CN102352207A - Cobalt salt adhesive for bonding ethylene propylene diene monomer rubber with copper or zinc framework and preparation method thereof - Google Patents
Cobalt salt adhesive for bonding ethylene propylene diene monomer rubber with copper or zinc framework and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cobalt salt adhesive for bonding ethylene propylene diene monomer rubber with a copper or zinc framework and a preparation method thereof. The adhesive is prepared from a composite adhesive, phenol formaldehyde resin and assistants, wherein the composite adhesive is prepared from a primary adhesive and an auxiliary adhesive; the primary adhesive comprises cobalt boroacylate and cobalt neodecanoate, and the auxiliary adhesive is cerium 2-ethylhexanoate; the phenol formaldehyde resin comprises a methyl donor and a methyl acceptor; and the assistants comprise a toughener, an activating agent, a vulcanization activator, a silane coupling agent and a vulcanizing agent. The preparation method comprises the following steps: dispersing the composite adhesive in the phenol formaldehyde resin carrier, and dissolving the mixture in a mixed solvent in cooperation with the assistants to prepare an adhesive cement, thereby obtaining the cobalt salt adhesive for bonding ethylene propylene diene monomer rubber with a copper or zinc framework. The cobalt salt adhesive has the advantages of high thermal stability, favorable dynamic mechanical properties and low cost, can be directly coated, and is applicable to high-strength bonding of ethylene propylene diene monomer rubber, including mixed rubber of ethylene propylene diene monomer rubber and natural rubber, regenerated rubber or regenerated rubber powder, with a copper, zinc, copper alloy, zinc alloy, zinc-plated or brass-plated framework.
Description
Technical field
The present invention relates to tamanori and preparation method, comprise that especially for terpolymer EP rubber mixed rubber and copper, zinc, copper alloy, the zinc alloy of terpolymer EP rubber and tree elastomer, reclaimed rubber or ground rubber, zinc-plated, brass-plating skeleton adherent terpolymer EP rubber and copper, zinc skeleton bind with cobalt salt tamanori and preparation method.
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, 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, 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 type 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 type tamanori; Dynamic properties is poor; From using the result to see; The adherent goods in use are prone to come unstuck, and troublesome poeration; Cost an arm and a leg.
Occur in recent years with rubber be the application type modification cobalt salt tamanori of carrier be a kind of be master's novel tamanori kind with the chemistry bonding; Except that having high strength bonding ability; Excellent properties such as anti-aging, heat-resisting oxygen, the moisture-proof that has also effectively kept direct addition type cobalt salt tamanori is warm, salt water resistance corrodes and fire-retardant; And can apply use; Adaptation to framework material is wide; Low price, safety and environmental protection are one type of very promising novel application type rubber---metal-to-metal adhesive kinds.
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, therefore the rubber item industry particularly the inflating valve industry be widely used.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 extremely difficult; 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 tree elastomer, styrene-butadiene rubber(SBR), polyisoprene rubber, even but the bonding of this type Ethylene Propylene Terpolymer mixed rubber and metallic framework 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 and is the master, is that the bonding ability of the application type modification cobalt salt tamanori of carrier sharply descends with rubber with the chemistry bonding, can not adapt to the needs of this type 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 terpolymer EP rubber and copper, the bonding of zinc skeleton, good, the direct coating use of heat aging property, relative low price, terpolymer EP rubber and copper, zinc 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 copper, zinc 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 the 2 ethyl hexanoic acid cerium; Resol comprises methyl donor and methyl receptor, and auxiliary agent comprises toughner, activator, vulcanization leveller, silane coupling agent, vulcanizing agent; Composite adhesive is scattered in the resol carrier and compounding aid, processes rubber cement by the mixed solvent dissolving, obtain terpolymer EP rubber and copper, the cobalt salt tamanori is used in the bonding of zinc skeleton, its component proportioning by mass percentage is:
(1) composite adhesive: in the composite adhesive quality is 100%, cobalt boracylate 50%～60%, new cobalt decanoate 35%～45%, 2 ethyl hexanoic acid cerium 4%～8%;
(2) mixed solvent: mixed with volume ratio 4:6 with ethyl acetate by xylenes, the density of mixed solvent is 0.878mg/ml;
(3) rubber cement: in the rubber cement quality is 100%; Composite adhesive 0.8%～1.6%; Methyl donor 7.1%～10.7%; 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 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 for use.It is main tamanori raw material that composite adhesive adopts cobalt boracylate and new cobalt decanoate, with the 2-ethylhexoate of 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 2 ethyl hexanoic acid cerium is CeR
3, R is the 2 ethyl hexanoic 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, more easily the different technology conditions of the different rubber item of adaptation producer.Adopted the 2 ethyl hexanoic acid cerium as helping tamanori to process composite adhesive simultaneously; Under cure conditions; Concerted catalysis through active cobalt ion and cerium ion; Improved the bonding power of sulphur and copper, zinc surface greatly; And the bonding of rubber and metal is to accomplish through 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 property product of Resorcinol.
It is amber thick liquid that terpolymer EP rubber and copper, zinc skeleton bind use cobalt salt tamanori finished product outward appearance; In the time of 20 ℃, being coated with-4, 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 copper, zinc skeleton bind the preparation method with the cobalt salt tamanori, and the concrete steps of this method are following:
(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 the 2 ethyl hexanoic acid cerium when being cooled to 150 ℃ again; Fusion forms the homogeneous liquation; Be cooled to room temperature, it is subsequent use 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 through 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 terpolymer EP rubber and copper; The two kinds of direct addition type cobalt salt of high level tamanori raw materials that the bonding of zinc skeleton is used cobalt salt tamanori component to adopt and can be had complementary advantages are the basis; Increased the 2 ethyl hexanoic acid cerium that ability and active cobalt ion form concerted catalysis; With resol is carrier; Make terpolymer EP rubber comprise terpolymer EP rubber and tree elastomer through modification; The mixed rubber of reclaimed rubber or ground rubber and copper; Zinc; Copper alloy; Zinc alloy; Zinc-plated; Brass-plating skeleton high strength is binded, and has 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 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 be used to the present invention is described and be not used in the restriction scope of the present invention; After having read the present invention, those skilled in the art all fall within the application's accompanying 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 copper, zinc 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 the 2 ethyl hexanoic acid cerium; Resol comprises methyl donor and methyl receptor, and auxiliary agent comprises toughner, activator, vulcanization leveller, silane coupling agent, vulcanizing agent; Composite adhesive is scattered in the resol carrier and compounding aid, processes rubber cement by the mixed solvent dissolving, obtain terpolymer EP rubber and copper, the cobalt salt tamanori is used in the bonding of zinc skeleton, its component proportioning by mass percentage is:
(1) composite adhesive: in the composite adhesive quality is 100%, cobalt boracylate 50%～60%, new cobalt decanoate 35%～45%, 2 ethyl hexanoic acid cerium 4%～8%;
(2) mixed solvent: mixed with volume ratio 4:6 with ethyl acetate by xylenes, the density of mixed solvent is 0.878mg/ml;
(3) rubber cement: in the rubber cement quality is 100%; Composite adhesive 0.8%～1.6%; Methyl donor 7.1%～10.7%; 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 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 for use.It is main tamanori raw material that composite adhesive adopts cobalt boracylate and new cobalt decanoate, with the 2-ethylhexoate of cerium for helping the tamanori raw material.What cobalt boracylate adopted is the 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 2 ethyl hexanoic acid cerium is CeR
3, R is the 2 ethyl hexanoic 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 property 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 copper, zinc 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 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.
Terpolymer EP rubber of the present invention and copper, zinc skeleton bind and use the best in quality per-cent proportioning of cobalt salt tamanori component to be:
(1) composite adhesive: in the composite adhesive quality is 100%, cobalt boracylate 55%, new cobalt decanoate 39%, 2 ethyl hexanoic acid cerium 6%;
(2) mixed solvent: mixed with volume ratio 4:6 with ethyl acetate by xylenes, the density of mixed solvent is 0.878mg/ml;
(3) rubber cement: in the rubber cement quality is 100%, and composite adhesive 1.2%, RA-50 are 8.6%, and 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%, xylenes 25.56%, ethyl acetate 39.84% in the mixed solvent.
Above-mentioned terpolymer EP rubber and copper, zinc 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 the 2 ethyl hexanoic acid cerium when being cooled to 150 ℃ again; Fusion forms the homogeneous liquation; Be cooled to room temperature, it is subsequent use to form solid and broken frustillatum;
(2) material pre-treatment: RF-90 resin and composite adhesive are pulverized through pulverizer, and screening obtains pulverulent material through 200 eye mesh screens; For adapting to the different solvability of each component raw material, xylenes 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 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 difference of the mixed solvent amount that use early stage is supplied mixed solvent continued stirring and dissolving and was obtained rubber cement in 20～24 hours; After the sampling detection is qualified; Pour colloidal mill into and grind, the rubber cement that leaches through 200 eye mesh screens is finished product.
Table 3: terpolymer EP rubber and copper, zinc 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 set forth terpolymer EP rubber of the present invention and copper, the bonding of the zinc skeleton adhesion mechanism with the 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 cerium ion; Under the concerted catalysis effect of two kinds of active metallic ions; Metal such as copper, zinc and sulphur generation chemical reaction; Generation can not generate its Cu like copper with stoichiometric metallic sulfide
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, 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 through chemical bond fully.Because the existence of a small amount of 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 copper, zinc 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 copper, zinc skeleton to copper, zinc skeleton.
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, more easily the different technology conditions of the different rubber item of adaptation producer.Simultaneously, owing to adopted the 2 ethyl hexanoic acid cerium, under cure conditions,, improved the bonding power of sulphur and copper, zinc surface greatly through the concerted catalysis of active cobalt ion and cerium ion as helping tamanori to process composite adhesive.Because the bonding of rubber and metal is to accomplish through 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 goods in bronsted lowry acids and bases bronsted lowry, therefore, make goods that wet and heat ageing resistant and salt water resistance aging resistance preferably arranged; Simultaneously, the boron acyl group also has good flame retardancy.In sum, be exactly that terpolymer EP rubber of the present invention and copper, the bonding of zinc skeleton belong to high strength cement properties and anti-aging, heat-resisting oxygen, the moisture-proof principle hot, the salt water resistance corrosive property that the cobalt salt tamanori can keep and expand former direct addition type cobalt salt tamanori.
For the mixed rubber of terpolymer EP rubber and tree elastomer, 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.Can know that from the adhesion mechanism of cobalt salt tamanori " sulphur bridge " quantity that forms under this situation can significantly reduce, make bonding strength reduce.When using resol as carrier; Sulphur in cobalt salt, 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 copper, zinc 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 the prescription I of table 1 and table 2, prescription II, prescription III, to the Ethylene Propylene Terpolymer mixed rubber and the copper alloy bar skeleton carries out the adherent cement properties and aging resistance is classified table 4 as:
Illustrate: the glue kind component of mixed rubber and quality percentage composition are terpolymer EP rubber 25%, tree elastomer 35%, reclaimed rubber 40%.
See from cement properties and aging resistance data that table 4 is listed: three assembly Fang Jun have good initial adhesive power and ageing resistance, prove absolutely that tamanori of the present invention has good heat-resistant, thermal stability, has good dynamic properties.
Claims (5)
1. terpolymer EP rubber and copper, zinc 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 the 2 ethyl hexanoic acid cerium; Resol comprises methyl donor and methyl receptor, and auxiliary agent comprises toughner, activator, vulcanization leveller, silane coupling agent, vulcanizing agent; Composite adhesive is scattered in the resol carrier and compounding aid, processes rubber cement by the mixed solvent dissolving, obtain terpolymer EP rubber and copper, the cobalt salt tamanori is used in the bonding of zinc skeleton, its component proportioning by mass percentage is:
(1) composite adhesive: in the composite adhesive quality is 100%, cobalt boracylate 50%～60%, new cobalt decanoate 35%～45%, 2 ethyl hexanoic acid cerium 4%～8%;
(2) mixed solvent: mixed with volume ratio 4:6 with ethyl acetate by xylenes, the density of mixed solvent is 0.878mg/ml;
(3) rubber cement: in the rubber cement quality is 100%; Composite adhesive 0.8%～1.6%; Methyl donor 7.1%～10.7%; 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 0.8%～1.8%, vulcanizing agent 0.8%～1.8%, mixed solvent 52%～74%.
2. terpolymer EP rubber according to claim 1 and copper, zinc 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 2 ethyl hexanoic acid cerium is CeR
3, R is the 2 ethyl hexanoic 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 copper, zinc 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 property product of Resorcinol.
4. terpolymer EP rubber according to claim 1 and copper, zinc skeleton bind uses the cobalt salt tamanori; It is characterized in that: it is amber thick liquid that terpolymer EP rubber and copper, zinc skeleton bind use cobalt salt tamanori finished product outward appearance; In the time of 20 ℃, being coated with-4, 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 copper, zinc skeleton bind the preparation method with the cobalt salt tamanori, it is characterized in that the concrete steps of this method are following:
(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 the 2 ethyl hexanoic acid cerium when being cooled to 150 ℃ again; Fusion forms the homogeneous liquation; Be cooled to room temperature, it is subsequent use 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 through 200 eye mesh screens is finished product.
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| CN101967360A (en) * | 2010-10-27 | 2011-02-09 | 镇江泛华新材料科技发展有限公司 | Cobalt salt bonding agent for bonding ethylene propylene diene monomer with copper or zinc framework and preparation method thereof |
| CN101985545A (en) * | 2010-10-27 | 2011-03-16 | 镇江泛华新材料科技发展有限公司 | Cobalt salt bonding agent for bonding nitrile butadiene rubber with bare steel framework and preparation method thereof |
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| CN101967360A (en) * | 2010-10-27 | 2011-02-09 | 镇江泛华新材料科技发展有限公司 | Cobalt salt bonding agent for bonding ethylene propylene diene monomer with copper or zinc framework and preparation method thereof |
| CN101985545A (en) * | 2010-10-27 | 2011-03-16 | 镇江泛华新材料科技发展有限公司 | Cobalt salt bonding agent for bonding nitrile butadiene rubber with bare steel framework and preparation method thereof |
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Application publication date: 20120215 |