CN102031079B - Cobalt salt adhesive for bonding nitrile rubber and copper/zinc frame and preparation method thereof - Google Patents
Cobalt salt adhesive for bonding nitrile rubber and copper/zinc frame and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cobalt salt adhesive for bonding nitrile rubber and a copper/zinc frame and a preparation method thereof. The adhesive comprises a compound adhesive, phenolic resin and assistants, wherein the compound adhesive comprises a main adhesive and an auxiliary adhesive, wherein the main adhesive comprises cobalt borate and cobalt neodecanoate; the auxiliary adhesive is compound organic salt containing nickel and vanadium; the phenolic resin comprises a methylene donor and a methylene acceptor; and the assistants comprise toughening agents, activating agents, vulcanization activators, silane coupling agents and vulcanizing agents. The preparation method comprises the following steps: dispersing the compound adhesive in the carrier phenolic resin, and dissolving by a mixed solvent under the actions of the assistants to obtain adhesive cement, thereby obtaining the cobalt salt adhesive for bonding the nitrile rubber and the copper/zinc frame. The cobalt salt adhesive provided by the invention has the advantages of high thermal stability, favorable dynamic mechanical properties and low cost, can be directly coated, and is suitable for high-strength bonding of mixed rubberof nitrile rubber and regenerated rubber or regenerated rubber powder and a copper/zinc/copper alloy/zinc alloy/zinc plated/brass-plated frame.
Description
Technical field
The present invention relates to tamanori and preparation method thereof, especially for the mixed rubber of paracril and reclaimed rubber or ground rubber and copper, zinc, copper alloy, zinc alloy, zinc-plated, paracril that the brass-plating skeleton binds and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile and preparation method thereof.
Background technology
At radial wire cord tire; the steel wire reinforcement travelling belt; the large-scale rubber item industry that the serializations such as wire braided hose are produced; to elastomericss and zinc-plated such as rubber; the high strength of the framework material that the brass-plated steel wire cord is woven into is binded and is usually adopted direct addition type cobalt salt adhesive; directly the addition type cobalt salt adhesive comprises cobalt stearate; solid cobaltic naphthenate; new cobalt decanoate; cobalt boracylate etc.; these cobalt salt adhesives particularly cobalt boracylate except having high-intensity cement properties; also have anti-aging; heat-resisting oxygen; wet-heat resisting; salt water resistance corrosion and the excellent properties such as fire-retardant are widely used in the production of Large Scale and Continuous rubber item.But this type of cobalt salt adhesive is direct addition type, can not apply use, and is only applicable to zinc-plated, brass-plated steel wire cord framework material, and is undesirable for the bonding effect of copper, zinc, copper alloy, zinc alloy framework material.
Protect string, bearing, sealing member, crawler belt, inflating valve etc. for middle-size and small-size rubber item such as rubber absorbers, rubber, because these product surface shapes are special, the single-piece glue consumption is little, usually adopt the batch production mode, but generally need to adopt coating rubber---metal-to-metal adhesive.At present, but the normally used coating rubber of these middle-size and small-size rubber item industries---the main dependence on import of metal-to-metal adhesive, this class tamanori realizes that the bonding of rubber and metal mainly relies on various kinds of resin in the tamanori to the infiltration of metallic surface, adsorb and adhere to, namely pass through electric attraction, the physical force such as Van der Waals force realize binding, occur without chemical reaction with the metallic surface, the bonding process belongs to physical process, this has just determined the heat aging performance of this class tamanori, dynamic properties is poor, from using the result, the goods that bind in use easily come unstuck, and troublesome poeration, expensive.
The application type modification cobalt salt adhesive take rubber as carrier that occurs in recent years is a kind of take the chemistry bonding as main novel tamanori kind, except having high strength bonding ability, anti-aging, heat-resisting oxygen, wet-heat resisting, the salt water resistance corrosion and the excellent properties such as fire-retardant that have also effectively kept direct addition type cobalt salt adhesive, and can apply use, adaptation to framework material is wide, low price, safety and environmental protection are very promising novel application type rubber---the metal-to-metal adhesive kinds of a class.But, many rubber item producers are for reducing the rubber item cost, a large amount of reclaimed rubber or ground rubbers of using in the prescription of rubber item, though reclaimed rubber is processed through desulfurization, but rubber molecular chain not exclusively is linear structure, and ground rubber then is the vulcanized rubber that has vulcanized, and almost completely is reticulated structure, this just so that the bonding ability of the application type modification cobalt salt adhesive take the chemistry bonding as the master, take rubber as carrier sharply descends, can not adapt to the needs of this class rubber item producer.
Summary of the invention
Goal of the invention: the present invention is directed to the problem that above-mentioned prior art exists, a kind of paracril that is applicable to contain reclaimed rubber or ground rubber and copper, zinc bonding, good, the direct coating use of heat aging property, relative low price, paracril easy to use and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile and preparation method thereof are provided.
Technical scheme: a kind of paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile, comprise composite adhesive and resol and auxiliary agent, composite adhesive is by main tamanori and help tamanori to form, wherein main tamanori comprises cobalt boracylate and new cobalt decanoate, helping tamanori is compound organic salt nickeliferous, vanadium, resol comprises methylene radical donor and methylene receptor, and auxiliary agent comprises toughner, activator, vulcanization leveller, silane coupling agent, vulcanizing agent; Be scattered in the resol carrier composite adhesive and compounding aid, make rubber cement by the mixed solvent dissolving, obtain paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile, its component by mass percentage proportioning is:
(1) composite adhesive: take the composite adhesive quality as 100%, cobalt boracylate 37%～58%, new cobalt decanoate 34%～55% helps tamanori 6%～10%; Wherein to help the tamanori quality as 100%, help that total metal content is 10% ± 0.5% in the tamanori;
(2) mixed solvent: mixed with volume ratio 4:6 with ethyl acetate by dimethylbenzene, the density of mixed solvent is 0.878g/ml;
(3) rubber cement: take the rubber cement quality as 100%, composite adhesive 0.8%～1.6%, methylene radical donor 7.1%～10.7%, methylene receptor 7.1%～10.7%, toughner 1.7%～4.5%, activator 5.7%～10.8%, vulcanization leveller 0.8%～1.8%, silane coupling agent 0.8%～1.8%, vulcanizing agent 0.8%～1.8%, mixed solvent 52%～74%.
Each component raw material of the present invention is all selected industrial raw material.Composite adhesive adopts cobalt boracylate and new cobalt decanoate.The molecular formula of cobalt boracylate is B(OCoR)
3, cobalt contents is 22.5% ± 0.7%, weight loss on heating≤1.5%, heptane insolubles 8.0% ± 1.0%, Qualitative Identification boracic; The molecular formula of new cobalt decanoate is CoR
2, cobalt contents is 20.5% ± 0.5%, 80 ℃～100 ℃ of softening temperatures; Compound organic salt nickeliferous, vanadium is the composite alkoxide of 2 ethyl hexanoic acid, naphthenic acid, sylvic acid, and the mol ratio of three kinds of acid is 0.50:0.35:0.15, and this compound organic salt molecular formula is 2MeR
23MeR
3, Me is composition metal in the formula, its content is 10% ± 0.5%, and 80 ℃～100 ℃ of softening temperatures, the mass ratio of nickel, vanadium is 4:6, R is the organic acid of three kinds of acid in the formula; Above percentage ratio is mass percent.Cobalt boracylate as leading kind in the direct addition type cobalt salt adhesive; performance is the most superior but the use processing condition are relatively harsher; new cobalt decanoate has preferably cement properties and uses processing condition relatively looser and stable; rubber cement mixes use by a certain percentage with cobalt boracylate and new cobalt decanoate; the excellent properties that had both kept direct addition type cobalt salt adhesive; make again the stringent process conditions of the single cobalt boracylate of original use become loose and stable, the different technology conditions of the different rubber item of easier adaptation producer.Adopted simultaneously compound organic salt conduct nickeliferous, vanadium to help tamanori to make composite adhesive, under cure conditions, concerted catalysis by active cobalt ion and nickel, vanadium ion, greatly improved the bonding power of sulphur and copper, zinc surface, and the bonding of rubber and metal is to finish by the bonding of chemical bond fully, the bond energy of this chemical bond is large, Heat stability is good, thereby this tamanori is being far superior to other main rubber---metal-to-metal adhesive that relies on the physics bonding between rubber and metal aspect thermotolerance and the dynamic properties.
The methylene radical donor is that the modification melamine resin adds inert support, and methylene receptor is the improvement product of Resorcinol.
Paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile finished product outward appearance are amber thick liquid, and being coated with-4 in the time of 20 ℃, to measure glass viscosity be 120min～140min, and density is 1.02g/ml ± 0.02g/ml, and the coated area when build is 20 μ m is 10m
2/ kg～12m
2/ kg.
The preparation method of paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile, the concrete steps of the method are as follows:
(1) composite adhesive preparation: under 120 ℃ of temperature with the new cobalt decanoate melting, then add cobalt boracylate, and progressively be warming up to 180 ℃ of formation molten baths, add compound organic salt insulation nickeliferous, vanadium and form the homogeneous liquation, be cooled to room temperature, it is for subsequent use to form solid and broken frustillatum;
(2) material pre-treatment: methylene receptor and composite adhesive are pulverized; Methylene receptor powder, composite adhesive powder, methylene radical donor, toughner at room temperature stir predissolve with mixed solvent respectively, and stirring velocity is 40～50 rev/mins;
(3) rubber cement preparation: the mixed solvent that in container, adds required mixed solvent total amount 30%, start and stir, add the good composite adhesive solution of predissolve, methylene receptor solution, methylene radical donor solution stirring is after 2～3 hours, add vulcanization leveller, silane coupling agent, vulcanizing agent stirred 1～2 hour, add again the good toughner solution stirring of predissolve after 5～6 hours, then add activator, replenish mixed solvent continuation stirring and dissolving and obtained rubber cement in 20～24 hours, after the sampling detection is qualified, pour colloidal mill into and grind, the rubber cement that leaches by 200 eye mesh screens is finished product.
Take resol as carrier, composite adhesive and auxiliary agent are dispersed in the resol carrier soln, be prepared into the rubber cement shape tamanori that can apply use, thereby realize the modification purpose, tamanori is become application type by original direct addition type.
Beneficial effect: advantage of the present invention be paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile component adopted the two kinds of direct addition type cobalt salt adhesive of high level raw materials can having complementary advantages for the basis, increased can and the active cobalt ion forms nickeliferous, the vanadium compound organic salt of concerted catalysis, take resol as carrier, by modification the paracril that contains reclaimed rubber or ground rubber and copper, zinc, copper alloy, zinc alloy, zinc-plated, brass-plating skeleton high strength are binded, satisfied the needs of rubber item processing.Tamanori after the modification had both kept the various excellent properties such as the high strength bonding of former direct addition type cobalt salt adhesive, anti-aging, heat-resisting oxygen, wet-heat resisting, salt water resistance corrosion, simultaneously can apply use again, result of use is obvious, Heat stability is good, dynamic properties is good, price is lower, easy to operate.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention, should understand these embodiment only is used for explanation the present invention and is not used in and limits the scope of the invention, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the modification of the various equivalent form of values of the present invention.
A kind of paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile, comprise composite adhesive and resol and auxiliary agent, composite adhesive is by main tamanori and help tamanori to form, wherein main tamanori comprises cobalt boracylate and new cobalt decanoate, helping tamanori is compound organic salt nickeliferous, vanadium, resol comprises methylene radical donor and methylene receptor, and auxiliary agent comprises toughner, activator, vulcanization leveller, silane coupling agent, vulcanizing agent; Be scattered in the resol carrier composite adhesive and compounding aid, make rubber cement by the mixed solvent dissolving, obtain paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile, its component by mass percentage proportioning is:
(1) composite adhesive: take the composite adhesive quality as 100%, cobalt boracylate 37%～58%, new cobalt decanoate 34%～55% helps tamanori 6%～10%; Wherein to help the tamanori quality as 100%, help that total metal content is 10% ± 0.5% in the tamanori;
(2) mixed solvent: mixed with volume ratio 4:6 with ethyl acetate by dimethylbenzene, the density of mixed solvent is 0.878g/ml;
(3) rubber cement: take the rubber cement quality as 100%, composite adhesive 0.8%～1.6%, methylene radical donor 7.1%～10.7%, methylene receptor 7.1%～10.7%, toughner 1.7%～4.5%, activator 5.7%～10.8%, vulcanization leveller 0.8%～1.8%, silane coupling agent 0.8%～1.8%, vulcanizing agent 0.8%～1.8%, mixed solvent 52%～74%.
Each component raw material of the present invention is all selected industrial raw material.Composite adhesive adopts cobalt boracylate and new cobalt decanoate.Cobalt boracylate adopts is BCo23 type in People's Republic of China's chemical industry standard (HG/T4072-2008), and molecular formula is B(OCoR)
3, cobalt contents is 22.5% ± 0.7%, weight loss on heating≤1.5%, heptane insolubles 8.0% ± 1.0%, Qualitative Identification boracic; The molecular formula of new cobalt decanoate is CoR
2, cobalt contents is 20.5% ± 0.5%, 80 ℃～100 ℃ of softening temperatures; Compound organic salt nickeliferous, vanadium is the composite alkoxide of 2 ethyl hexanoic acid, naphthenic acid, sylvic acid, and the mol ratio of three kinds of acid is 0.50:0.35:0.15, and this compound organic salt molecular formula is 2MeR
23MeR
3, Me is composition metal in the formula, its content is 10% ± 0.5%, and 80 ℃～100 ℃ of softening temperatures, the mass ratio of nickel, vanadium is 4:6, R is the organic acid of three kinds of acid in the formula; Above percentage ratio is mass percent.
The preparation method of the compound organic salt of nickeliferous, vanadium is: use through 120
#The mixed organic acid soda soap extraction composition metal positively charged ion of industrial naptha dilution after the water phase separated, boils off 120
#Industrial naptha obtains the composition metal organic salt of liquid nickeliferous, vanadium, namely obtains compound organic salt nickeliferous, vanadium after the cooling and helps the tamanori product.
The methylene radical donor is that the modification melamine resin adds inert support, and the industry product code name is RA-50, and physical property is white powder; Methylene receptor is the improvement product of Resorcinol, and the industry product code name is RF-90, and physical property is amber sheet or particle.
Toughner, activator, vulcanization leveller, silane coupling agent, vulcanizing agent adopt the conventional auxiliary agent that uses in the rubber item production, for example toughner is selected chlorinated rubber, its molecular formula is C10H11C17, and physical property is white soft powder, density 〉=1.5g/ml; Activator is selected white carbon black; Vulcanization leveller is selected active zinc flower; Silane coupling agent is selected KH-550; Vulcanizing agent is selected common sulphur or insoluble sulfur.
Table 1～table 2 is the constituent mass per distribution ratio of paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile:
Table 1: composite adhesive proportioning table (take the composite adhesive quality as 100%)
Illustrate: the tamanori that helps that this compound cobalt salt adopts is compound organic salt nickeliferous, vanadium, and the composition metal total amount is 10.2%, wherein nickel: vanadium=4:6.
Table 2: tamanori product compositions proportioning table (take the tamanori quality product as 100%)
Illustrate: the used composite adhesive of prescription I is the prescription I in the table 1 in this table, and the used composite adhesive of prescription II is the prescription II in the table 1, and the used composite adhesive of prescription III is the prescription III in the table 1; It is 100kg that the tamanori product once prepares weight.
The best in quality per-cent proportioning of paracril of the present invention and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile component is:
(1) composite adhesive: take the composite adhesive quality as 100%, cobalt boracylate 46%, new cobalt decanoate 46% helps tamanori 8%;
(2) mixed solvent: mixed with volume ratio 4:6 with ethyl acetate by dimethylbenzene, the density of mixed solvent is 0.878g/ml;
(3) rubber cement: take the rubber cement quality as 100%, composite adhesive 1.2%, RA-50 are that 8.6%, RF-90 is 8.6%, chlorinated rubber 2.8%, white carbon black 8.2%, active zinc flower 1.4%, KH-550 is 1.4%, sulphur 1.4%, dimethylbenzene 25.56%, ethyl acetate 39.84% in the mixed solvent.
The preparation method of above-mentioned paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile comprises following concrete steps:
(1) composite adhesive preparation: under 120 ℃ of temperature with the new cobalt decanoate melting, then add cobalt boracylate, and progressively be warming up to 180 ℃ and form molten baths, in the time of 180 ℃, add compound organic salt insulation nickeliferous, vanadium and form the homogeneous liquation, be cooled to room temperature, it is for subsequent use to form solid and broken frustillatum;
(2) material pre-treatment: RF-90 resin and composite adhesive are pulverized by pulverizer, and screening obtains pulverulent material through 200 eye mesh screens; For adapting to the different solvability of each component raw material, dimethylbenzene and ethyl acetate are mixed the formation mixed solvent according to volume ratio 4:6; RF-90 toner, composite adhesive powder, RA-50, chlorinated rubber at room temperature stir predissolve with mixed solvent respectively, and stirring velocity is 40～50 rev/mins; The dissolution time of chlorinated rubber is 24～28 hours, and the dissolution time of RF-90 toner, composite adhesive powder, RA-50 was respectively 6～8 hours; The consumption of the mixed solvent of dissolving chlorinated rubber is 25% of required mixed solvent total amount, and the consumption of the mixed solvent of dissolving RF-90 toner, composite adhesive powder, RA-50 is respectively 10% of required mixed solvent total amount;
(3) rubber cement preparation: the mixed solvent that in the stainless steel reactor that band stirs, adds required mixed solvent total amount 30%, start and stir, progressively add the good composite adhesive solution of predissolve in batches, the RF-90 resin solution, the RA-50 resin solution stirred after 2～3 hours, add active zinc flower, KH-550, sulphur stirred 1～2 hour, add again the good chlorinated rubber solution stirring of predissolve after 5～6 hours, then add white carbon black, and the mixed solvent amount of using according to required mixed solvent total amount and predissolve, the continuation stirring and dissolving obtained rubber cement in 20～24 hours after the difference of the mixed solvent amount that use early stage was supplied mixed solvent, after the sampling detection is qualified, pour colloidal mill into and grind, the rubber cement that leaches by 200 eye mesh screens is finished product.
Table 3: the quality and technical index of paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile finished product
To the theoretical investigation of cobalt salt adhesive, at present prevailing is catalytic theory according to both at home and abroad, can be set forth the adhesion mechanism of paracril of the present invention and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile by catalytic theory.Cobalt salt adhesive is (100 ℃～200 ℃) under heating condition, and cracking discharges the active cobalt ion, under the katalysis of active cobalt ion, and metal and the sulphur generation chemical reactions such as copper, zinc, generation can not with stoichiometric metallic sulfide, generate its Cu such as copper
2S
x, its reaction equation is:
2Cu＋XS＝Cu
2S
x
Cu
2S
xIn the S atom the other end then enter on the net structure node of rubber, namely at metal and rubber intermediate formation " sulphur bridge ", sulphur and metal be combined into ionic linkage, the bond energy of ionic linkage is at 586kJ/mol～1047kJ/mol; The combination of the combination between the sulphur atom and sulphur and rubber is covalent linkage, and the bond energy of covalent linkage is 63kJ/mol～712kJ/mol, and this just makes rubber and metal carry out the high-tenacity bonding by chemical bond fully.Because the existence of a small amount of nickel, vanadium ion, it and cobalt ion form " concerted catalysis ", activity and the catalytic capability of cobalt ion have greatly been improved, strengthened the response capacity of sulphur and metallic surface, enlarge tamanori of the present invention to the subject range of metallic framework, also effectively solved simultaneously the technical barrier that direct addition type cobalt salt adhesive can not effectively bind paracril and mixed rubber thereof and copper, zinc skeleton.
In direct addition type cobalt salt adhesive, cobalt boracylate is the most superior tamanori kind of performance, but its use processing condition are relatively harsher; New cobalt decanoate also has preferably cement properties, and the processing condition of use are relatively looser and stable, and these characteristics have determined that these two kinds are the leading kinds in the at present direct addition type cobalt salt adhesive.Rubber cement of the present invention has adopted cobalt boracylate and new cobalt decanoate to mix by a certain percentage use; both made rubber cement of the present invention keep the excellent properties of direct addition type cobalt salt adhesive; make again the stringent process conditions of the single cobalt boracylate of original use become loose and stable, the different technology conditions of the different rubber item of easier adaptation producer.Simultaneously, because the compound organic salt that has adopted nickeliferous, vanadium is as helping tamanori to make composite adhesive, under cure conditions, by the concerted catalysis of active cobalt ion and nickel, vanadium ion, greatly improved the bonding power of sulphur and copper, zinc surface.Because the bonding of rubber and metal is to finish by the bonding of chemical bond fully, the bond energy of this chemical bond is large, Heat stability is good, this has just determined that rubber cement of the present invention is being far superior to other main rubber---metal-to-metal adhesive that relies on the physics bonding between rubber and metal aspect thermotolerance and the dynamic properties.In direct addition type cobalt salt cracking process, except discharging the active cobalt ion, discharge simultaneously the boron acyl group, the boron acyl group has two sexual functions, can in and the bronsted lowry acids and bases bronsted lowry in the goods, therefore so that goods have preferably wet and heat ageing resistant and salt water resistance aging resistance; Simultaneously, the boron acyl group also has good flame retardant properties.In sum, be exactly the principle place that paracril of the present invention and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile can keep and expand the high strength cement properties of former direct addition type cobalt salt adhesive and anti-aging, heat-resisting oxygen, wet-heat resisting, salt water resistance corrosive property.
For the mixed rubber of paracril and reclaimed rubber or ground rubber, though wherein reclaimed rubber is processed through desulfurization, but still exist partial mesh topology rubber, and ground rubber almost all is reticulated structure rubber.Different from rubber, reclaimed rubber or ground rubber are difficult to form new reticulated structure when sulfuration.From the adhesion mechanism of cobalt salt adhesive as can be known, " sulphur bridge " quantity that forms under this situation can greatly reduce, so that bonding strength reduces.When being carrier with resol, except the concerted catalysis of active cobalt ion and nickel, vanadium ion forms the sulphur bridge sulphur and metal reaction in the rubber cement, resol can also with rubber generation crosslinking reaction, can between sizing material surface and metallic surface, pass through again the physical force such as Van der Waals force, hydrogen bond and form the physics bonding, bonding strength is increased greatly, therefore, alkyd resin based application type modification cobalt salt adhesive is that a kind of existing chemistry binds function, has again physics to bind the novel tamanori kind of function.
With now widely used application type rubber---metal-to-metal adhesive is compared, natural rubber of the present invention and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile have following advantage: (1) is because adopted chemical bonding, binding to compare with traditional physics has similar high strength to bind ability, have simultaneously better ageing-resistant performance, particularly heat-proof aging and salt water resistance corrosive nature; (2) use easy to operate, use at present rubber---metal-to-metal adhesive is divided into primer, face glue usually, need first during use coat primer in the metallic surface, until its solvent evaporates to the greatest extent after, be coated with again top glue, again until solvent evaporates to the greatest extent after, just can carry out hot sulfurization and bind.Rubber cement of the present invention only needs primary coating, after solvent evaporates is most, can carries out hot sulfurization and bind; (3) reduce customer using cost, product price of the present invention is about 60% of similar imported product, adds product coated area of the present invention greater than imported product, 50% of the not enough similar imported product of therefore actual use cost.
The rubber cement of the present invention that makes according to the prescription I of table 1 and table 2, prescription II, prescription III, cement properties and aging resistance that butyronitrile mixed rubber and copper alloy bar skeleton bind are classified as table 4:
| Cement properties (bonding strength N/mm) | The prescription I | The prescription II | The prescription III |
| Before aging | 582 | 590 | 578 |
| After the thermal ageing | 460 | 470 | 440 |
| After the steam aging | 540 | 560 | 540 |
| After moisture is aging | 530 | 540 | 520 |
| After salt solution is aging | 520 | 550 | 540 |
Illustrate: the glue kind component of mixed rubber and quality percentage composition are paracril 65%, reclaimed rubber 35%.
From table 4 listed cement properties and aging resistance data: three assembly Fang Jun have good initial adhesive power and ageing resistance, prove absolutely that tamanori of the present invention has good resistance toheat, thermal stability, has good dynamic properties.
Claims (4)
1. a paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile, it is characterized in that: comprise composite adhesive and resol and auxiliary agent, composite adhesive is by main tamanori and help tamanori to form, wherein main tamanori comprises cobalt boracylate and new cobalt decanoate, helping tamanori is compound organic salt nickeliferous, vanadium, resol comprises methylene radical donor and methylene receptor, and auxiliary agent comprises toughner, activator, vulcanization leveller, silane coupling agent, vulcanizing agent; Be scattered in the resol carrier composite adhesive and compounding aid, make rubber cement by the mixed solvent dissolving, obtain paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile, its component by mass percentage proportioning is:
(1) composite adhesive: take the composite adhesive quality as 100%, cobalt boracylate 37%～58%, new cobalt decanoate 34%～55% helps tamanori 6%～10%; Wherein to help the tamanori quality as 100%, help that total metal content is 10% ± 0.5% in the tamanori;
(2) mixed solvent: mixed with volume ratio 4:6 with ethyl acetate by dimethylbenzene, the density of mixed solvent is 0.878g/mL;
(3) rubber cement: take the rubber cement quality as 100%, composite adhesive 0.8%～1.6%, methylene radical donor 7.1%～10.7%, methylene receptor 7.1%～10.7%, toughner 1.7%～4.5%, activator 5.7%～10.8%, vulcanization leveller 0.8%～1.8%, silane coupling agent 0.8%～1.8%, vulcanizing agent 0.8%～1.8%, mixed solvent 52%～74%;
Wherein: the molecular formula of cobalt boracylate is B(OCoR)
3, cobalt contents is 22.5% ± 0.7%, weight loss on heating≤1.5%, heptane insolubles 8.0% ± 1.0%, Qualitative Identification boracic; The molecular formula of new cobalt decanoate is CoR
2, cobalt contents is 20.5% ± 0.5%, 80 ℃～100 ℃ of softening temperatures; Compound organic salt nickeliferous, vanadium is the composite alkoxide of 2 ethyl hexanoic acid, naphthenic acid, sylvic acid, and the mol ratio of three kinds of acid is 0.50:0.35:0.15, and this compound organic salt molecular formula is 2MeR
23MeR
3, Me is composition metal in the formula, its content is 10% ± 0.5%, and 80 ℃～100 ℃ of softening temperatures, the mass ratio of nickel, vanadium is 4:6, and R is the organic acid of three kinds of acid in the formula, and above percentage ratio is mass percent.
2. paracril according to claim 1 and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile, it is characterized in that: the methylene radical donor is that the modification melamine resin adds inert support, methylene receptor is the improvement product of Resorcinol.
3. paracril according to claim 1 and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile, it is characterized in that: paracril and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile finished product outward appearance are amber thick liquid, being coated with 4 in the time of 20 ℃, to measure glass viscosity be 120min～140min, density is 1.02g/mL ± 0.02g/mL, and the coated area when build is 20 μ m is 10m
2/ kg～12m
2/ kg.
4. the preparation method of paracril according to claim 1 and copper, zinc skeleton cobalt salt adhesive for adhesion of acrylonitrile is characterized in that the concrete steps of the method are as follows:
(1) composite adhesive preparation: under 120 ℃ of temperature with the new cobalt decanoate melting, then add cobalt boracylate, and progressively be warming up to 180 ℃ of formation molten baths, add compound organic salt insulation nickeliferous, vanadium and form the homogeneous liquation, be cooled to room temperature, it is for subsequent use to form solid and broken frustillatum;
(2) material pre-treatment: methylene receptor and composite adhesive are pulverized; Methylene receptor powder, composite adhesive powder, methylene radical donor, toughner at room temperature stir predissolve with mixed solvent respectively, and stirring velocity is 40～50 rev/mins;
(3) rubber cement preparation: the mixed solvent that in container, adds required mixed solvent total amount 30%, start and stir, add the good composite adhesive solution of predissolve, methylene receptor solution, methylene radical donor solution stirring is after 2～3 hours, add vulcanization leveller, silane coupling agent, vulcanizing agent stirred 1～2 hour, add again the good toughner solution stirring of predissolve after 5～6 hours, then add activator, replenish mixed solvent continuation stirring and dissolving and obtained rubber cement in 20～24 hours, after the sampling detection is qualified, pour colloidal mill into and grind, the rubber cement that leaches by 200 eye mesh screens is finished product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010521541 CN102031079B (en) | 2010-10-27 | 2010-10-27 | Cobalt salt adhesive for bonding nitrile rubber and copper/zinc frame and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010521541 CN102031079B (en) | 2010-10-27 | 2010-10-27 | Cobalt salt adhesive for bonding nitrile rubber and copper/zinc frame and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102031079A CN102031079A (en) | 2011-04-27 |
| CN102031079B true CN102031079B (en) | 2013-04-10 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517397A (en) * | 2003-01-16 | 2004-08-04 | 住友橡胶工业株式会社 | Rubber composition and pneumatic-tyre using the rubber composition |
| CN1660948A (en) * | 2004-02-26 | 2005-08-31 | 住友橡胶工业株式会社 | Rubber composition for belt layer steel cord and steel cord coated by the same |
| CN1916100A (en) * | 2006-05-28 | 2007-02-21 | 严忠庆 | Cobalt salt adhesive in use for bonding rubber - metal in high tenacity, and preparation |
| CN101560366A (en) * | 2009-05-27 | 2009-10-21 | 镇江泛华新材料科技发展有限公司 | Coating-type binder used for bounding nitrile butadiene rubber and metal framework and preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517397A (en) * | 2003-01-16 | 2004-08-04 | 住友橡胶工业株式会社 | Rubber composition and pneumatic-tyre using the rubber composition |
| CN1660948A (en) * | 2004-02-26 | 2005-08-31 | 住友橡胶工业株式会社 | Rubber composition for belt layer steel cord and steel cord coated by the same |
| CN1916100A (en) * | 2006-05-28 | 2007-02-21 | 严忠庆 | Cobalt salt adhesive in use for bonding rubber - metal in high tenacity, and preparation |
| CN101560366A (en) * | 2009-05-27 | 2009-10-21 | 镇江泛华新材料科技发展有限公司 | Coating-type binder used for bounding nitrile butadiene rubber and metal framework and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| "橡胶与骨架材料的粘合机理";蒲启君;《橡胶工业》;19991110;第46卷(第11期);第683-695页 * |
| 蒲启君."橡胶与骨架材料的粘合机理".《橡胶工业》.1999,第46卷(第11期),第683-695页. |
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