CN101967359B - Cobalt salt adhesive for adhering natural rubbers and bare-steel frameworks and preparation method thereof - Google Patents
Cobalt salt adhesive for adhering natural rubbers and bare-steel frameworks and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cobalt salt adhesive for adhering natural rubbers and bare-steel frameworks and a preparation method thereof. The adhesive consists of a composite adhesive, phenolic resins and an auxiliary agent, wherein the composite adhesive consists of a main adhesive and an auxiliary adhesive, the main adhesive consists of cobalt boroacylate and cobalt neocaprate, and the auxiliary adhesive is 2-ethylhexoic vanadium; the phenolic resins comprise a methyl donor and a methyl acceptor; the auxiliary agent comprises a toughening agent, an activating agent, a curing activator, a silane coupling agent and a vulcanizing agent; the composite adhesive is dispersed in the vector of the phenolic resin, and is matched with the auxiliary agent; and the mixed solvent is dissolved to prepare adhesive cement so as to obtain the cobalt salt adhesive for adhering natural rubbers and bare-steel frameworks. The cobalt salt adhesive has the advantages of good thermal stability, good dynamic mechanical performance, direct coating application and low cost, and can be used for high-strength adhesion of natural rubbers which contain reclaimed rubbers and reclaimed rubber powder as well as mixed rubbers comprising the natural rubber and universal synthesized rubbers and the bare-steel framework materials.
Description
Technical field
The present invention relates to tamanori and preparation method thereof, comprise natural rubber and the natural rubber that binds with the mixed rubber of general purpose synthetic rubber and naked Steel Skeleton and naked Steel Skeleton cobalt salt adhesive for adhesion of acrylonitrile and preparation method thereof especially for the natural rubber that contains reclaimed rubber or ground rubber.
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, then can't realize binding for naked Steel Skeleton material.
Protect string, bearing, sealing member, crawler belt 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, the normally naked Steel Skeleton of used skeleton, 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, also can adapt to natural rubber binds the high strength of naked Steel Skeleton material, 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 and 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 rubber that is applicable to contain reclaimed rubber or ground rubber and the bonding of naked Steel Skeleton, good, the direct coating use of heat aging property, relative low price, natural rubber easy to use and naked Steel Skeleton cobalt salt adhesive for adhesion of acrylonitrile and preparation method thereof are provided.
Technical scheme: a kind of natural rubber and naked Steel 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 diethyl caproic acid 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 natural rubber and naked Steel 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 40%～60%, new cobalt decanoate 35%～55% helps tamanori diethyl caproic acid vanadium 3%～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%～1.8%, methylene radical donor 9.4%～12%, methylene receptor 7.8%～10%, toughner 2.3%～5%, activator 7.5%～12%, vulcanization leveller 1%～2%, silane coupling agent 1.1%～2%, vulcanizing agent 1.1%～2%, mixed solvent 53%～67.0%.
Each component raw material of the present invention is all selected industrial raw material.It is main tamanori raw material that composite adhesive adopts cobalt boracylate and new cobalt decanoate, with the diethyl hexanoate of vanadium for helping the tamanori raw material.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; The molecular formula of diethyl caproic acid vanadium is VR
3, R is diethyl caproic acid root in the formula, content of vanadium is 9.5% ± 0.5%; 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, more easily adapt to the different technology conditions of different rubber item producer.Adopted simultaneously diethyl caproic acid vanadium as helping tamanori to make composite adhesive, under cure conditions, concerted catalysis by active cobalt ion and vanadium ion, greatly improved the bonding power on sulphur and naked steel 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.
Natural rubber and naked Steel 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 18min～20min, and density is 0.85g/ml ± 0.05g/ml, and the coated area when build is 20 μ m is 12m
2/ kg～16m
2/ kg.
The preparation method of natural rubber and naked Steel 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 ℃ and form molten baths, add again diethyl caproic acid vanadium when being cooled to 150 ℃, melting forms the homogeneous liquation, be cooled to room temperature, form solid and broken frustillatum for subsequent use;
(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 natural rubber and naked Steel 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 the diethyl caproic acid vanadium of concerted catalysis, take resol as carrier, make the natural rubber that contains reclaimed rubber or ground rubber comprise natural rubber and bind with the mixed rubber of general purpose synthetic rubber and naked Steel Skeleton high strength by modification, 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 natural rubber and naked Steel 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 diethyl caproic acid 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 natural rubber and naked Steel 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 40%～60%, new cobalt decanoate 35%～55% helps tamanori diethyl caproic acid vanadium 3%～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%～1.8%, methylene radical donor 9.4%～12%, methylene receptor 7.8%～10%, toughner 2.3%～5%, activator 7.5%～12%, vulcanization leveller 1%～2%, silane coupling agent 1.1%～2%, vulcanizing agent 1.1%～2%, mixed solvent 53%～67.0%.
Each component raw material of the present invention is all selected industrial raw material.It is main tamanori raw material that composite adhesive adopts cobalt boracylate and new cobalt decanoate, with the diethyl hexanoate of vanadium for helping the tamanori raw material.Cobalt boracylate adopts is BCo23 type in People's Republic of China's chemical industry standard (HG/T 4072-2008), 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; The molecular formula of diethyl caproic acid vanadium is VR
3, R is diethyl caproic acid root in the formula, content of vanadium is 9.5% ± 0.5%; Above percentage ratio is mass percent.
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 natural rubber and naked Steel Skeleton cobalt salt adhesive for adhesion of acrylonitrile:
Table 1: composite adhesive proportioning table (take the composite adhesive quality as 100%)
Illustrate: the synthetic weight of composite adhesive is the 100kg meter.
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 natural rubber of the present invention and naked Steel Skeleton cobalt salt adhesive for adhesion of acrylonitrile component is:
(1) composite adhesive: take the composite adhesive quality as 100%, cobalt boracylate 58.4%, new cobalt decanoate 35.8% helps tamanori diethyl caproic acid vanadium 5.8%;
(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 1.5%, RA-50 are that 10.8%, RF-90 is 9%, chlorinated rubber 3.5%, white carbon black 10.5%, active zinc flower 1.5%, KH-550 is 1.5%, sulphur 1.6%, dimethylbenzene 24.04%, ethyl acetate 36.06% in the mixed solvent.
The preparation method of above-mentioned natural rubber and naked Steel 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, in the time of 120 ℃, progressively add cobalt boracylate, and progressively be warming up to 180 ℃ and form molten baths, add again diethyl caproic acid vanadium when being cooled to 150 ℃, melting forms the homogeneous liquation, be cooled to room temperature, form solid and broken frustillatum for subsequent use;
(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 natural rubber and naked Steel Skeleton cobalt salt adhesive for adhesion of acrylonitrile finished product
To the theoretical investigation of cobalt salt adhesive, at present prevailing is catalytic theory, can be set forth the adhesion mechanism of natural rubber of the present invention and naked Steel Skeleton cobalt salt adhesive for adhesion of acrylonitrile by catalytic theory according to both at home and abroad.Under cure conditions (150 ℃～200 ℃), composite adhesive is subjected to thermo-cracking to discharge active cobalt ion and a small amount of active vanadium ion, under the concerted catalysis effect of two kinds of active metallic ions, the metallic surface of naked steel and sulphur generation chemical reaction, generation can not be with stoichiometric metallic sulfide, and its reaction equation is:
Fe＋XS＝FeS
x
FeS
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 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 naked steel metallic surface, enlarge tamanori of the present invention to the subject range of metallic framework, also effectively solved simultaneously direct addition type cobalt salt adhesive to natural rubber and the technical barrier that can not effectively bind with mixed rubber and the naked Steel Skeleton of general purpose synthetic rubber thereof.
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, more easily adapt to the different technology conditions of different rubber item producer.Simultaneously, owing to having adopted diethyl caproic acid vanadium as helping tamanori to make composite adhesive, under cure conditions, by the concerted catalysis of active cobalt ion and vanadium ion, greatly improved the bonding power on sulphur and naked steel 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 natural rubber of the present invention and naked Steel 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 natural rubber that contains a large amount of reclaimed rubbers or ground rubber and with the mixed rubber of general purpose synthetic 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, sulphur in cobalt salt, vanadic salts catalysis rubber cement and metal reaction form the sulphur bridge, 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 naked Steel 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, classify table 4 as to the natural rubber that contains a large amount of reclaimed rubbers or ground rubber and with cement properties and aging resistance that mixed rubber and the naked Steel Skeleton of general purpose synthetic rubber binds:
| Cement properties (bonding strength N/mm) | The prescription I | The prescription II | The prescription III |
| Before aging | 14.8 | 15.5 | 15.1 |
| After the thermal ageing | 13.6 | 14.7 | 14.0 |
| After salt solution is aging | 13.3 | 13.8 | 13.1 |
Illustrate: glue kind component and the quality percentage composition of mixed rubber are: reclaimed rubber 40%, ground rubber 25%, natural rubber 35%.
From table 4 listed cement properties and aging resistance data: three assembly Fang Jun have good initial adhesive power and ageing resistance, the II of wherein filling a prescription the best, prove absolutely that natural rubber of the present invention and naked Steel Skeleton cobalt salt adhesive for adhesion of acrylonitrile have good resistance toheat, thermal stability, have good dynamic properties.
Claims (4)
1. a natural rubber and naked Steel 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 diethyl caproic acid 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 natural rubber and naked Steel 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 40%～60%, new cobalt decanoate 35%～55% helps tamanori diethyl caproic acid vanadium 3%～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%～1.8%, methylene radical donor 9.4%～12%, methylene receptor 7.8%～10%, toughner 2.3%～5%, activator 7.5%～12%, vulcanization leveller 1%～2%, silane coupling agent 1.1%～2%, vulcanizing agent 1.1%～2%, mixed solvent 53%～67.0%;
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; The molecular formula of diethyl caproic acid vanadium is VR
3, R is diethyl caproic acid root in the formula, content of vanadium is 9.5% ± 0.5%; Above percentage ratio is mass percent.
2. natural rubber according to claim 1 and naked Steel 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. natural rubber according to claim 1 and naked Steel Skeleton cobalt salt adhesive for adhesion of acrylonitrile, it is characterized in that: natural rubber and naked Steel 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 18min～20min, density is 0.85g/ml ± 0.05g/ml, and the coated area when build is 20 μ m is 12m
2/ kg～16m
2/ kg.
4. the preparation method of natural rubber according to claim 1 and naked Steel 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 ℃ and form molten baths, add again diethyl caproic acid vanadium when being cooled to 150 ℃, melting forms the homogeneous liquation, be cooled to room temperature, form solid and broken frustillatum for subsequent use;
(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.
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| CN108485513A (en) * | 2018-05-03 | 2018-09-04 | 江苏通用科技股份有限公司 | Load the bead wire skeleton and preparation method thereof of cobalt salt |
| US11597859B2 (en) | 2020-01-24 | 2023-03-07 | Oatey Co. | Solvent cement formulations having extended shelf life |
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|---|---|---|---|---|
| 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 |
| CN101560364A (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 bonding natural rubber and bare steel framework and preparation method |
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| JP5335252B2 (en) * | 2008-02-01 | 2013-11-06 | 東洋ゴム工業株式会社 | Steel cord bonding rubber composition and pneumatic tire |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101560364A (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 bonding natural rubber and bare steel framework and preparation method |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2009-179299A 2009.08.13 |
| 吕百龄等."粘合体系助剂".《实用橡胶手册》.2001,(第1版),第232-235页. |
| 蒲启军."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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| CN101967359A (en) | 2011-02-09 |
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