanical property, the aging resistance and the Mooney viscosity stability of the composite rubber are improved.

specifically, further smash the sizing material at the granulation in-process to spray the washing to the sizing material, further detach impurity, ash content and water-soluble material, make purity, the uniformity of product obtain improving, make the micelle diameter reduce, thereby be convenient for carry out comparatively even and abundant permanent sticky processing to the sizing material, also be favorable to going on of stoving process simultaneously, with the even degree of improvement stoving.

The granulation tank is provided with a spraying device for spraying and removing impurities from the rubber material in the granulation process; meanwhile, the condition that the sizing material is condensed and bonded due to low hardness and overlarge viscosity of the sizing material is avoided, and the granulation effect is improved. Preferably, the size after granulation has a diameter of 6 to 12 mm.

specifically, the compound constant viscosity agent prepared in advance in the step S1 is used for spraying or soaking the granulated rubber material; for natural rubber, the addition of inorganic ammonium salt containing zinc-ammonia complex ions and organic amine compounds can reduce the Mooney viscosity of the natural rubber, thereby avoiding gelation of the prepared composite rubber caused by rise of the Mooney viscosity, improving the stability of the Mooney viscosity of the composite rubber, reducing or even eliminating rubber plastication or rubber drying procedures, reducing energy consumption, reducing production cost, further meeting the requirement of post vulcanization treatment of the rubber, improving vulcanization speed and saving energy consumption;

furthermore, as the composite constant-adhesion agent contains zinc-ammonia complex ions, part of the zinc-ammonia complex ions are combined with rubber particles in the process of carrying out constant-adhesion treatment on a rubber material by using a composite constant-adhesion machine, so that the zinc-ammonia complex ions can be pyrolyzed to separate out zinc ions in the later high-temperature plastication and vulcanization processes of the prepared composite rubber, and the zinc ions can be combined with a vulcanization accelerator, so that the activity of the vulcanization accelerator is improved, the vulcanization speed is accelerated, the vulcanization period is shortened, the consumption of the vulcanization accelerator is reduced, and the production cost is reduced; in addition, zinc ions can also react with sulfhydryl groups to generate shorter vulcanization crosslinking bonds in the vulcanization process of rubber, so that the crosslinking density is improved, the acting force between chemical bonds and the stability of the chemical bonds are enhanced, the mechanical property of the vulcanized rubber is improved, and the heat-resistant aging resistance of the vulcanized rubber is ensured. Meanwhile, by adding the composite constant adhesive containing the zinc-ammonia complex ions, the addition of zinc oxide in the conventional rubber vulcanization process can be reduced or even avoided in the later vulcanization processing process of the rubber, and the production cost is reduced.

Specifically, in the drying process, a drying furnace dries the sizing material by adopting saturated steam, and comprises a moisture extraction part, a high-temperature drying part, a low-temperature drying part and a cooling part, wherein the moisture extraction part is communicated with the high-temperature drying part, the high-temperature drying part is communicated with the low-temperature drying part, and the low-temperature drying part is communicated with the cooling part; namely, the processes of dehumidifying, high-temperature drying, low-temperature drying and cooling are sequentially carried out on the sizing material in the drying process. Wherein the vapor pressure of the saturated vapor is 0.7-0.9 MPa; the drying temperature of the high-temperature drying part is 95-120 ℃, the drying temperature of the low-temperature drying part is 80-115 ℃, and the sizing material can be more fully dried through two-stage drying processes, and the sizing material subjected to high-temperature drying has higher temperature, and then is subjected to low-temperature drying processes, so that the heat loss is reduced to the greatest extent, and the production cost is favorably reduced.

In one embodiment of the present invention, the drying furnace is provided with 35 parking spaces, wherein the dehumidification part has 3 parking spaces, the high-temperature drying part has 15 parking spaces, the low-temperature drying part has 14 parking spaces, and the cooling part has 3 parking spaces, and the circulation drying is performed by a way of getting in and out of one car.

In addition, the cooling part is a cooling cabinet, and an air supplementing fan is arranged on the cooling cabinet to enable the whole cooling cabinet to be in a negative pressure state; the drying furnace also comprises an automatic steam pressure adjusting device, the automatic steam pressure adjusting device is connected with the steam pipeline, and the temperatures of the dehumidification part, the high-temperature drying part, the low-temperature drying part and the cooling part are controlled by adjusting the steam pressure in the steam pipeline;

the drying furnace is provided with a rubber vehicle limiting device at an outlet so as to ensure the cooling time of the rubber material in the cooling part. The boiler steam pipeline increases the drain valve, and the increasing heat efficiency, boiler tail gas are used for heating carwash pond, improve carwash efficiency. Boiler return water has waste heat, can send to in the technology pond through the pipeline simultaneously, can add hot water pool temperature and sizing material when the temperature is low, makes the sizing material processing more easily, and production output and efficiency promote greatly, so more energy saving consumes, and the return water also obtains utilizing.

In the method for preparing the composite rubber by using the solid rubber material as the raw material, the rubber material from the crusher is more fully sheared and kneaded, so that the rubber material is further crushed and mixed, the defects that the rubber material is not sufficient in kneading, uneven in mixing and poor in tearing effect, the rubber material cannot better reach proper hardness, is not flaked, has more broken rubber and is uneven in mixing in the creping process, has low removal rate of impurities (DIRT) and ASH content (ASH), cannot guarantee product quality and consistency and the like caused by the conventional direct creping granulation process, the impurities and ASH content in the rubber material can be further removed, the consistency of the rubber material is improved, the rubber material obtains better hardness, is more beneficial to sheet pressing, and provides favorable conditions for subsequent granulation.

Meanwhile, the preparation method can lead different raw materials to be well mixed after being crushed, and lead the rubber material to be further kneaded and uniformly mixed through secondary extrusion. The particle size of the extruded rubber material is further reduced, so that the rubber material is easier to mix uniformly in the subsequent process, raw materials in different batches and different quality conditions are ensured to be sufficiently mixed uniformly, and the consistency and the stability of the physical and chemical properties of the finished product are integrally improved. The process makes full use of the raw materials with different quality conditions, greatly relieves the limitation of raw material selection, and improves the added value of products.

In the preparation method, the size particles obtained by multistage crepe and granulation are smaller, so that the diameter of the colloidal particles is reduced, the specific surface area of the colloidal particles is increased, uniform and sufficient constant viscosity treatment is favorably carried out on the size, the Mooney viscosity stability of the compound rubber is improved, the drying, baking and deep drying of the size are favorably carried out, and uneven baking and generation of raw rubber caused by overlarge granulation are avoided.

In addition, no matter in any process of crushing, extruding, creping and granulating the rubber material, the water spraying washing is always carried out on the rubber material, so that impurities, ash, water-soluble substances and partial protein in the rubber material are ensured to be separated out along with the water spraying washing process, the impurity content and the ash content of the finally prepared composite rubber are reduced, the water-soluble substance content and the protein content of the composite rubber are favorably controlled, and the composite rubber has good mechanical performance and ageing resistance.

Meanwhile, as the solid rubber material is adopted as the raw material, in order to further ensure that the composite rubber has better water-soluble substance content and protein content index so as to have good mechanical property and aging resistance, the raw material index of the solid rubber material is also limited in the invention, specifically, the water-soluble substance content of the solid rubber material is between 1.5 and 2.5 percent, and the protein content is between 1.5 and 2.1 percent.

Experimental example 4

Taking solid rubber materials with different water-soluble substance contents and different protein contents, producing the composite rubber according to the composite rubber preparation method, taking intermediate values of other related parameters in the process, detecting the water-soluble substance contents and the protein contents of the prepared composite rubber, and correspondingly detecting the mechanical properties and the ageing resistance of the composite rubber.

As shown in table 4, when a solid rubber material with a water soluble content of 1.5% to 2.5% and a protein content of 1.5% to 2.1% is used as a raw material, the water soluble content and the protein content of the prepared composite rubber meet the requirements of the invention on the composite rubber, and the tensile strength, the tear strength, the elongation at break, the tensile strength after aging and the elongation at break after aging of the prepared composite rubber have good levels, i.e., the composite rubber not only has good mechanical properties, but also has excellent aging resistance, and the data of the composite rubber have statistical significance (p is less than 0.01).

TABLE 4 influence of water-soluble content index and protein content index in solid rubber material on the resulting composite rubber

In addition, through experimental example 4, in the case where the specific mechanism is not temporarily clear, the researchers of the present application unexpectedly found through a large number of experimental procedures that, in the case where the water-soluble content of the solid gum is between 1.5% and 2.5%, the protein content is between 1.5% and 2.1%, and the absolute value of the difference between the water-soluble content and the protein content of the solid gum is not more than 0.8%, the water-soluble content and the protein content of the obtained composite rubber meet the requirements of the present invention on the composite rubber, and the obtained composite rubber has excellent mechanical properties and aging resistance, the data of which have statistical significance (p < 0.05).

In addition, the preparation method of the composite rubber is a production process of a waterline, and the invention also provides another preparation method of the composite rubber as a main production process, specifically, the preparation method takes solid rubber as a raw material, cuts the rubber into preset weight according to a proportion, puts the weight into a dry-stirring machine, and sprays a composite constant adhesive according to a preset proportion at the inlet of the dry-stirring machine; and (3) fully and uniformly stirring the rubber material and the composite constant binder, extruding the rubber material out of a dry stirring machine under the action of extrusion and shearing, cooling the rubber material in a cooling cabinet by using a blast cooling or negative pressure draft cooling mode after the rubber material enters a cooling hopper through a vibrating screen, and discharging the rubber material after the temperature of the rubber material is lower than 55 ℃ to obtain the composite rubber.

Wherein, in the production process of the main line, two dry stirring machines are connected in series through a conveyer belt, and a constant viscosity agent spraying device is arranged on both the two machines. The discharge port of the first processor is modified, so that the yield of the first processor is increased, the rubber material continues to be processed by the second processor after passing through the first processor, the performance is stable, and the energy consumption and labor cost are reduced; and a stirrer is arranged in the constant-viscosity agent spraying device to prevent the constant-viscosity agent from being separated out and ensure the solution concentration to be stable. A peristaltic pump is adopted in the feeding process of the constant-viscosity agent spraying device, so that the feeding amount is accurate.

Similarly, in the trunk production process, the solid rubber material comprises at least one of standard rubber, rubber cup rubber balls, crepe rubber, air-dried rubber sheets and raw rubber sheets; taking inorganic ammonium salt solution with the concentration of 2.5-6.0mol/L as leaching liquid, leaching zinc ore at 90-102 ℃, filtering the leaching liquid, and cooling the filtrate to room temperature to obtain inorganic ammonium salt solution containing zinc-ammonia complex ions; dissolving an organic amine compound in a polar aprotic organic solvent to prepare 2.0-3.2mol/L organic amine compound solution; adding inorganic ammonium salt solution containing zinc-ammonia complex ions into the organic amine compound solution to prepare the composite constant adhesive. In the production process of the trunk line, related production equipment is less, the production flow is simpler and has certain operational value, and the production cost is favorably reduced.

In the specific production process of the composite rubber in the water line, because a large number of production devices are involved, in order to fully explain the production process of the water line, as shown in fig. 2-3, two identical production lines capable of simultaneously performing steps S2 to S7 are included, and one of the two production lines is taken as an example for explanation; conveying solid rubber materials to a first crusher 1 through a conveyor 2 for primary crushing, enabling crushed rubber particles to enter a first flotation tank 5 for water washing, arranging a rubber poking device in the first flotation tank 5, enabling silt on the surface of the rubber sheets to be separated and settled more effectively to achieve the purpose of impurity removal, conveying the rubber particles subjected to impurity removal through a rubber poking device to a third crusher 10 through a bucket elevator for secondary crushing, putting the crushed rubber particles into a third flotation tank 13 for water washing, also arranging a rubber poking device in the third flotation tank 13, conveying the rubber materials to a double-roller extruder 12 through the bucket elevator for extrusion, enabling the extruded rubber materials to enter a next flotation tank for flotation washing, then conveying the rubber materials to a single-roller extruder 16 through the bucket elevator for extrusion again, and after two-stage crushing washing and two-stage extrusion washing, enabling large blocks of raw rubber sheets to be changed into small rubber sheets or rubber particles, the non-glue materials such as silt and the like attached to the surface of the rubber sheet are basically removed under the mechanical action of soaking, shearing, extruding, washing and the like, so that the subsequent pressing and granulating are facilitated.

Furthermore, the rubber particles are crushed by two crushers, extruded twice by a single-roller machine and/or a double-roller machine, washed under the rotation action of a glue spreader, lifted by a bucket elevator and conveyed between the crushing and extruding procedures, so that the aim of flowing washing and sand settling is fulfilled, and the impurity removal effect is ensured. The sizing material from the crusher enters a double-roller machine for extrusion, the sizing material is kneaded and extruded under the action of the double-roller machine, and is cut into small blocks by a driven knife at a discharge port, so that the sizing material is further crushed and mixed, the consistency of the sizing material is improved, the sizing material obtains better softness, and a creper is more favorable for pressing the blocky sizing material into sheets.

In the crepe process, the first crepe system 24 comprises four crepers for creping, and a conveying device 25 is arranged between any two adjacent crepers and used for conveying the sizing material; the sizing material carries out in succession the crepe through four crepers, is carried to first granulator 27 and carries out the granulation, makes the breakage that the micelle is more after the granulation, and the micelle diameter is littleer, further dispels impurity, ash content in the sizing material, makes purity, the uniformity of product obtain better improvement, accomplishes the micelle of granulation process through the granulator, carries out the homocline through step S8 after handling, and the rethread is taken out the glue pump and is carried out the stoving process in conveying to drying system.

Preferably, the crepe system comprises four crepers for creping, two adjacent crepers transmit sizing materials through a bucket elevator and/or a conveyor, and a spraying device is arranged above the bucket elevator and/or the conveyor and used for spraying and washing the sizing materials; in each crepe process, the crepe machine carries out kneading and shearing, reduces broken rubber generated in the production process, ensures the crepe effect and avoids pollution or waste of rubber falling to the ground.

The crepe machine is characterized in that a pair of pattern rollers with a speed ratio rub and shear each other, block glue is pressed into thin sheets, then a granulation process is carried out in a granulator, the glue is further smashed, impurities and ash are further removed, the purity and consistency of products are improved, and the diameter of colloidal particles is reduced.

Meanwhile, in the processes of creping and granulating, the sizing material is sprayed by a spraying device; specifically, spraying water is used for spraying the sizing material in the running process of the crepe machine, and the kneaded impurities flow away with the water; the sheet pressed by the creper passes through the granulator, the glue is cut into very small particles by the granulator which runs at high speed, the water spray is arranged on the granulator, the glue floats on the granulating pool, the impurities are settled and taken away along with the water, and the impurities are further removed.

The other production line in the production line of the invention is the same as the production line, namely, the other production line has the same related production devices of crushing, floating washing, extruding, crepe, granulating and the like, and the description is omitted. The two production lines are simultaneously carried out, so that the yield of rubber products is increased, and the production efficiency is improved.

Further, still be provided with milk mark waste water circulation device 61, congeal mark waste water circulation device 62 and clear water circulation device 63 in the compounded rubber production process, realize that spraying system's rivers are gone into and the categorised discharge of waste water, avoid causing environmental pollution, reduce the waste water treatment cost.

In step S9, the steam drying system is a steam drying oven, including a drying oven 42, the rubber particles after constant viscosity treatment enter the drying oven 42 through a vibrating screen 39 and a glue feeder 40, hot steam is delivered into the drying oven 42 through an air intake system, drying colloidal particles entering a drying furnace 42, arranging a cooling fan 45 at one end of the drying furnace 42, cooling the dried colloidal particles before the colloidal particles exit the drying furnace 42 by the cooling fan 45, discharging the cooled gas or cooling water out of the drying furnace through an induced draft fan arranged at a rubber inlet device 40, discharging the dried colloidal particles out of the drying furnace 42 under the action of a parking space brake 46 to realize drying of the colloidal particles, detecting and judging whether the dried colloidal particles are qualified products, and if the colloidal particles are qualified products, placing the colloidal particles in an area to be delivered for the next step of processing and production of rubber products; if the products are unqualified, the products are placed in a region to be processed, and degraded for use or returned to the pretreatment for processing again according to the unqualified degree of the products.

Preferably, the air inlet system include air-blower 43, second air-blower 44, improve the efficiency that the micelle was dried in drying furnace 42, set up temperature sensor in drying furnace 42, adjust the air output of air-blower 43, second air-blower 44 through control system, carry out automatic control to the stoving temperature in drying furnace 42, guarantee the suitability of drying to the micelle of different raw materials, different weight, different quality requirements.

Or, the blower 43 is configured to send hot steam into the drying oven 42, and the second blower 44 is used for discharging the cooled steam out of the drying oven 42 and feeding the cooled steam back to the steam oven for further recycling under the action of the second blower 44, so that waste of heat is reduced, and cost is saved.

Further, drying furnace 42 sets up dehumidifying fan 41 in the one side of keeping away from cooling blower 45, dehumidifying fan 41 set up in the one side of being close to into gluey ware 40, through dehumidifying fan 41 blast air, form powerful wind pressure, can deeply pierce through the sizing material, take away most moisture.

Preferably, after the gas or the cooling water cooled by the drying furnace 42 is discharged from the drying furnace through the induced draft fan, the gas or the cooling water is returned to the steam furnace through the return line to be reheated to generate steam, and the steam is applied to drying of the drying furnace 42, so that waste of water resources and heat is avoided, and drying cost is reduced.

Further, the glue car that holds the micelle is that the upper end sets up the open-ended cuboid setting, is provided with the filtration pore in the bottom of glue car, and the glue car that the micelle had been accomplished in the splendid attire removes in drying furnace 42 under the effect of parking stall stopper 46, and the steam that gets into in drying furnace 42 gets into from drying furnace 42 bottom, and the filtration pore pair micelle through the glue car lower extreme is from ascending stoving from bottom to top, can improve the volume that holds of the micelle in each glue car, and the heat of make full use of steam improves drying efficiency, guarantees the stoving effect, reduces drying cost.

Preferably, the diameter of the filtering holes is not more than 5cm, preferably not more than 3cm, as an example of the present invention, the diameter of the filtering holes is 1cm, and this arrangement ensures the drying effect of the steam from bottom to top and the discharge efficiency of the cooling water, avoids the pollution or waste of the smaller particles, and reduces the production cost.

Further, each row can set up a plurality of gluey cars in drying furnace 42, also can set up many rows of gluey cars simultaneously in drying furnace 42, should set up and make drying furnace 42 can dry the colloidal particle in the many rows of gluey cars in batches, guarantees stoving effect and drying efficiency.

Preferably, the drying furnace 42 includes a dehumidifying section, a high-temperature drying section, a low-temperature drying section, and a cooling section, the dehumidifying section is communicated with the high-temperature drying section, the high-temperature drying section is communicated with the low-temperature drying section, and the low-temperature drying section is communicated with the cooling section; be provided with 35 parking stalls in the drying furnace 42, wherein the portion of dehumidifying has 3 parking stalls, and high temperature drying portion has 15 parking stalls, and low temperature drying portion has 14 parking stalls, and the cooling portion has 3 parking stalls, adopts the mode of going into the car and going out of the car to carry out circulation drying. The steam pressure of the saturated steam used in the drying furnace 42 is 0.7-0.9 Mpa; the drying temperature of the high-temperature drying part is 95-120 ℃, and the drying temperature of the low-temperature drying part is 80-115 ℃; the glue inlet and outlet time is 3-6 minutes per car.

the drying furnace also comprises an air pressure automatic regulating device which controls the temperature of the dehumidifying part, the high-temperature drying part, the low-temperature drying part and the cooling part.

Meanwhile, as another embodiment of the present invention, the drying temperature of the steam in the drying oven 42 is set to be a temperature range of a plurality of drying grades, and the temperature ranges of different drying grades are set to be 80-170 ℃, the plurality of drying grades can be formed in different areas of the same drying oven 42, or the temperature control system can gradually control the temperature in the drying oven 42 to realize the change of the drying grade temperature range, for example, the first temperature control grade is a temperature range of 80-100 ℃, the second temperature control grade is a temperature range of 100-125 ℃, the third temperature control grade is a temperature range of 125-155 ℃, the fourth temperature control grade is a temperature range of 155-170 ℃, the requirements of different rubber materials or rubbers with different functions on the drying temperature are different, and the temperature range of the drying grade has a great influence on the drying efficiency of the rubber particles, the setting of the stoving grade between different temperature regions has guaranteed the effect that the micelle was dried on the one hand, improves drying efficiency, and on the other hand has improved the utilization ratio of heat source greatly, has further reduced the cost that rubber was dried.

The drying system provided by the invention can convert saturated steam with a certain pressure into temperature under a corresponding pressure, provides steam with a certain temperature required by the process to the drying furnace 42 by controlling the steam pressure, and provides a very stable heat source for the drying furnace.

The rubber sizing material is firstly subjected to a dehumidifying process, and is blown by a dehumidifying fan to form strong wind pressure, so that the rubber sizing material can be deeply penetrated through, and most of moisture is taken away. After the sizing material is dehumidified, the moisture content is obviously reduced, the sizing material is easier to dry, the consumption of a heat source can be reduced due to the reduction of moisture, and energy conservation and consumption reduction are really achieved. The dehumidified rubber material enters a plurality of set drying levels, the rubber material is dried and cured in batches and in stages, the drying effect and the drying efficiency are guaranteed, and the cured rubber material directly enters a cooling stage after being acted by a cooling fan. And the cooling fan blows external cold air into the drying vehicle, the temperature of the sizing material is reduced to be below 55 ℃ from the original 100-80 ℃, so that the phenomenon that the sizing material is rewetted due to overhigh temperature when the sizing material is discharged from the drying vehicle is avoided, and particularly in places with high humidity, the sizing material needs to be discharged from the drying vehicle at a low temperature.

On the basis of the preparation method of the composite rubber and the related production equipment, the solid rubber materials with different water-soluble substance contents and protein contents are adopted as raw materials to prepare the composite rubber.

Example 1

A composite rubber adopts a raw rubber sheet with water-soluble substance content of 1.5% and protein content of 1.5% as a raw material, and comprises the following steps:

s1, leaching the calamine at 100 ℃ by taking an ammonium chloride solution with the concentration of 2.5mol/L as a leaching solution; filtering the leaching solution, and cooling the filtrate to room temperature to obtain an ammonium chloride solution containing zinc-ammonia complex ions; dissolving diethanolamine in dimethylacetamide to obtain 3.0mol/L diethanolamine solution, and adding ammonium chloride solution containing zinc-ammonia complex ion into the diethanolamine solution to obtain composite constant adhesive; wherein the ratio of the mass of the calamine to the volume of the ammonium chloride solution is 120 g/L; the volume ratio of the ammonium chloride solution containing the zinc-ammonia complex ions to the diethanolamine solution is 1: 1.5;

s2, crushing the solid rubber, and carrying out floating washing in water;

s3, extruding the floated rubber material, and floating in water;

s4, judging whether the rubber material meets at least one of the conditions that the surface temperature of the rubber material is less than or equal to 10 ℃ or the Shore hardness of the rubber material is more than or equal to 50HA, and if not, directly performing the step S5; if so, adding an oxalic acid aqueous solution into the crepe machine, and then performing step S5;

s6, judging whether the Shore hardness of the rubber material is less than or equal to 20HA, and if not, directly performing the step S7; if so, adding an ammonia water solution into the granulation tank, and then performing step S7;

s7, putting the rubber material subjected to crepe into a granulation tank for granulation treatment, and spraying and washing the rubber material;

The prepared composite rubber is detected, the content of water-soluble substances is 1.0%, the content of protein is 1.3%, the Mooney viscosity stability is shown in Table 5, and the mechanical property and the aging resistance are shown in Table 7.

Example 2

The composite rubber adopts crepe rubber with water soluble matter content of 2.5% and protein content of 1.8% as material and includes the following steps:

s1, leaching hemimorphite at 90 ℃ by taking ammonium nitrate solution with the concentration of 6.0mol/L as leaching liquid; filtering the leaching solution, and cooling the filtrate to room temperature to obtain an ammonium nitrate solution containing zinc-ammonia complex ions; hexamethylphosphoramide is taken as a solvent, aniline is dissolved in hexamethylphosphoramide to prepare 2.0mol/L aniline solution, and ammonium nitrate solution containing zinc-ammonia complex ions is added into the aniline solution to prepare a composite constant adhesive for later use; wherein the ratio of the mass of the hemimorphite to the volume of the ammonium nitrate solution is 150 g/L; the volume ratio of the ammonium nitrate solution containing the zinc-ammonia complex ions to the aniline solution is 1: 2.0;

s2, crushing the solid rubber, and carrying out floating washing in water;

s3, extruding the floated rubber material, and floating in water;

The prepared composite rubber is detected, the content of water-soluble substances is 2.0 percent, the content of protein is 1.5 percent, the Mooney viscosity stability is shown in Table 5, and the mechanical property and the aging resistance are shown in Table 7.

Example 3

A composite rubber adopts an air-dried film with 2.0 percent of water-soluble substance and 2.1 percent of protein content and a raw film as raw materials, and comprises the following steps:

s1, leaching the hydrozincite at 102 ℃ by taking an ammonium sulfate solution with the concentration of 3.0mol/L as a leaching solution; filtering the leaching solution, and cooling the filtrate to room temperature to obtain an ammonium sulfate solution containing zinc-ammonia complex ions; dissolving cyclohexylamine in dimethylformamide by using dimethylformamide as a solvent to prepare a 3.2mol/L cyclohexylamine solution, and adding an ammonium sulfate solution containing zinc-ammonia complex ions into the cyclohexylamine solution to prepare a composite constant adhesive for later use; wherein the ratio of the mass of the hydrozincite to the volume of the ammonium sulfate solution is 100 g/L; the volume ratio of the ammonium sulfate solution containing the zinc-ammonia complex ions to the cyclohexylamine solution is 1: 1.8;

s2, crushing the solid rubber, and carrying out floating washing in water;

s3, extruding the floated rubber material, and floating in water;

The prepared composite rubber is detected, the content of water-soluble substances is 1.5%, the content of protein is 1.8%, the Mooney viscosity stability is shown in Table 5, and the mechanical property and the aging resistance are shown in Table 7.

Example 4

A composite rubber adopts standard rubber with 2.1% of water-soluble substance and 1.8% of protein as raw materials, and comprises the following steps:

s1, leaching the willemite at 98 ℃ by taking an ammonium chloride solution with the concentration of 4.5mol/L as a leaching solution; filtering the leaching solution, and cooling the filtrate to room temperature to obtain an ammonium chloride solution containing zinc-ammonia complex ions; dissolving tripropylamine in 1, 3-dimethyl-2-imidazolidinone to obtain a tripropylamine solution with the concentration of 2.5mol/L by using 1, 3-dimethyl-2-imidazolidinone as a solvent, and adding an ammonium chloride solution containing zinc-ammonia complex ions into the tripropylamine solution to obtain a composite constant adhesive for later use; wherein the ratio of the mass of the willemite to the volume of the ammonium chloride solution is 125 g/L; the volume ratio of the ammonium chloride solution containing the zinc ammine complex ions to the tripropylamine solution is 1: 1.6;

s2, crushing the solid rubber, and carrying out floating washing in water;

s3, extruding the floated rubber material, and floating in water;

The prepared composite rubber is detected, the content of water-soluble substances is 1.6%, the content of protein is 1.5%, the Mooney viscosity stability is shown in Table 5, and the mechanical property and the aging resistance are shown in Table 7.

Example 5

s1, dissolving hydroxylamine hydrochloride in 1, 3-dimethyl-2-imidazolidinone by taking 1, 3-dimethyl-2-imidazolidinone as a solvent to prepare 2.1mol/L hydroxylamine hydrochloride solution for later use;

s2, crushing the solid rubber, and carrying out floating washing in water;

s3, extruding the floated rubber material, and floating in water;

s8, spraying or soaking the granulated rubber material by using hydroxylamine hydrochloride solution;

The prepared composite rubber is detected, the content of water-soluble substances is 1.5%, the content of protein is 1.5%, the Mooney viscosity stability is shown in Table 5, and the mechanical property and the aging resistance are shown in Table 7.

Comparative example 1

Taking example 6 of patent application document CN1188429C as a comparative example, the specific method is as follows:

propionyl hydrazine with equal weight is mixed with water to prepare a viscosity stabilizer with the concentration of 50 percent (weight), 0.2phr of viscosity stabilizer is added into the natural rubber latex, and the natural rubber is prepared after the processes of drying and the like.

Comparative example 2

Constant viscosity natural rubber was prepared according to the protocol of example 2 described in patent application CN 103627044B.

Mooney viscosity stability tests were conducted on the compounded rubbers obtained in examples 1 to 5 of the present invention and the natural rubbers obtained in comparative examples 1 to 2, and are specifically shown in Table 5.

The method for detecting the Mooney viscosity stability comprises the following steps: the Mooney viscosity is detected according to the standard GB/T1232.1-2016, the Mooney viscosity ML (original) of the rubber at the completion of production is detected, then the rubber is placed in an oven at 60 ℃ for 7 days, the Mooney viscosity ML (old) after aging is detected, and the difference delta between the Mooney viscosity ML (old) and the Mooney viscosity ML (original) is calculated, wherein the smaller the difference delta is, the better the viscosity stability of the rubber is.

Accordingly, 5 times are carried out for each example and comparative example, and the mean value of the difference Δ and the standard deviation S are obtained. Wherein, the smaller the average value is, the better the viscosity stabilizing effect of the rubber is; the smaller the standard deviation S, the better the consistency of the Mooney viscosity index of the natural rubber of different batches.

TABLE 5 Mooney viscosity stability test for Natural rubber

As can be seen from Table 5, compared with the prior art, the composite constant adhesive used in the invention, especially the composite constant adhesive obtained by mixing the inorganic ammonium salt containing the zinc-ammonia complex ion and the organic amine compound, can effectively avoid the gelation of the prepared composite rubber caused by the increase of the Mooney viscosity, and improve the stability of the Mooney viscosity of the composite rubber; meanwhile, the polar aprotic organic solvent is used, so that the dispersing performance of the organic amine compound is improved, and the inorganic ammonium salt solution containing the zinc-ammonia complex ions and the organic amine compound solution are promoted to be uniformly mixed, namely, the full and uniform mixing of the organic constant binder component and the inorganic constant binder component is ensured; meanwhile, in the composite constant viscosity agent, water and a polar aprotic organic solvent are compounded to serve as a solvent of the composite constant viscosity agent, so that the dispersibility of the constant viscosity agent in constant viscosity treatment of a solid rubber material is improved, the uniform contact between the composite constant viscosity agent and the solid rubber material is ensured, the reaction uniformity between active groups in rubber and the constant viscosity agent is improved, the constant viscosity treatment efficiency is improved, the Mooney viscosity stability of natural rubber is also ensured, and the Mooney viscosity indexes of different batches of composite rubber have better consistency.

That is, as shown in the data in Table 5, the Mooney viscosity stabilizing property of the natural rubber is remarkably superior to that of the natural rubbers obtained in comparative examples 1 and 2, and the data thereof has statistical significance (p < 0.01).

Meanwhile, the use of the polar aprotic organic solvent in the present invention is specifically described by the following experimental examples 5 to 14 and comparative experimental examples 1 to 5:

examples 5 to 14 and comparative examples 1 to 5 were carried out under the same conditions as in example 4, except that the organic constant viscosity agent (tripropylamine solution, example 4) was prepared using a different solvent, and the details and results are shown in table 6.

TABLE 6

According to the invention, any polar aprotic organic solvent of dimethylformamide, dimethylacetamide, hexamethylphosphoramide and 1, 3-dimethyl-2-imidazolidinone is used as a solvent to prepare an organic constant adhesive, and the organic constant adhesive is compounded with an inorganic constant adhesive to prepare a composite constant adhesive, and finally the composite constant adhesive is applied to the preparation of composite rubber.

By detecting the Mooney viscosity stability of the natural rubber, the specific data are shown in Table 6, and it can be seen that when any polar aprotic organic solvent of dimethylformamide, dimethylacetamide, hexamethylphosphoramide, 1, 3-dimethyl-2-imidazolidinone is used as the solvent, the invention not only ensures that the organic amine compound can be uniformly dispersed in the solvent, but also the polar aprotic organic solvent can solvate cations, can promote the inorganic ammonium salt solution containing zinc-ammonia complex ions to be uniformly mixed with the organic amine compound solution, ensures the sufficient and uniform mixing of the organic constant viscosity agent component and the inorganic constant viscosity agent component, enhances the dispersing performance of the constant viscosity agent, ensures that the constant viscosity agent and the solid rubber material are more uniformly contacted, thereby improving the Mooney viscosity stability of the composite rubber, so that the Mooney viscosity indexes of different batches of compound rubber have better consistency.

Therefore, as can be seen from comparison of the data in table 6, the composite rubber prepared by using one or more of dimethylformamide, dimethylacetamide, hexamethylphosphoramide and 1, 3-dimethyl-2-imidazolidinone as a solvent has better stability of mooney viscosity, the mooney viscosity index of different batches of composite rubber has better consistency, and the data has statistical significance (p < 0.01).

In addition, under the condition that a specific mechanism is not temporarily defined, researchers of the application unexpectedly find that when one or more combinations of dimethylformamide, dimethylacetamide, hexamethylphosphoramide and 1, 3-dimethyl-2-imidazolidinone are used as a solvent through a large number of experimental processes, the final product prepared by using a plurality of combinations as the solvent has better stability of the Mooney viscosity, Mooney viscosity indexes of different batches of compound rubber have better consistency and the data have statistical significance (p is less than 0.05) compared with the final product prepared by using a single substance as the solvent;

in addition, even more unexpected to the researchers in this application, when several combinations of dimethylformamide, dimethylacetamide, hexamethylphosphoramide and 1, 3-dimethyl-2-imidazolidinone are used as the solvent, especially when any three combinations are used as the solvent, the final product has better stability of mooney viscosity, the mooney viscosity index of different batches of compound rubber has better consistency, and the data has statistical significance (p < 0.05).

Comparative example 3

Natural rubber was prepared according to the protocol of the examples described in patent application CN200910094210.0, and its mechanical properties and aging resistance were examined, as shown in Table 7.

TABLE 7 mechanical and ageing resistance of Natural rubber Table (100 ℃ X72 h ageing resistance test)

Detecting the tensile strength, the tearing strength and the elongation at break of the rubber according to the standard GB/T528-2009; after heat aging (aging at 100 ℃ for 72 hours) in a ventilation oven, the tensile strength after aging and the elongation at break after aging of the rubber are detected according to the standard GB/T528-2009, which is the same as the following.

As can be seen from Table 7, the invention correspondingly controls the water-soluble material content index and the protein content index in the rubber, and simultaneously performs constant viscosity treatment on the rubber by the composite constant viscosity agent, thereby avoiding gelation caused by crosslinking reaction among active groups in a natural rubber molecular chain to the maximum extent, and ensuring the mechanical property and the aging resistance of the composite rubber; therefore, the compounded rubber prepared by the invention is obviously superior to the rubber prepared by the comparative example 3 in mechanical property and ageing resistance, and the data has statistical significance (p is less than 0.01).

Comparative example 4

Taking example 3 of patent application document CN106519324A as a comparative example, the specific method is as follows:

a wear-resistant and skid-resistant rubber material for tires comprises the following main raw materials in parts by weight: 35 parts of natural rubber, 20 parts of polyisoprene, 12 parts of polyacrylamide, 8 parts of straw fiber, 10 parts of polytetrahydrofuran ether glycol, 1.3 parts of titanium dioxide, 5 parts of an auxiliary agent, 2 parts of a vulcanizing agent and 3 parts of calcium carbonate; the auxiliary agent comprises 8 parts of polyvinylpyrrolidone, 3 parts of tin oxide, 8 parts of tris (hydroxymethyl) aminomethane, 3 parts of zinc silicate, 9 parts of 2-mercaptobenzimidazole zinc salt and 9 parts of N-acetylglycine; the vulcanizing agent is triazole dimercaptoamine salt.

A preparation method of a wear-resistant and skid-resistant rubber material for tires comprises the following specific steps:

firstly, mixing natural rubber, polyisoprene, polyacrylamide and straw fiber uniformly at a stirring speed of 2000r/min for 1.5h at a stirring temperature of 45 ℃, adding polytetrahydrofuran ether glycol, titanium dioxide, an auxiliary agent, a vulcanizing agent and calcium carbonate after stirring, carrying out water bath treatment, adding the auxiliary agent while stirring after water bath, and placing under a granulator for drying and granulation to obtain the wear-resistant and skid-resistant rubber material for the tire.

Based on the raw material ratio and the preparation method in the comparative example 4, the natural rubber in the comparative example 4 was replaced with the compounded rubber prepared in the examples 1 to 5 of the present invention, and the compounded rubber was used as examples 6 to 10, and the rubber materials prepared in the examples 6 to 10 and the comparative example 4 were tested for mechanical properties and aging resistance, as shown in table 8.

TABLE 8 mechanical Properties of rubber materials

As can be seen from Table 8, the compounded rubber obtained by the present invention has good mechanical properties and aging resistance; meanwhile, by adding a composite constant adhesive, particularly a composite constant adhesive formed by mixing inorganic ammonium salt containing zinc-ammonia complex ions and an organic amine compound, gelation caused by a crosslinking reaction among active groups in a natural rubber molecular chain is avoided to the maximum extent, and the mechanical property and the aging resistance of the composite rubber are further ensured; meanwhile, the addition of the zinc-ammonia complex ions can not only accelerate the vulcanization speed, but also generate shorter vulcanization crosslinking bonds in the vulcanization process of the rubber, ensure that stronger acting force exists between the chemical bonds, and improve the crosslinking density, thereby improving the mechanical property of the rubber material; meanwhile, the addition of the zinc-ammonia complex ions can not only accelerate the vulcanization speed, but also enable the rubber to generate shorter vulcanization cross-linking bonds in the vulcanization process, enhance the stability of the chemical bonds of the rubber, and ensure that the composite rubber has good aging resistance, thereby improving the aging resistance of rubber products.

Therefore, the rubber material obtained from the compounded rubber of the present invention was significantly superior in mechanical properties and aging resistance to the rubber material obtained in comparative example 4, and the data thereof was statistically significant (p < 0.01).

Comparative example 5

Based on embodiment 4 of the present invention, the specific method is as follows:

s2, crushing the solid rubber, and carrying out floating washing in water;

s3, extruding the floated rubber material, and floating in water;

s4, conducting crepe on the extruded rubber material to enable the rubber material to be in a continuous sheet shape, and meanwhile conducting spray washing on the rubber material;

s5, putting the rubber material subjected to crepe into a granulation tank for granulation treatment, and spraying and washing the rubber material;

s6, spraying or soaking the granulated rubber material by using the composite constant viscosity agent in the step S1;

and S7, sending the rubber material to a drying furnace, dehumidifying, drying at high temperature and low temperature, and cooling to room temperature to obtain the composite rubber.

The example 4 and the comparative example 5 of the present invention were performed 5 times, respectively, to prepare 5 sets of composite rubbers, and the mechanical properties and the aging resistance thereof were measured, respectively, as shown in table 9.

TABLE 9 mechanical Properties and aging resistance of compounded rubbers in different groups (100 ℃ X72 h aging resistance test)

The invention sets two stages of judging process and corresponding treatment for the state of the rubber material in the production and preparation process, so that the rubber material has better hardness and viscosity all the time in the processing process, the processing performance of the rubber material is ensured, the processing processes of crepe, granulation, constant viscosity treatment, drying and the like are convenient to carry out, the production efficiency is favorably improved, the mechanical property and the aging resistance of the composite rubber are favorably improved, and the consistency of the composite rubber of different production batches on the product performance is favorably improved.

It can be seen from table 9 that the determination process and the corresponding processing for the rubber material state are set in the production process, that is, the composite rubber prepared by the method of the present invention is significantly better than the composite rubber prepared in the production process without controlling the rubber material state in terms of mechanical properties, aging resistance and consistency of products of different batches, and the data has statistical significance (p < 0.01).

The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the scope of protection of the present application.

Claims

1. The composite rubber is characterized in that a solid rubber material is treated by a composite constant-viscosity agent to prepare the composite rubber; the composite rubber has the impurity content of 0.05-0.16%, the ash content of 0.5-1.0%, the nitrogen content of less than or equal to 0.6%, the volatile matter content of less than or equal to 0.8%, the plasticity retention rate of more than or equal to 40%, the Mooney viscosity ML/(1 '+ 4') of 55-72 ℃ at 100 ℃, the copper content of less than or equal to 8mg, the manganese content of less than or equal to 10mg and the water soluble matter content of 0.8-2.4%; the composite constant viscosity agent comprises an organic constant viscosity agent and an inorganic constant viscosity agent, wherein the organic constant viscosity agent is an organic amine compound solution taking a polar aprotic organic solvent as a solvent; the inorganic constant adhesive is an inorganic ammonium salt solution containing zinc-ammonia complex ions;

the composite rubber is prepared by taking a solid rubber material as a raw material, and comprises the following steps:

s2, crushing the solid rubber, and carrying out floating washing in water;

s3, extruding the floated rubber material, and floating in water;

s9, sending the rubber material to a drying furnace, dehumidifying, drying at high temperature and drying at low temperature, and cooling to room temperature to obtain the composite rubber;

the first condition comprises at least one of the surface temperature of the sizing material is less than or equal to 10 ℃ or the Shore hardness of the sizing material is more than or equal to 40 HA;

2. The compounded rubber of claim 1, wherein the compounded constant viscosity agent comprises an organic constant viscosity agent and an inorganic constant viscosity agent;

the organic constant viscosity agent comprises an organic amine compound, wherein the organic amine compound comprises at least one compound of hydroxylamines, fatty amines, alcamines, alicyclic amines and aromatic amines;

3. The compounded rubber of claim 1, wherein the polar aprotic organic solvent comprises one or more of dimethylformamide, dimethylacetamide, hexamethylphosphoramide, 1, 3-dimethyl-2-imidazolidinone.

4. The compounded rubber of claim 1, wherein the solid gum material comprises at least one of standard rubber, cuffed rubber, crepe rubber, air-dried rubber, and film stock.

5. The composite rubber according to claim 1, wherein in step S1, the ratio of the mass of the zinc ore to the volume of the inorganic ammonium salt solution is 100-150 g/L; the ratio of the volume of the inorganic ammonium salt solution containing the zinc-ammonia complex ions to the volume of the organic amine compound solution is 1: 1.5-2.0;

the zinc ore comprises at least one of calamine, willemite and hydrozincite.

6. The compounded rubber of claim 1, wherein the organic diacid includes at least one of oxalic acid, succinic acid, malonic acid;

7. The compounded rubber according to claim 1, wherein the drying furnace dries the rubber compound by using saturated steam, and comprises a moisture extraction part, a high-temperature drying part, a low-temperature drying part and a cooling part, wherein the moisture extraction part is communicated with the high-temperature drying part, the high-temperature drying part is communicated with the low-temperature drying part, and the low-temperature drying part is communicated with the cooling part;

8. The compounded rubber according to claim 1, wherein the solid rubber is used as raw material, the rubber is cut into a preset weight according to a proportion, and the cut rubber is put into a dry mixer, a constant viscosity agent spray head is arranged at the inlet of the dry mixer, and the compounded constant viscosity agent is sprayed according to a preset proportion; and (3) fully and uniformly stirring the rubber material and the composite constant binder, extruding the rubber material out of a dry stirring machine under the action of extrusion and shearing, cooling the rubber material in a cooling cabinet by using a blast cooling or negative pressure draft cooling mode after the rubber material enters a cooling hopper through a vibrating screen, and discharging after the temperature of the rubber material is lower than 55 ℃ to obtain the composite rubber.