CN114957784A - Foaming agent master batch and preparation method thereof - Google Patents
Foaming agent master batch and preparation method thereof Download PDFInfo
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- CN114957784A CN114957784A CN202210542425.XA CN202210542425A CN114957784A CN 114957784 A CN114957784 A CN 114957784A CN 202210542425 A CN202210542425 A CN 202210542425A CN 114957784 A CN114957784 A CN 114957784A
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Abstract
The invention relates to a foaming agent master batch and a preparation method thereof, wherein the foaming agent master batch comprises the following preparation raw materials in parts by weight: 1-5 parts of styrene block copolymer, 4-25 parts of mineral oil, 3-15 parts of paraffin, 10-30 parts of polyolefin, 30-75 parts of microsphere foaming agent and 1-2 parts of auxiliary agent, wherein the melting point of the polyolefin is 40-70 ℃, and the foaming starting temperature of the microsphere foaming agent is not less than 100 ℃. The foaming agent master batch prepared by the scheme of the invention can be produced by a double-screw extruder, and the quality of the foaming agent master batch before and after production is stable.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to foaming agent master batches and a preparation method thereof.
Background
With the wide attention on energy conservation and environmental protection, light weight becomes one of the focuses of the plastic industry, and the application requirements of the foaming material are increased. Foamed thermoplastic elastomer (TPE) materials are typically prepared by mixing a TPE with a blowing agent under agitation. However, the microsphere foaming agent is powdery, the TPE is granular, the foaming agent is unevenly distributed in the TPE in the production process, the problems of unstable foaming, uneven foaming and the like of products are easily caused, and the problems can be effectively reduced or avoided by adopting the foaming agent master batch.
At present, the traditional foaming agent master batch mainly takes ethylene-vinyl acetate copolymer as a carrier, and when the foaming agent master batch is extruded by a double-screw extruder in the preparation process, the problem that the foaming agent content in the foaming agent master batch before and after production is large in difference exists, and the foaming agent master batch needs to be processed by the double-screw extruder twice. If the processing is carried out by an internal mixer, the production efficiency is lower. Therefore, how to provide a foaming agent master batch which can be produced by a common double-screw extruder, is stable in production and does not need to be extruded twice is a problem which needs to be solved urgently.
Disclosure of Invention
Based on this, it is necessary to provide a method for producing a stable foaming agent master batch.
The invention aims to provide a foaming agent master batch, which comprises the following preparation raw materials in parts by weight: 1-5 parts of styrene block copolymer, 4-25 parts of mineral oil, 3-15 parts of paraffin, 10-30 parts of polyolefin, 30-75 parts of microsphere foaming agent and 1-2 parts of auxiliary agent, wherein the melting point of the polyolefin is 40-70 ℃, and the foaming starting temperature of the microsphere foaming agent is not less than 100 ℃.
In one embodiment, the styrene block copolymer is one or more of a styrene-ethylene-butylene-styrene block copolymer elastomer, a styrene-ethylene-propylene-styrene block copolymer elastomer, and a styrene-butadiene-styrene block copolymer.
In one embodiment, the molecular weight of the styrenic block copolymer is from 6 to 13 million.
In one embodiment, the preparation raw material also comprises 2-6 parts of anhydride modifier.
In one embodiment, the anhydride modifier is one or two of anhydride modified ethylene propylene diene monomer and anhydride modified ethylene copolymer; and/or the melting point of the anhydride modifier is 40-70 ℃.
In one embodiment, the mineral oil is one or two of paraffin oil and naphthenic oil; and/or the ratio of the mineral oil to the styrene block copolymer is (3-5): 1.
in one embodiment, the auxiliary agent is one or more of a lubricant, a dispersant and an antioxidant.
In one embodiment, the lubricant is one or more of oleamide, zinc stearate, calcium stearate, erucamide, and silicone.
The invention also aims to provide a preparation method of the foaming agent master batch, which comprises the following steps:
mixing the styrenic block copolymer with the mineral oil; then adding the paraffin, the polyolefin, the microsphere foaming agent, the anhydride modifier and the auxiliary agent to prepare a mixture;
and heating the mixture to be molten, plasticizing, extruding and granulating to prepare the foaming agent master batch.
In one embodiment, the heating temperature is 75 ℃ to 100 ℃.
The invention also aims to provide a foaming thermoplastic elastomer material which is characterized in that the foaming agent master batch or the foaming agent master batch prepared by the preparation method of the foaming agent master batch is adopted for foaming.
Compared with the prior art, the invention has the following advantages and beneficial effects:
according to the invention, researches show that the foaming agent master batch can be produced by a double-screw extruder by using the styrene block copolymer as a foaming agent carrier, reasonably matching the raw materials in parts by weight, adding the mineral oil, the paraffin, the polyolefin, the anhydride modifier and the auxiliary agent in a matching manner and mutually coordinating the components, and the foaming agent master batch has stable quality before and after production and does not need to be extruded twice.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The following is a description of preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The invention provides a foaming agent master batch, which comprises the following preparation raw materials in parts by weight: 1-5 parts of styrene block copolymer, 4-25 parts of mineral oil, 3-15 parts of paraffin, 10-30 parts of polyolefin, 30-75 parts of microsphere foaming agent and 1-2 parts of auxiliary agent, wherein the melting point of the polyolefin is 40-70 ℃, and the foaming starting temperature of the microsphere foaming agent is not less than 100 ℃.
Further, the foaming starting temperature of the microsphere foaming agent is 100-230 ℃.
Without limitation, the microsphere foaming agent can be any one or more of Aksu 950DU80, 951DU120, 980DU12 and Hunan Xiang technology FARIDA TEPF019, and mineral oil of other companies or models can meet the requirements.
Without limitation, the mineral oil may be any one or more of dadmal POE 6202/6102, dow POE GR216, 8150, 8100, and mineral oils of other companies or models may also meet the requirements.
In one example, the polyolefin has a melting point of 40 ℃ to 70 ℃. The melting point is lower than 70 ℃ which is beneficial to plasticization, and the temperature is higher than 40 ℃ which can avoid agglomeration of master batches in the storage process.
The foaming agent master batch provided by the invention has excellent extrusion processing performance by selecting proper raw materials and mass percentage, can prevent the microsphere foaming agent from foaming when passing through a double-screw extruder, is beneficial to realizing the coating of the microsphere foaming agent and the molding of the master batch, has good overall fluidity, and can be uniformly covered on the surface of a material to be foamed when in use, so that the foaming of a foamed product is more uniform. The foaming agent master batch has smooth surface, so that the internal friction among materials in use can be reduced, the foaming agent is prevented from being exploded in advance when being mixed, and the foam holes are more uniform.
In one example, the styrene block copolymer is one or more of a styrene-ethylene-butylene-styrene block copolymer elastomer, a styrene-ethylene-propylene-styrene block copolymer elastomer, and a styrene-butadiene-styrene block copolymer.
In one example, the molecular weight of the styrenic block copolymer is 6 to 13 ten thousand.
Without limitation, the styrene block copolymer used in the present application may be any one or more of SEBS YH501T, SEBS 6153, SEBS 7550, SEBS G1650, seepy 4033, SBS 3535/3546, and any other type or company of styrene block copolymer may meet the requirements.
The styrene block copolymer has excellent processability, good coating property on a microsphere foaming agent and good compatibility with most thermoplastic elastomer materials. After the powdery styrene block copolymer fully absorbs the mineral oil, the surface of the powdery styrene block copolymer has adhesiveness, the powdery styrene block copolymer is uniformly distributed in the microsphere foaming agent, and the microsphere foaming agent with lower bulk density is adhered, so that the bulk density of the microsphere foaming agent is increased, the layering phenomenon cannot occur when the materials are stirred and mixed, and a more uniform mixed material is obtained.
In one example, unless otherwise specified, the composition does not contain other components not specifically specified except for inevitable impurities.
In one example, the preparation raw material further comprises 2-6 parts of an anhydride modifier.
In one example, the acid anhydride modifier is one or two of acid anhydride modified ethylene propylene diene monomer and acid anhydride modified ethylene copolymer; and/or the melting point of the anhydride modifier is 40-70 ℃.
Without limitation, the anhydride-modified product used in the present invention may be one or more of N416, N493, and N525 from dupont, and other companies or models of anhydride-modified products may suffice.
The acid anhydride part in the acid anhydride modifier molecule has good compatibility with the shell of the microsphere foaming agent, and the main body part has compatibility with polyolefin, so that the whole compatibility of the foaming agent master batch is better, and the surface of the foaming agent master batch is smoother.
In one example, the anhydride modifier has a melting point of 40 to 70 ℃. The melting point is lower than 70 ℃ which is beneficial to plasticization, and the temperature is higher than 40 ℃ which can avoid agglomeration of master batches in the storage process.
In one example, the mineral oil is one or both of a paraffinic oil and a naphthenic oil; and/or the ratio of the mineral oil to the styrene block copolymer is (3-5): 1.
in one example, the mineral oil is at least one of a paraffinic oil and a naphthenic oil.
Without limitation, the mineral oil used in the present invention may be one or more of handi sunshine 32#, crambe 26#, KN4006, KN4010, midsea oil 60N and Kerun 500N, and other companies or models of mineral oil may also meet the requirements.
In one example, the paraffin wax is one or more of a crude paraffin wax, a fully refined paraffin wax, and a semi-refined paraffin wax.
The paraffin wax adopted by the invention can be one or more of crude paraffin wax, Kunlun 56#, 58#, 60#, 64# fully refined paraffin wax and Chinese petrochemical 58#, 60#, 64# semi-refined paraffin wax, and paraffin wax of other companies or models can also meet the requirements without limitation.
In one example, the auxiliary agent is one or more of a lubricant, a dispersant and an antioxidant.
In one example, the lubricant is one or more of oleamide, zinc stearate, calcium stearate, erucamide, and silicone.
Without limitation, the auxiliary agent adopted by the invention can be one or more of antioxidant 168, 1076 of basf, zinc stearate AV300 of Hanwei, pure silicone master batch ATC-5310, AC-6002, AT502 and Yuntai YY-603, and the auxiliary agent of other companies or models can also meet the requirements.
The invention also aims to provide a preparation method of the foaming agent master batch, which comprises the following steps:
mixing the styrenic block copolymer with the mineral oil; then adding the paraffin, the polyolefin, the microsphere foaming agent, the anhydride modifier and the auxiliary agent to prepare a mixture;
and heating the mixture to be molten, plasticizing, extruding and granulating to prepare the foaming agent master batch.
In one example, the heating temperature is 75 ℃ to 100 ℃.
In one example, the number of extrusions is one.
In one example, the preparation method of the foaming master batch comprises the following steps:
weighing 1-5 parts of styrene block copolymer and 4-25 parts of mineral oil according to the mass parts of the preparation raw materials, adding the raw materials into a high-speed mixer, stirring and mixing, and performing oil absorption treatment, wherein the stirring speed is 8-20 Hz, and the time is 10-20 min;
weighing 3-15 parts of paraffin, 10-30 parts of polyolefin, 30-75 parts of microsphere foaming agent, 2-6 parts of anhydride modifier and 1-2 parts of auxiliary agent according to the mass parts of the preparation raw materials, adding into a high-speed mixer, and stirring with the mixture of the styrene block copolymer and the mineral oil at the stirring speed of 30-50 Hz for 5-10 min to obtain a uniform mixture;
pouring the uniform mixture into a feed hopper of a shearing double-screw extruder, heating and melting at 75-100 ℃, plasticizing, extruding, carrying out underwater grain cutting or air cooling grain cutting, and finally screening and drying by a vibrating screen to obtain the microsphere foaming agent master batch which is beautiful, easy to disperse, well distributed and high in content and takes the thermoplastic elastomer as the carrier.
The preparation method of the microsphere foaming agent master batch taking the thermoplastic elastomer as the carrier has simple process flow and low requirement on equipment, and is suitable for large-scale industrial production.
The invention also provides a foaming thermoplastic elastomer material which is characterized in that the foaming agent master batch or the foaming agent master batch prepared by the preparation method of the foaming agent master batch is adopted for foaming. According to the invention, through research, the styrene block copolymer is used as a foaming agent carrier, the raw materials are reasonably matched in parts by weight, the mineral oil, the paraffin, the polyolefin, the anhydride modifier and the auxiliary agent are added in a matching manner, the components are cooperated with each other, the obtained foaming agent master batch is uniformly foamed, the foaming agent master batch can be produced by a double-screw extruder, the quality of the foaming agent master batch before and after production is stable, and two times of extrusion are not needed.
The following are specific examples.
Example 1: preparation of foaming agent master batch
The preparation method comprises the following steps:
adding 1 part of styrene block copolymer YH501T and 4 parts of mineral oil 26# into a high-speed mixer, mixing, and stirring for 15 minutes at the rotation speed of 10 Hz;
then adding 4 parts of paraffin 58#, 14 parts of polyolefin 6202, 75 parts of microsphere foaming agent 950DU80, 2 parts of anhydride modified substance N416, 0.1 part of auxiliary agent 168, 0.1 part of auxiliary agent 1010 and 0.5 part of AV300, and stirring for 5 minutes at the rotating speed of 40Hz to obtain a uniform mixture;
adding the mixture into a blanking hopper of a shearing double-screw extruder, heating the mixture to be molten and plasticized by double screws at 85 ℃, extruding the mixture, cutting the mixture into granules under water, screening the granules by a vibrating screen, and drying the granules to obtain the foaming agent master batch.
Example 2: preparation of foaming agent master batch
The preparation method comprises the following steps:
adding 2 parts of styrene block copolymer YH501T and 8 parts of mineral oil 26# into a high-speed mixer, mixing, and stirring for 15 minutes at the rotation speed of 10 Hz;
then adding 6 parts of paraffin 58#, 20 parts of polyolefin 6202, 60 parts of microsphere foaming agent 950DU80, 4 parts of anhydride modified substance N416, 0.1 part of auxiliary agent 168, 0.1 part of auxiliary agent 1010 and 0.5 part of AV300, and stirring for 5 minutes at the rotating speed of 40Hz to obtain a uniform mixture;
adding the mixture into a blanking hopper of a shearing double-screw extruder, heating the mixture to be molten and plasticized by double screws at 85 ℃, extruding the mixture, cutting the mixture into granules under water, screening the granules by a vibrating screen, and drying the granules to obtain the foaming agent master batch.
Example 3: preparation of foaming agent master batch
The preparation method comprises the following steps:
adding 4 parts of styrene block copolymer YH501T and 16 parts of mineral oil 26# into a high-speed mixer, mixing, and stirring for 15 minutes at the rotation speed of 10 Hz;
then adding 9 parts of paraffin 58#, 22 parts of polyolefin 6202, 45 parts of microsphere foaming agent 950DU80, 4 parts of anhydride modified substance N416, 0.1 part of auxiliary agent 168, 0.1 part of auxiliary agent 1010 and 0.5 part of AV300, and stirring for 5 minutes at the rotating speed of 40Hz to obtain a uniform mixture;
and adding the mixture into a feeding hopper of a shearing double-screw extruder, heating the mixture to be molten and plasticized by double screws at 85 ℃, extruding the mixture, cutting the mixture into granules under water, screening the granules by a vibrating screen, and drying the granules to obtain the foaming agent master batch.
Example 4: preparation of foaming agent master batch
The preparation method comprises the following steps:
adding 5 parts of styrene block copolymer YH501T and 20 parts of mineral oil 26# into a high-speed mixer, mixing, and stirring for 15 minutes at the rotation speed of 10 Hz;
then adding 15 parts of paraffin 58#, 26 parts of polyolefin 6202, 30 parts of microsphere foaming agent 950DU80, 4 parts of anhydride modified substance N416, 0.1 part of auxiliary agent 168, 0.1 part of auxiliary agent 1010 and 0.5 part of AV300, and stirring for 5 minutes at the rotating speed of 40Hz to obtain a uniform mixture;
adding the mixture into a blanking hopper of a shearing double-screw extruder, heating the mixture to be molten and plasticized by double screws at 85 ℃, extruding the mixture, cutting the mixture into granules under water, screening the granules by a vibrating screen, and drying the granules to obtain the foaming agent master batch.
Example 5: preparation of foaming agent master batch
The preparation method of example 5 is substantially the same as that of example 1 except that: the styrene block copolymer YH501T was replaced by a styrene block copolymer YH503T having a higher molecular weight, and the contents of the respective components were exactly the same as those in example 1.
The method comprises the following specific steps:
adding 1 part of styrene block copolymer YH503T and 4 parts of mineral oil 26# into a high-speed mixer, mixing, and stirring for 15 minutes at the rotation speed of 10 Hz;
then adding 4 parts of paraffin 58#, 14 parts of polyolefin 6202, 75 parts of microsphere foaming agent 950DU80, 2 parts of anhydride modified substance N416, 0.1 part of auxiliary agent 168, 0.1 part of auxiliary agent 1010 and 0.5 part of AV300, and stirring for 5 minutes at the rotating speed of 40Hz to obtain a uniform mixture;
adding the mixture into a blanking hopper of a shearing double-screw extruder, heating the mixture to be molten and plasticized by double screws at 85 ℃, extruding the mixture, cutting the mixture into granules under water, screening the granules by a vibrating screen, and drying the granules to obtain the foaming agent master batch.
Example 6: preparation of foaming agent master batch
The production method of example 6 is substantially the same as that of example 1 except that: the anhydride-modified product N416 was omitted by replacing the anhydride-modified product with the same mass of polyolefin 6202, and the contents of the remaining components were exactly the same as those in example 1.
The method comprises the following specific steps:
adding 1 part of styrene block copolymer YH501T and 4 parts of mineral oil 26# into a high-speed mixer, mixing, and stirring for 15 minutes at the rotation speed of 10 Hz;
then adding 4 parts of paraffin 58#, 16 parts of polyolefin 6202, 75 parts of microsphere foaming agent 950DU80, 0.1 part of auxiliary agent 168, 0.1 part of auxiliary agent 1010 and 0.5 part of AV300, and stirring for 5 minutes at the rotating speed of 40Hz to obtain a uniform mixture;
and adding the mixture into a feeding hopper of a shearing double-screw extruder, heating the mixture to be molten and plasticized by double screws at 85 ℃, extruding the mixture, cutting the mixture into granules under water, screening the granules by a vibrating screen, and drying the granules to obtain the foaming agent master batch.
Comparative example 1: preparation of foaming agent master batch
The preparation method of comparative example 1 is substantially the same as that of example 1 except that: the polyolefin 6202 was replaced with a polyolefin 8480 having a melting point of 99 ℃ and the contents of the respective components were exactly the same as in example 1. Aiming at comparing the influence of polyolefin with low melting point and high melting point on the processing and forming of the foaming agent master batch.
The method comprises the following specific steps:
adding 1 part of styrene block copolymer YH501T and 4 parts of mineral oil 26# into a high-speed mixer, mixing, and stirring for 15 minutes at the rotation speed of 10 Hz;
then adding 4 parts of paraffin 58#, 14 parts of polyolefin 8480, 75 parts of microsphere foaming agent 950DU80, 2 parts of anhydride modified N416, 0.1 part of auxiliary agent 168, 0.1 part of auxiliary agent 1010 and 0.5 part of AV300, and stirring for 5 minutes at the rotating speed of 40Hz to obtain a uniform mixture;
adding the mixture into a blanking hopper of a shearing double-screw extruder, heating the mixture to be molten and plasticized by double screws at 85 ℃, extruding the mixture, cutting the mixture into granules under water, screening the granules by a vibrating screen, and drying the granules to obtain the foaming agent master batch.
Comparative example 2: preparation of foaming agent master batch
The preparation method of comparative example 2 is substantially the same as that of example 1 except that: the microsphere foaming agent 950DU80 is replaced by 551DU40 with the foaming starting temperature of 94-99 ℃, and the contents of the other components are completely the same as those in the example 1. Aiming at comparing the influence of the initial foaming temperature of the microsphere foaming agent on the processing and forming of the foaming agent master batch.
The method comprises the following specific steps:
adding 1 part of styrene block copolymer YH501T and 4 parts of mineral oil 26# into a high-speed mixer, mixing, and stirring for 15 minutes at the rotation speed of 10 Hz;
then adding 4 parts of paraffin 58#, 14 parts of polyolefin 6202, 75 parts of microsphere foaming agent 551DU40, 2 parts of anhydride modified substance N416, 0.1 part of auxiliary agent 168, 0.1 part of auxiliary agent 1010 and 0.5 part of AV300, and stirring for 5 minutes at the rotating speed of 40Hz to obtain a uniform mixture;
adding the mixture into a blanking hopper of a shearing double-screw extruder, heating the mixture to be molten and plasticized by double screws at 85 ℃, extruding the mixture, cutting the mixture into granules under water, screening the granules by a vibrating screen, and drying the granules to obtain the foaming agent master batch.
Comparative example 3: preparation of foaming agent master batch
The preparation method of comparative example 3 is substantially the same as that of example 1 except that: the styrene block copolymer YH501T and mineral oil # 26 were omitted, and the same mass of polyolefin 6202 was replaced, and the contents of the other components were exactly the same as those in example 1. Aiming at comparing the influence of the styrene block copolymer and the mineral oil on the processing and forming of the foaming agent master batch.
The method comprises the following specific steps:
adding 4 parts of paraffin 58#, 19 parts of polyolefin 6202, 75 parts of microsphere foaming agent 950DU80, 2 parts of anhydride modified substance N416, 0.1 part of auxiliary agent 168, 0.1 part of auxiliary agent 1010 and 0.5 part of AV300 into a high-speed mixer for mixing, and stirring at the rotating speed of 40Hz for 5 minutes to obtain a uniform mixture;
adding the mixture into a blanking hopper of a shearing double-screw extruder, heating the mixture to be molten and plasticized by double screws at 85 ℃, extruding the mixture, cutting the mixture into granules under water, screening the granules by a vibrating screen, and drying the granules to obtain the foaming agent master batch.
Comparative example 4: preparation of foaming agent master batch
The preparation method of comparative example 4 is substantially the same as that of example 1 except that: adopts the traditional ethylene-vinyl acetate as the carrier of the foaming agent master batch.
The method comprises the following specific steps:
stirring 20 parts of ethylene-vinyl acetate copolymer UE654, 3 parts of paraffin 58#, 2 parts of silane coupling agent KH-550, 75 parts of microsphere foaming agent 950DU80, 0.1 part of auxiliary agent 168, 0.1 part of auxiliary agent 1010 and 0.5 part of AV300 at the rotating speed of 40Hz for 5 minutes to obtain a uniform mixture;
adding the mixture into a blanking hopper of a shearing double-screw extruder, heating the mixture to be molten and plasticized by double screws at 85 ℃, extruding the mixture, cutting the mixture into granules under water, screening the granules by a vibrating screen, and drying the granules to obtain the foaming agent master batch.
The foaming agent master batches prepared in examples 1 to 6 and comparative examples 1 to 4 were subjected to a performance test. Wherein the melt index is measured according to ASTM D-1238(110 ℃, 5 kg); the test standard for specific gravity is ASTM D-792; the molding effect of the foaming agent master batch is evaluated by observation, and all the foaming agent master batches are stably molded for 5 minutes and cannot be molded for 0 minute; the surface effect was evaluated by observation, and the total surface was flat and smooth for 5 minutes and the total surface was rough for 0 minutes, and the test results are shown in table 1 below.
TABLE 1 foaming agent masterbatch Performance test results
| Effect of formation | Melt index | Specific gravity of | Surface effects | |
| Example 1 | 5 | 12 | 0.82 | 5 |
| Example 2 | 5 | 21 | 0.84 | 5 |
| Example 3 | 5 | 22 | 0.86 | 5 |
| Example 4 | 5 | 45 | 0.86 | 5 |
| Example 5 | 5 | 7 | 0.82 | 3 |
| Example 6 | 5 | 10 | 0.82 | 3 |
| Comparative example 1 | 0 | - | - | - |
| Comparative example 2 | 0 | - | - | - |
| Comparative example 3 | 3 | 5 | 0.85 | 3 |
| Comparative example 4 | 2 | 2 | 0.86 | 3 |
The foaming agent master batches of the embodiments 1-6 are easy to form, are produced by adopting a common double-screw extruder, are stable in production and do not need to be extruded twice. The foaming agent master batch obtained in the embodiments 1 to 4 has a flat and smooth surface and high fluidity. Example 5 compared with the test results of example 1, when the low molecular weight styrene block copolymer was replaced with the high molecular weight styrene block copolymer, the foaming agent masterbatch had a poor surface effect and a reduced fluidity. In example 6, the surface of the obtained foaming agent master batch was rough compared with example 1, except that the acid anhydride modifier N416 was not contained. Comparative example 1 compared with the test results of example 1, the polyolefin 6202 having a melting temperature of 60 ℃ was replaced with 8480 having a melting temperature of 99 ℃, and the obtained pellets had poor flowability and could not be plasticized and pelletized under the heating condition of 75 ℃ to 100 ℃ in a twin screw. Comparative example 2 compared with example 1, the foaming agent 950DU80 was replaced by 551DU40 with the foaming initiation temperature of 94 ℃ to 99 ℃ and the mixture began to foam during the twin-screw extrusion process and could not be pelletized. Compared with the example 1, the styrene block copolymer and the mineral oil are omitted, the polyolefin 6202 is replaced, the foaming agent master batch cannot be stably formed, the surface is rough, materials cannot be uniformly distributed during processing, the production is unstable, and the obtained particles are different greatly.
Example 7: preparation of foamed thermoplastic elastomer material
4 parts of the foaming agent master batch prepared in the example 1 (wherein the mass percentage of the microsphere foaming agent is about 75%) and 96 parts of TPE GP210-60 parts of Jialun rubber and plastic Limited company are uniformly stirred, and then the mixture is added into an injection molding machine for continuously injecting 20 samples with the specification of 60mm multiplied by 6mm to obtain a foaming sample.
Example 8: preparation of foamed thermoplastic elastomer material
4 parts of the foaming agent master batch prepared in the example 2 (wherein the mass percentage of the microsphere foaming agent is about 60%) and 96 parts of TPE GP210-60 parts of Jialun rubber and plastic Limited company are uniformly stirred, and then the mixture is added into an injection molding machine for continuously injecting 20 sample plates with the specification of 60mm multiplied by 6mm, so as to obtain the foaming sample plate.
Example 9: preparation of foamed thermoplastic elastomer material
4 parts of the foaming agent master batch prepared in the embodiment 3 (wherein the mass percentage of the microsphere foaming agent is about 45%) and 96 parts of TPE GP210-60 parts of Jialun rubber and plastic Limited company are uniformly stirred, and then the mixture is added into an injection molding machine for continuously injecting 20 sample plates with the specification of 60mm multiplied by 6mm, so as to obtain the foaming sample plate.
Example 10: preparation of foamed thermoplastic elastomer material
4 parts of the foaming agent master batch prepared in the embodiment 4 (wherein the mass percentage of the microsphere foaming agent is about 30%) and 96 parts of TPE GP210-60 parts of Jialun rubber and plastic Limited company are uniformly stirred, and then the mixture is added into an injection molding machine for continuously injecting 20 sample plates with the specification of 60mm multiplied by 6mm, so as to obtain the foaming sample plate.
Example 11: preparation of foamed thermoplastic elastomer material
4 parts of the foaming agent master batch prepared in the example 5 (wherein the mass percentage of the microsphere foaming agent is about 75%) and 96 parts of TPE GP210-60 parts of Jialun rubber and plastic Limited company are uniformly stirred, and then the mixture is added into an injection molding machine for continuously injecting 20 samples with the specification of 60mm multiplied by 6mm to obtain a foaming sample.
Example 12: preparation of foamed thermoplastic elastomer material
4 parts of the foaming agent master batch prepared in the embodiment 6 (wherein the mass percentage of the microsphere foaming agent is about 75%) and 96 parts of TPE GP210-60 parts of Jialun rubber and plastic Limited company are uniformly stirred, and then the mixture is added into an injection molding machine for continuously injecting 20 samples with the specification of 60mm multiplied by 6mm to obtain a foaming sample plate.
Comparative example 5: preparation of foamed thermoplastic elastomer material
3 parts of microsphere foaming agent 950DU80 and 97 parts of TPE GP210-60 parts of Jialun rubber and plastic Limited company are uniformly stirred, and then the mixture is added into an injection molding machine for continuous injection molding of 20 samples with the specification of 60mm multiplied by 6mm, so as to obtain the foaming sample.
Comparative example 6: preparation of foamed thermoplastic elastomer material
4 parts of the foaming agent master batch (wherein the mass percentage of the microsphere foaming agent is about 75%) which is prepared in the comparative example 4 and takes ethylene-vinyl acetate as a carrier and 96 parts of TPE GP210-60 parts of the Furan rubber and plastic company Limited are uniformly stirred, and then the mixture is added into an injection molding machine for continuously injecting 20 samples with the specification of 60mm multiplied by 6mm, so as to obtain a foaming sample plate.
The performance and effect tests were performed on the foamed thermoplastic elastomer materials obtained in examples 7 to 12 and comparative examples 5 to 6. Wherein, the specific gravities of 20 foaming sample plates were tested according to the test standard ASTM D-792, and the variance was calculated as the foaming stability evaluation parameter. The bubble effect is evaluated by electron microscope observation, the bubble is uniform and does not break into 5 minutes, and the bubble is non-uniform and completely breaks into 0 minute. The surface effect was evaluated by observation, and the total surface was flat by 5 minutes and the total surface roughness by 0 minutes, and the test results are shown in table 2.
TABLE 2 Performance test results of foamed thermoplastic elastomer materials
| Average specific gravity | Stability of foaming | Bubble effect | Surface effects | |
| Example 7 | 0.40 | 0.00144 | 4 | 4 |
| Example 8 | 0.53 | 0.00131 | 4 | 4 |
| Example 9 | 0.65 | 0.00185 | 4 | 5 |
| Example 10 | 0.72 | 0.00212 | 4 | 5 |
| Example 11 | 0.42 | 0.00155 | 4 | 4 |
| Example 12 | 0.44 | 0.00188 | 3 | 4 |
| Comparative example 5 | 0.47 | 0.00854 | 1 | 4 |
| Comparative example 6 | 0.46 | 0.01241 | 3 | 3 |
The foamed thermoplastic elastomer material of example 7 was low in specific gravity, stable in foaming, uniform in cells, and uniform in foaming after foaming, and comparative examples 5 to 6 were larger in specific gravity, poor in foaming stability, more in cell breakage, and non-uniform in foaming after foaming, compared with example 7. It can be seen from examples 7-10 that as the content of the foaming agent is reduced, the specific gravity after foaming is increased, the foam cells are close to each other, and examples 9 and 10 have better surface effects but relatively poor foaming stability. Example 12 had inferior foaming stability and more cell breakage compared to example 7.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The foaming agent master batch is characterized in that the foaming agent master batch is prepared from the following raw materials in parts by weight: 1-5 parts of styrene block copolymer, 4-25 parts of mineral oil, 3-15 parts of paraffin, 10-30 parts of polyolefin, 30-75 parts of microsphere foaming agent and 1-2 parts of auxiliary agent, wherein the melting point of the polyolefin is 40-70 ℃, and the foaming starting temperature of the microsphere foaming agent is not less than 100 ℃.
2. The blowing agent masterbatch of claim 1 wherein the styrene block copolymer is one or more of a styrene-ethylene-butylene-styrene block copolymer elastomer, a styrene-ethylene-propylene-styrene block copolymer elastomer, and a styrene-butadiene-styrene block copolymer.
3. The foaming agent masterbatch according to any one of claims 1 to 2, wherein the molecular weight of the styrene block copolymer is 6 to 13 ten thousand.
4. The foaming master batch of any one of claims 1-2, wherein the raw materials further comprise 2-6 parts of an anhydride modifier.
5. The foaming master batch of claim 4, wherein the anhydride modifier is one or two of anhydride modified ethylene propylene diene monomer and anhydride modified ethylene copolymer; and/or the melting point of the anhydride modifier is 40-70 ℃.
6. The foaming master batch according to any one of claims 1 to 2, wherein the mineral oil is one or two of paraffin oil and naphthenic oil; and/or the ratio of the mineral oil to the styrene block copolymer is (3-5): 1.
7. The foaming master batch according to any one of claims 1-2, wherein the auxiliary agent is one or more of a lubricant, a dispersant and an antioxidant.
8. The foaming concentrate of claim 7, wherein the lubricant is one or more of oleamide, zinc stearate, calcium stearate, erucamide, and silicone.
9. The method for preparing the foaming agent masterbatch according to any one of claims 1 to 8, wherein the method comprises the following steps:
mixing the styrenic block copolymer with the mineral oil; then adding the paraffin, the polyolefin, the microsphere foaming agent, the anhydride modifier and the auxiliary agent to prepare a mixture;
and heating the mixture to be molten, plasticizing, extruding and granulating to prepare the foaming agent master batch.
10. A foaming thermoplastic elastomer material is characterized in that foaming agent master batch of any one of claims 1-8 or the foaming agent master batch prepared by the preparation method of the foaming agent master batch of claim 9 is adopted for foaming.
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| DE102013224275A1 (en) * | 2013-11-27 | 2015-05-28 | Basf Se | Process for the preparation of expandable, thermoplastic polymer particles with improved blowing agent retention capacity |
| CN105694484A (en) * | 2016-03-11 | 2016-06-22 | 福州市昊旺材料科技有限公司 | TPE (thermoplastic elastomer) foamed master batch and preparation method thereof |
| CN110709454A (en) * | 2017-06-09 | 2020-01-17 | 株式会社钟化 | Expanded polyolefin resin particle, method for producing expanded polyolefin resin particle, and molded article obtained by in-mold expansion of polyolefin resin |
| CN114316311A (en) * | 2021-11-23 | 2022-04-12 | 快思瑞科技(上海)有限公司 | Foamed composite material and preparation method thereof |
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| DE102013224275A1 (en) * | 2013-11-27 | 2015-05-28 | Basf Se | Process for the preparation of expandable, thermoplastic polymer particles with improved blowing agent retention capacity |
| CN105694484A (en) * | 2016-03-11 | 2016-06-22 | 福州市昊旺材料科技有限公司 | TPE (thermoplastic elastomer) foamed master batch and preparation method thereof |
| CN110709454A (en) * | 2017-06-09 | 2020-01-17 | 株式会社钟化 | Expanded polyolefin resin particle, method for producing expanded polyolefin resin particle, and molded article obtained by in-mold expansion of polyolefin resin |
| CN114316311A (en) * | 2021-11-23 | 2022-04-12 | 快思瑞科技(上海)有限公司 | Foamed composite material and preparation method thereof |
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