CN101962522A - Cobalt salt adhesive for adhering ethylen e-propylene-diene mischpolymere and bare steel framework and preparation method thereof - Google Patents
Cobalt salt adhesive for adhering ethylen e-propylene-diene mischpolymere and bare steel framework and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cobalt salt adhesive for adhering ethylen e-propylene-diene mischpolymere and a bare steel framework and a preparation method thereof. The adhesive comprises a compound adhesive, phenolic resin and aids, wherein the compound adhesive consists of a main adhesive and an auxiliary adhesive; the main adhesive comprises cobalt boroacylate and cobalt neocaprate; the auxiliary adhesive is vanadium isooctanoate and cerium isooctanoate; the phenolic resin comprises a methyl donor and a methyl receptor; and the aids comprise a toughening agent, an activator, a curing activator, a silane coupling agent and a curing agent. The preparation method comprises the following steps of: dispersing the compound adhesive in the phenolic resin carrier, and matching with the aids; and adhsdissolving by using a mixed solvent to prepare adhesive cement to obtain the cobalt salt adhesive for adhering the ethylen e-propylene-diene mischpolymere and the bare steel framework. The cobalt salt adhesive has the advantages of high thermal stability, high dynamic mechanical properties, direct coating, low cost, and application to adhering ethylen e-propylene-diene mischpolymere including mixed rubber of the ethylen e-propylene-diene mischpolymere, natural rubber, reclaimed rubber or reclaimed rubber powder and the bare steel framework material.
Description
Technical field
The present invention relates to tamanori and preparation method thereof, comprise mixed rubber and naked Steel Skeleton adherent terpolymer EP rubber and naked Steel Skeleton bonding cobalt salt tamanori and preparation method thereof of terpolymer EP rubber and natural rubber, reclaimed rubber or ground rubber especially for terpolymer EP rubber.
Background technology
At radial wire cord tire; steel wire strengthens travelling belt; the large-scale rubber item industry that 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 adopted direct addition type cobalt salt tamanori usually; directly addition type cobalt salt tamanori comprises cobalt stearate; solid cobaltic naphthenate; new cobalt decanoate; cobalt boracylate etc.; these cobalt salt tamanoris particularly cobalt boracylate except that having high-intensity cement properties; also have anti-aging; heat-resisting oxygen; moisture-proof heat; salt water resistance corrosion and 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 tamanori is direct addition type, can not apply use, and only is 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, 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, adopt the batch production mode usually, 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, promptly pass through electric attraction, physical force such as Van der Waals force realize binding, not having chemical reaction with the metallic surface takes place, 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 adherent goods in use easily come unstuck, and troublesome poeration, cost an arm and a leg.
What occur in recent years is that the application type modification cobalt salt tamanori of carrier is a kind of novel tamanori kind based on the chemistry bonding with rubber, except that having high strength bonding ability, anti-aging, heat-resisting oxygen, moisture-proof heat, the salt water resistance corrosion and the excellent properties such as fire-retardant that have also effectively kept direct addition type cobalt salt tamanori, 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.
Terpolymer EP rubber is owing to have good aging properties, anti-day Hou Xingneng, resistance toheat, electrical insulation capability, resistance to chemical corrosion and good elasticity and incompressible deformability, and therefore particularly inflating valve industry, sealing member industry etc. are widely used in the rubber item industry.But because pure terpolymer EP rubber is all very poor from stickiness and mutual viscosity, pure glue brute force is low, and cost an arm and a leg, the bonding that adds pure terpolymer EP rubber and metallic framework material is particularly extremely difficult with the bonding of naked Steel Skeleton material, therefore normally used in rubber item industries such as inflating valve, bridge cushion blocking, all kinds of sealing members is terpolymer EP rubber and the mixed rubber of natural rubber, styrene-butadiene rubber(SBR), polyisoprene rubber, even but the bonding of this class Ethylene Propylene Terpolymer mixed rubber and naked Steel Skeleton material also is to perplex a rubber circle difficult problem for many years.Particularly many producers are for reducing the manufacturing cost of goods, also use reclaimed rubber or ground rubber in a large number, though reclaimed rubber is handled through desulfurization, but rubber molecular chain not exclusively is a linear structure, ground rubber then is a sulfurized vulcanized rubber, almost completely be reticulated structure, this just makes based on the chemistry bonding, with rubber to be that the bonding ability of the application type modification cobalt salt tamanori of carrier sharply descends, and 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, provide a kind of bonding of terpolymer EP rubber goods, good, the direct coating use of heat aging property, relative low price, terpolymer EP rubber and naked Steel Skeleton easy to use of containing reclaimed rubber or ground rubber of being applicable to bind with cobalt salt tamanori and preparation method.
Technical scheme: a kind of terpolymer EP rubber and naked Steel Skeleton bind uses the cobalt salt tamanori, 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 and diethyl caproic acid cerium, resol comprises methyl donor and methyl 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 the bonding of terpolymer EP rubber and naked Steel Skeleton and use the cobalt salt tamanori, its component proportioning by mass percentage is:
(1) composite adhesive: in the composite adhesive quality is 100%, cobalt boracylate 40%～60%, and new cobalt decanoate 35%～55% helps tamanori 5%～10%; Be 100% wherein to help the tamanori quality, diethyl caproic acid vanadium 70%, diethyl caproic acid cerium 30%;
(2) mixed solvent: mixed at 4: 6 with volume ratio with ethyl acetate by dimethylbenzene, the density of mixed solvent is 0.878mg/ml;
(3) rubber cement: in the rubber cement quality is 100%, composite adhesive 1%～2%, methyl donor 8.5%～12.8%, methyl receptor 7.1%～10.7%, toughner 1.7%～4.5%, activator 5.7%～10.8%, vulcanization leveller 0.8%～1.8%, silane coupling agent 1%～2%, vulcanizing agent 0.8%～1.8%, mixed solvent 60%～72%.
Each component raw material of the present invention is all selected industrial raw material for use.It is main tamanori raw material that composite adhesive adopts cobalt boracylate and new cobalt decanoate, with the diethyl hexanoate of vanadium, cerium 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 evaluation 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 a diethyl caproic acid root in the formula, content of vanadium is 9.5% ± 0.5%; The molecular formula of diethyl caproic acid cerium is CeR
3, R is a diethyl caproic acid root in the formula, cerium content is 8.0% ± 0.5%; Above percentage ratio is mass percent.Cobalt boracylate as leading kind in the direct addition type cobalt salt tamanori; performance is the most superior but the use processing condition are relatively harsher; new cobalt decanoate has preferably cement properties and uses processing condition 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 tamanori; make the stringent process conditions of the single cobalt boracylate of original use become loose and stable again, the different technology conditions of the different rubber item of easier adaptation producer.Adopted diethyl caproic acid vanadium and diethyl caproic acid cerium as helping tamanori to make composite adhesive simultaneously, under cure conditions, concerted catalysis by active cobalt ion and vanadium, cerium ion, improved the bonding power on sulphur and naked steel surface greatly, 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 big, Heat stability is good, thereby this tamanori is being far superior to other main physics adherent rubber---metal-to-metal adhesive that relies between rubber and metal aspect thermotolerance and the dynamic properties.
The methyl donor adds inert support for the modification melamine resin, and the methyl receptor is the improvement product of Resorcinol.
It is amber thick liquid that terpolymer EP rubber and naked Steel Skeleton bind with cobalt salt tamanori finished product outward appearance, being coated with-4 in the time of 20 ℃, to measure glass viscosity be 160min～180min, density is 1.05mg/ml ± 0.05mg/ml, and the coated area when build is 20 μ m is 8m
2/ kg～10m
2/ kg.
Terpolymer EP rubber and naked Steel Skeleton bind the preparation method with the cobalt salt tamanori, and the concrete steps of this method are as follows:
(1) composite adhesive preparation: under 120 ℃ of temperature with the new cobalt decanoate fusion, add cobalt boracylate then, and progressively be warming up to 180 ℃ and form molten baths, add diethyl caproic acid vanadium and diethyl caproic acid cerium when being cooled to 150 ℃ again, fusion forms the homogeneous liquation, be cooled to room temperature, it is standby to form solid and broken frustillatum;
(2) material pre-treatment: methyl receptor and composite adhesive are pulverized; Methyl receptor powder, composite adhesive powder, methyl 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, methyl receptor solution, methyl donor solution stirring is after 2～3 hours, add vulcanization leveller, silane coupling agent, vulcanizing agent stirred 1～2 hour, add the good toughner solution stirring of predissolve again after 5～6 hours, add activator then, 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.
With resol is carrier, and composite adhesive and auxiliary agent are dispersed in the resol carrier soln, is prepared into the rubber cement shape tamanori that can apply use, thereby realizes the modification purpose, and tamanori is become application type by original direct addition type.
Beneficial effect: advantage of the present invention is that terpolymer EP rubber and naked Steel Skeleton bind that to have adopted the two kinds of direct addition type cobalt salt of high level tamanori raw materials can having complementary advantages with cobalt salt tamanori component be basic, as to have increased energy and active cobalt ion formation concerted catalysis diethyl caproic acid vanadium and diethyl caproic acid cerium, are carrier with resol, make terpolymer EP rubber comprise that the mixed rubber of terpolymer EP rubber and natural rubber, reclaimed rubber or ground rubber and naked Steel Skeleton high strength bind by modification, satisfied the needs of rubber item processing.Tamanori after the modification had both kept various excellent properties such as the high strength bonding of former direct addition type cobalt salt tamanori, anti-aging, heat-resisting oxygen, moisture-proof heat, salt water resistance corrosion, simultaneously can apply use again, result of use obviously, 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 to the present invention is described and is not used in and limit the scope of the invention, after having read the present invention, those skilled in the art all fall within the application's claims institute restricted portion to the modification of the various equivalent form of values of the present invention.
A kind of terpolymer EP rubber and naked Steel Skeleton bind uses the cobalt salt tamanori, 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 and diethyl caproic acid cerium, resol comprises methyl donor and methyl 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 the bonding of terpolymer EP rubber and naked Steel Skeleton and use the cobalt salt tamanori, its component proportioning by mass percentage is:
(1) composite adhesive: in the composite adhesive quality is 100%, cobalt boracylate 40%～60%, and new cobalt decanoate 35%～55% helps tamanori 5%～10%; Be 100% wherein to help the tamanori quality, diethyl caproic acid vanadium 70%, diethyl caproic acid cerium 30%;
(2) mixed solvent: mixed at 4: 6 with volume ratio with ethyl acetate by dimethylbenzene, the density of mixed solvent is 0.878mg/ml;
(3) rubber cement: in the rubber cement quality is 100%, composite adhesive 1%～2%, methyl donor 8.5%～12.8%, methyl receptor 7.1%～10.7%, toughner 1.7%～4.5%, activator 5.7%～10.8%, vulcanization leveller 0.8%～1.8%, silane coupling agent 1%～2%, vulcanizing agent 0.8%～1.8%, mixed solvent 60%～72%.
Each component raw material of the present invention is all selected industrial raw material for use.It is main tamanori raw material that composite adhesive adopts cobalt boracylate and new cobalt decanoate, with the diethyl hexanoate of vanadium, cerium 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 evaluation 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 a diethyl caproic acid root in the formula, content of vanadium is 9.5% ± 0.5%; The molecular formula of diethyl caproic acid cerium is CeR
3, R is a diethyl caproic acid root in the formula, cerium content is 8.0% ± 0.5%; Above percentage ratio is mass percent.
The methyl donor adds inert support for the modification melamine resin, and the industry product code name is RA-50, and physical property is a white powder; The methyl 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 for use, its molecular formula is C10H11C17, and physical property is white soft powder, density 〉=1.5g/ml; Activator is selected white carbon black for use; Vulcanization leveller is selected active zinc flower for use; Silane coupling agent is selected KH-550 for use; Vulcanizing agent is selected common sulphur or insoluble sulfur for use.
Table 1～table 2 is that terpolymer EP rubber and naked Steel Skeleton bind the constituent mass per distribution ratio with the cobalt salt tamanori:
Table 1: composite adhesive proportioning table (is 100% in the composite adhesive quality)
Illustrate: the synthetic weight of composite adhesive is the 100kg meter.
Table 2: tamanori product compositions proportioning table (is 100% in the tamanori quality product)
Illustrate: the used composite adhesive of formula I is the formula I in the table 1 in this table, and the used composite adhesive of formula I I is the formula I I in the table 1, and the used composite adhesive of formula I II is the formula I II in the table 1; It is 100kg that the tamanori product once prepares weight.
The best in quality per-cent proportioning that terpolymer EP rubber of the present invention and naked Steel Skeleton bind with cobalt salt tamanori component is:
(1) composite adhesive: in the composite adhesive quality is 100%, main tamanori 92%, and wherein cobalt boracylate 50%, and new cobalt decanoate 42% helps tamanori 8%.
(2) mixed solvent: mixed at 4: 6 with volume ratio with ethyl acetate by dimethylbenzene, the density of mixed solvent is 0.878mg/ml;
(3) rubber cement: in the rubber cement quality is 100%, and composite adhesive 1.5%, RA-50 are 10.5%, and RF-90 is 9%, chlorinated rubber 3%, white carbon black 8%, active zinc flower 1.4%, KH-550 is 1.4%, sulphur 1.3%, dimethylbenzene 25.56%, ethyl acetate 38.34% in the mixed solvent.
Above-mentioned terpolymer EP rubber and naked Steel Skeleton bind the preparation method with the cobalt salt tamanori, comprise following concrete steps:
(1) composite adhesive preparation: under 120 ℃ of temperature with the new cobalt decanoate fusion, in the time of 120 ℃, progressively add cobalt boracylate, and progressively be warming up to 180 ℃ and form molten baths, add diethyl caproic acid vanadium and diethyl caproic acid cerium when being cooled to 150 ℃ again, fusion forms the homogeneous liquation, be cooled to room temperature, it is standby 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 at 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 a 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 the good chlorinated rubber solution stirring of predissolve again after 5～6 hours, add white carbon black then, 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: terpolymer EP rubber and naked Steel Skeleton bind the quality and technical index with cobalt salt tamanori finished product
To the theoretical investigation of cobalt salt tamanori, at present prevailing is catalytic theory according to both at home and abroad, can be set forth the adhesion mechanism of terpolymer EP rubber of the present invention and naked Steel Skeleton bonding usefulness cobalt salt tamanori by catalytic theory.Under cure conditions (100 ℃～200 ℃), composite adhesive is subjected to thermo-cracking to discharge active cobalt ion and a small amount of active vanadium, cerium ion, under the concerted catalysis effect of three 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, just 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 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, cerium ion, it and cobalt ion form " concerted catalysis ", the activity and the catalytic capability of cobalt ion have been improved greatly, strengthened the response capacity of sulphur and naked steel metallic surface, enlarged the subject range of tamanori of the present invention, also solved simultaneously direct addition type cobalt salt tamanori effectively the effective adherent technical barrier of terpolymer EP rubber and mixed rubber thereof and naked Steel Skeleton to metallic framework.
In direct addition type cobalt salt tamanori, cobalt boracylate is the most superior tamanori kind of performance, but its use processing condition are relatively harsher; New cobalt decanoate also has cement properties preferably, and the processing condition of use are 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 tamanori.Rubber cement of the present invention has adopted cobalt boracylate and new cobalt decanoate to mix use by a certain percentage; both made rubber cement of the present invention keep the excellent properties of direct addition type cobalt salt tamanori; make the stringent process conditions of the single cobalt boracylate of original use become loose and stable again, the different technology conditions of the different rubber item of easier adaptation producer.Simultaneously, owing to adopted diethyl caproic acid vanadium and diethyl caproic acid cerium as helping tamanori to make composite adhesive, under cure conditions, the concerted catalysis by active cobalt ion and vanadium, cerium ion has improved the bonding power on sulphur and naked steel surface greatly.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 big, Heat stability is good, this has just determined rubber cement of the present invention being far superior to other main physics adherent rubber---metal-to-metal adhesive that relies between rubber and metal aspect thermotolerance and the dynamic properties.In direct addition type cobalt salt cracking process, except that discharging the active cobalt ion, discharge the boron acyl group simultaneously, the boron acyl group has two sexual functions, can in and the bronsted lowry acids and bases bronsted lowry in the goods, therefore, make goods that wet and heat ageing resistant and salt water resistance aging resistance preferably be arranged; Simultaneously, the boron acyl group also has good flame retardancy.In sum, be exactly that terpolymer EP rubber of the present invention and naked Steel Skeleton bind the principle place that can keep and expand the high strength cement properties of former direct addition type cobalt salt tamanori and anti-aging, heat-resisting oxygen, moisture-proof heat, salt water resistance corrosive property with the cobalt salt tamanori.
For the mixed rubber of terpolymer EP rubber and natural rubber, reclaimed rubber or ground rubber, though wherein reclaimed rubber is handled through desulfurization, but still exist partial mesh topology rubber, and ground rubber almost all is a reticulated structure rubber.Different with rubber, reclaimed rubber or ground rubber are difficult to form new reticulated structure when sulfuration.From the adhesion mechanism of cobalt salt tamanori as can be known, " sulphur bridge " quantity that forms under this situation can significantly reduce, and makes bonding strength reduce.When being carrier with resol, sulphur in cobalt salt, vanadic salts and cerium salt 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 physical force such as Van der Waals force, hydrogen bond again and form the physics bonding, bonding strength is increased greatly, therefore, alkyd resin based application type modification cobalt salt tamanori is that a kind of existing chemistry binds function, has physics to bind the novel tamanori kind of function again.
With present widely used application type rubber---metal-to-metal adhesive is compared, terpolymer EP rubber of the present invention and naked Steel Skeleton bind and have following advantage with the cobalt salt tamanori: (1) is because adopted chemical bonding, binding to compare with traditional physics has similar high strength to bind ability, have better ageing-resistant performance, particularly heat-proof aging and salt water resistance corrosive nature simultaneously; (2) use easy to operate, use at present rubber---metal-to-metal adhesive is divided into primer, face glue usually, need earlier during use coat primer in the metallic surface, treat that its solvent evaporates to the greatest extent after, be coated with top glue again, treat that again 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, treat that solvent evaporates to the greatest extent after, can carry out hot sulfurization and bind; (3) reduce customer using cost, product price of the present invention is about 60% of a 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 formula I, formula I I, the formula I II of table 1 and table 2, to the Ethylene Propylene Terpolymer mixed rubber and naked Steel Skeleton carries out the adherent cement properties and aging resistance is classified table 4 as:
| Cement properties (bonding strength N/mm) | Formula I | Formula I I | Formula I II |
| 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: the glue kind component of mixed rubber and quality percentage composition are terpolymer EP rubber 25%, natural rubber 35%, reclaimed rubber 40%.
From table 4 listed cement properties and aging resistance data: three assembly Fang Jun have good initial adhesive power and ageing resistance, formula I I the best wherein, prove absolutely that tamanori of the present invention has good heat-resistant, thermal stability, has good dynamic properties.
Terpolymer EP rubber of the present invention and naked Steel Skeleton bind the rubber item industries such as obturator, bridge cushion blocking, harbour snubber, inflating valve that can be widely used in making hot material conveyor belt, rubber steam hose, resistance to chemical attack with the cobalt salt tamanori.
Claims (5)
1. a terpolymer EP rubber and naked Steel Skeleton bind and use the cobalt salt tamanori, 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 and diethyl caproic acid cerium, resol comprises methyl donor and methyl 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 the bonding of terpolymer EP rubber and naked Steel Skeleton and use the cobalt salt tamanori, its component proportioning by mass percentage is:
(1) composite adhesive: in the composite adhesive quality is 100%, cobalt boracylate 40%～60%, and new cobalt decanoate 35%～55% helps tamanori 5%～10%; Be 100% wherein to help the tamanori quality, diethyl caproic acid vanadium 70%, diethyl caproic acid cerium 30%;
(2) mixed solvent: mixed at 4: 6 with volume ratio with ethyl acetate by dimethylbenzene, the density of mixed solvent is 0.878mg/ml;
(3) rubber cement: in the rubber cement quality is 100%, composite adhesive 1%～2%, methyl donor 8.5%～12.8%, methyl receptor 7.1%～10.7%, toughner 1.7%～4.5%, activator 5.7%～10.8%, vulcanization leveller 0.8%～1.8%, silane coupling agent 1%～2%, vulcanizing agent 0.8%～1.8%, mixed solvent 60%～72%.
2. terpolymer EP rubber according to claim 1 and naked Steel Skeleton bind uses the cobalt salt tamanori, and it is characterized in that: 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 evaluation 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 a diethyl caproic acid root in the formula, content of vanadium is 9.5% ± 0.5%; The molecular formula of diethyl caproic acid cerium is CeR
3, R is a diethyl caproic acid root in the formula, cerium content is 8.0% ± 0.5%; Above percentage ratio is mass percent.
3. terpolymer EP rubber according to claim 1 and naked Steel Skeleton bind uses the cobalt salt tamanori, and it is characterized in that: the methyl donor adds inert support for the modification melamine resin, and the methyl receptor is the improvement product of Resorcinol.
4. terpolymer EP rubber according to claim 1 and naked Steel Skeleton bind uses the cobalt salt tamanori, it is characterized in that: it is amber thick liquid that terpolymer EP rubber and naked Steel Skeleton bind with cobalt salt tamanori finished product outward appearance, being coated with-4 in the time of 20 ℃, to measure glass viscosity be 160min～180min, density is 1.05mg/ml ± 0.05mg/ml, and the coated area when build is 20 μ m is 8m
2/ kg～10m
2/ kg.
5. terpolymer EP rubber according to claim 1 and naked Steel Skeleton bind the preparation method with the cobalt salt tamanori, it is characterized in that the concrete steps of this method are as follows:
(1) composite adhesive preparation: under 120 ℃ of temperature with the new cobalt decanoate fusion, add cobalt boracylate then, and progressively be warming up to 180 ℃ and form molten baths, add diethyl caproic acid vanadium and diethyl caproic acid cerium when being cooled to 150 ℃ again, fusion forms the homogeneous liquation, be cooled to room temperature, it is standby to form solid and broken frustillatum;
(2) material pre-treatment: methyl receptor and composite adhesive are pulverized; Methyl receptor powder, composite adhesive powder, methyl 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, methyl receptor solution, methyl donor solution stirring is after 2～3 hours, add vulcanization leveller, silane coupling agent, vulcanizing agent stirred 1～2 hour, add the good toughner solution stirring of predissolve again after 5～6 hours, add activator then, 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105214117A CN101962522A (en) | 2010-10-27 | 2010-10-27 | Cobalt salt adhesive for adhering ethylen e-propylene-diene mischpolymere and bare steel framework and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105214117A CN101962522A (en) | 2010-10-27 | 2010-10-27 | Cobalt salt adhesive for adhering ethylen e-propylene-diene mischpolymere and bare steel framework and preparation method thereof |
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| CN101962522A true CN101962522A (en) | 2011-02-02 |
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| CN (1) | CN101962522A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352208A (en) * | 2011-11-07 | 2012-02-15 | 镇江泛华新材料科技发展有限公司 | Cobalt salt adhesive for bonding ethylene propylene diene monomer rubber with bare steel skeleton and preparation method thereof |
| CN109609054A (en) * | 2018-11-28 | 2019-04-12 | 江苏麒祥高新材料有限公司 | No cobalt composition metal caprate adhesion promoter and preparation method thereof, application |
| US11597859B2 (en) | 2020-01-24 | 2023-03-07 | Oatey Co. | Solvent cement formulations having extended shelf life |
| CN117264598A (en) * | 2023-09-20 | 2023-12-22 | 江阴市三良橡塑新材料有限公司 | Cobalt salt composite adhesive and preparation method thereof |
-
2010
- 2010-10-27 CN CN2010105214117A patent/CN101962522A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352208A (en) * | 2011-11-07 | 2012-02-15 | 镇江泛华新材料科技发展有限公司 | Cobalt salt adhesive for bonding ethylene propylene diene monomer rubber with bare steel skeleton and preparation method thereof |
| CN109609054A (en) * | 2018-11-28 | 2019-04-12 | 江苏麒祥高新材料有限公司 | No cobalt composition metal caprate adhesion promoter and preparation method thereof, application |
| US11597859B2 (en) | 2020-01-24 | 2023-03-07 | Oatey Co. | Solvent cement formulations having extended shelf life |
| US11976222B2 (en) | 2020-01-24 | 2024-05-07 | Oatey Co. | Solvent cement formulations having extended shelf life |
| CN117264598A (en) * | 2023-09-20 | 2023-12-22 | 江阴市三良橡塑新材料有限公司 | Cobalt salt composite adhesive and preparation method thereof |
| CN117264598B (en) * | 2023-09-20 | 2024-04-19 | 江阴市三良橡塑新材料有限公司 | Cobalt salt composite adhesive and preparation method thereof |
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Application publication date: 20110202 |