阅读说明：本技术 一种橡胶增粘剂的制备方法 (A kind of preparation method of rubber tackifier ) 是由 曹建康 于 2019-07-30 设计创作，主要内容包括：本发明公开了一种橡胶增粘剂的制备方法,属于橡胶添加剂制备技术领域。本发明以丙烯酸、甲基丙烯酸为单体,加入蒸馏水、十二烷基磺酸钠、碳酸氢钠等物质,经过加热搅拌反应后继续掺加环氧大豆油、引发剂,经过交联反应再以氨水调节pH,得到丙烯酸酯胶乳,将乙烯-醋酸乙烯酯共聚物、苯基硅油、气相二氧化硅混合得到流变填料,将流变填料、蛭石粉、丙烯酸酯胶乳按一定质量比混合得到流渗剂,将聚乙烯醇溶液与正丁醛置于缩合反应釜中反应,分层后去除上层废液,加入流渗剂、无机粘结填料、粘结增强剂,保温搅拌处理,得到橡胶增粘剂。(The invention discloses a kind of preparation methods of rubber tackifier, belong to rubber additive preparation technical field.The present invention is with acrylic acid, methacrylic acid is monomer, distilled water is added, dodecyl sodium sulfate, the substances such as sodium bicarbonate, continue to add epoxidized soybean oil after heating stirring is reacted, initiator, pH is adjusted with ammonium hydroxide again by cross-linking reaction, obtain acrylate latex, by ethylene-vinyl acetate copolymer, phenyl silicone oil, fumed silica is mixed to get rheology filler, by rheology filler, vermiculite power, acrylate latex is mixed to get stream penetration enhancer by certain mass ratio, poly-vinyl alcohol solution is placed in condensation reaction kettle with n-butanal and is reacted, upper layer waste liquid is removed after layering, stream penetration enhancer is added, inorganic bond filler, bond reinforcing agent, insulated and stirred processing, obtain rubber tackifier.)

1. a kind of preparation method of rubber tackifier, it is characterised in that specific preparation step are as follows:

The poly-vinyl alcohol solution that mass fraction is 40% is squeezed into condensation reaction kettle through filter and cools down, it is cooled to 10~ N-butanal, benzene sulfonic acid are sequentially added after 15 DEG C, and 40~50 parts of stream penetration enhancers are added into condensation reaction kettle after reacting 40~50min, The reaction was continued until react and is mutually layered in condensation reaction kettle, after reacting mutually layering in above-mentioned condensation reaction kettle temperature reaction 10~ 15h is separated by filtration removal upper layer waste liquid, continues that inorganic bond filler is added into condensation reaction kettle, bonds reinforcing agent, be warming up to 70~78 DEG C, insulated and stirred handles 45~50min, obtains rubber tackifier；

The specific preparation step of inorganic bond filler are as follows:

The sierozem power of 300 mesh, the talcum powder of 400 mesh, pulverized limestone, dolomite, polyvinyl alcohol, In are added into high speed disperser 2~3h of high speed dispersion under 3000~4000r/min revolving speed, obtains inorganic bond filler；

The specific preparation step of stream penetration enhancer are as follows:

It takes vermiculite to be put into 30~40min of ball milling in ball mill, crosses 400 meshes and obtain vermiculite power, by vermiculite power, rheology filler, third Olefin(e) acid ester gum cream is 1 ︰, 4 ︰ 10 mixing in mass ratio, obtains stream penetration enhancer；

The specific preparation step of bonding reinforcing agent are as follows:

The sodium hydroxide solution that 70~75g beta-cyclodextrin and 100~130mL mass fraction are 50% is added into beaker, at room temperature After stirring 10~15min, 5~10g2 is added, 3- epoxypropyltrimethylchloride chloride places the beaker in water-bath, heating 50~55 DEG C, 3~4h of insulation reaction are warming up to, filtering removal filtrate obtains bonding reinforcing agent, spare.

2. a kind of preparation method of rubber tackifier according to claim 1, it is characterised in that: the rubber tackifier In specific preparation step each raw material in parts by weight, including mass fraction be 40% 60~70 parts of poly-vinyl alcohol solution, n-butanal 40~50 parts, 4~5 parts of benzene sulfonic acid, stream 40~50 parts of penetration enhancer, 10~12 parts of inorganic bond filler, bond 20~25 parts of reinforcing agent.

3. a kind of preparation method of rubber tackifier according to claim 1, it is characterised in that: the rubber tackifier Control reaction temperature is 55~60 DEG C when temperature reaction after reacting mutually layering in above-mentioned condensation reaction kettle in specific preparation step.

4. a kind of preparation method of rubber tackifier according to claim 1, it is characterised in that: the inorganic bond is filled out Expect each component raw material in specific preparation step, according to parts by weight, the talcum of 25~30 parts of sierozem power, 400 mesh including 300 mesh 8~10 parts of powder, 50~55 parts of pulverized limestone, 30~40 parts of dolomite, 100~120 parts of polyvinyl alcohol.

5. a kind of preparation method of rubber tackifier according to claim 1, it is characterised in that: the stream penetration enhancer is specific Vermiculite power, rheology filler, acrylate latex mixing mass ratio are 1 ︰, 4 ︰ 10 in preparation step.

6. a kind of preparation method of rubber tackifier according to claim 1, it is characterised in that: the stream penetration enhancer is specific Rheology filler is mixed to get by EVA resin, phenyl silicone oil, fumed silica with mass ratio for 3 ︰, 2 ︰ 1 in preparation step, wherein Vinyl acetate mass content is 25~30% in EVA resin.

7. a kind of preparation method of rubber tackifier according to claim 1, it is characterised in that: the stream penetration enhancer is specific The specific preparation step of acrylate latex in preparation step are as follows:

Epoxidized soybean oil, distilled water, dodecyl sodium sulfate, sodium bicarbonate, acrylic acid and methyl-prop are added into three-necked flask Olefin(e) acid, then 1~3 part of potassium peroxydisulfate is added dropwise with the drop rate of 3~5mL/min into four-hole boiling flask with dropping funel, it drips Bi Hou, 30~40min of insulation reaction continue to be heated to 90~100 DEG C, and 45~55min of insulation reaction is cooled to 55~60 DEG C, it is 6.0~7.0 that the ammonium hydroxide for being 20% with mass fraction, which adjusts pH, and discharging obtains acrylate latex.

8. a kind of preparation method of rubber tackifier according to claim 7, it is characterised in that: the acrylic adhesive Each raw material in newborn specific preparation step, according to parts by weight, including 20~30 parts of epoxidized soybean oil, 50~60 parts of distilled water, ten 10~15 parts of dialkyl sulfonates, 4~5 parts of sodium bicarbonate, 40~45 parts of acrylic acid, 20~30 parts, 1~3 part of methacrylic acid Potassium peroxydisulfate.

Technical field

The invention discloses a kind of preparation methods of rubber tackifier, belong to rubber additive preparation technical field.

Background technique

In order to which the rubber product of function admirable is made, unvulcanized gum material has had to enough viscosity, is convenient for work Production and storage during skill.Viscosity described herein refer to itself adhesive force of unvulcanized gum material or with other need Adhesive force between the material to be bonded.This viscosity plays highly important work in the technical process of manufacture rubber product With.In the production process of radial, rubber raw materials and compounding agent are uniform through mixing before vulcanization, and film is made and wraps Cover steel cord, then sulfidization molding.Therefore gum material needs good viscosity to meet mutual bonding force and the glue between sizing material Bonding force between material and steel cord.

May be used as the substance of rubber tackifier, there are many types.Such as aliphatic and aromatic hydrocarbon resins, benzo furan Furane resins, polyterpene resin, terpene phenolic, rosin and rosin derivative, alkyl phenolic resin, alkyl phenol acetylene resin etc., it is available Make rubber tackifier.

Hydrocarbon resins is in general cheaper than alkyl phenolic resin, but to reach same viscosity, then the amount of its needs is past Past larger, the three times of about alkyl phenolic resin are even more.When the tackifier retained in rubber have when quantity is larger The tendency for reducing rubber product performance, so alkyl phenolic resin is usually preferentially selected, because its dosage is less.However, Addition alkyl phenolic resin tackifier often reduce gum material to the bonding force of wire or other reinforcement materials.Due to this A reason, when the bonding force between rubber and reinforcement material becomes key factor, hydrocarbon resins can be still selected sometimes, In In this case the tackifier of addition more amount be may require that, thus will affect the quality of rubber product to a certain extent.

Therefore some rubber industries, such as radial industry, urgently demand has the rubber of more preferable comprehensive performance Tackifier product.In order to preferably solve the problems, such as this, many researchers use a variety of methods and carry out to alkyl phenolic resin Study on the modification.

If related patent discloses a kind of compound containing vinyl, such as styrene, alkyl phenolic resin is increased The method that stick is modified；It is a kind of to use primary amine or secondary amine compound, such as morpholine and diethanol amine, alkyl phenolic resin is increased The method that stick is modified.A kind of primary amine or secondary amine compound are reacted with alkyl phenolic resin, then further with ring The method that the technique of oxide reaction is modified alkyl phenolic resin tackifier.It is a kind of to use primary amine or secondary amine compound, pine The method that fragrant, long chain fatty acids are modified alkyl phenolic resin tackifier.

Summary of the invention

Present invention mainly solves the technical issues of, it is bad for the adhesion strength between rubber tackifier and ground, for a long time Lasting adhesiveness inadequate defect when use, provides a kind of preparation method of rubber tackifier.

In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:

A kind of rubber tackifier the preparation method comprises the following steps:

The poly-vinyl alcohol solution that mass fraction is 40% is squeezed into condensation reaction kettle through filter and cools down, it is cooled to 10~ N-butanal, benzene sulfonic acid are sequentially added after 15 DEG C, and 40~50 parts of stream penetration enhancers are added into condensation reaction kettle after reacting 40~50min, The reaction was continued until react and is mutually layered in condensation reaction kettle, after reacting mutually layering in above-mentioned condensation reaction kettle temperature reaction 10~ 15h is separated by filtration removal upper layer waste liquid, continues that inorganic bond filler is added into condensation reaction kettle, bonds reinforcing agent, be warming up to 70~78 DEG C, insulated and stirred handles 45~50min, obtains rubber tackifier；

The preparation of inorganic bond filler:

The sierozem power of 300 mesh, the talcum powder of 400 mesh, pulverized limestone, dolomite, polyvinyl alcohol, In are added into high speed disperser 2~3h of high speed dispersion under 3000~4000r/min revolving speed, obtains inorganic bond filler；

Flow the preparation of penetration enhancer:

It takes vermiculite to be put into 30~40min of ball milling in ball mill, crosses 400 meshes and obtain vermiculite power, by vermiculite power, rheology filler, third Olefin(e) acid ester gum cream is 1 ︰, 4 ︰ 10 mixing in mass ratio, obtains stream penetration enhancer；

Bond the preparation of reinforcing agent:

The sodium hydroxide solution that 70~75g beta-cyclodextrin and 100~130mL mass fraction are 50% is added into beaker, at room temperature After stirring 10~15min, 5~10g2 is added, 3- epoxypropyltrimethylchloride chloride places the beaker in water-bath, heating 50~55 DEG C, 3~4h of insulation reaction are warming up to, filtering removal filtrate obtains bonding reinforcing agent, spare.

Rubber tackifier preparation in each raw material in parts by weight, including mass fraction be 40% poly-vinyl alcohol solution 60~ 70 parts, 40~50 parts of n-butanal, 4~5 parts of benzene sulfonic acid, stream 40~50 parts of penetration enhancer, 10~12 parts of inorganic bond filler, bonding enhancing 20~25 parts of agent.

Reaction temperature is controlled when temperature reaction after reacting mutually layering in above-mentioned condensation reaction kettle in rubber tackifier preparation It is 55~60 DEG C.

Each component raw material in the preparation of inorganic bond filler, according to parts by weight, 25~30 parts of sierozem power including 300 mesh, 100~120 parts of 30~40 parts of 50~55 parts of 8~10 parts of talcum powder, pulverized limestone, dolomite, the polyvinyl alcohol of 400 mesh.

Flowing vermiculite power, rheology filler, acrylate latex mixing mass ratio in penetration enhancer preparation is 1 ︰, 4 ︰ 10.

Rheology filler is that 3 ︰, 2 ︰ 1 is mixed with mass ratio by EVA resin, phenyl silicone oil, fumed silica in stream penetration enhancer preparation Conjunction obtains, and wherein vinyl acetate mass content is 25~30% in EVA resin.

Flow the preparation of acrylate latex in penetration enhancer preparation:

Epoxidized soybean oil, distilled water, dodecyl sodium sulfate, sodium bicarbonate, acrylic acid and methyl-prop are added into three-necked flask Olefin(e) acid, then 1~3 part of potassium peroxydisulfate is added dropwise with the drop rate of 3~5mL/min into four-hole boiling flask with dropping funel, it drips Bi Hou, 30~40min of insulation reaction continue to be heated to 90~100 DEG C, and 45~55min of insulation reaction is cooled to 55~60 DEG C, it is 6.0~7.0 that the ammonium hydroxide for being 20% with mass fraction, which adjusts pH, and discharging obtains acrylate latex.

Each raw material in acrylate latex preparation, according to parts by weight, including 20~30 parts of epoxidized soybean oil, distilled water 50 ~60 parts, 10~15 parts of dodecyl sodium sulfate, 4~5 parts of sodium bicarbonate, 40~45 parts of acrylic acid, methacrylic acid 20~30 Part, 1~3 part of potassium peroxydisulfate.

The beneficial effects of the present invention are:

(1) objects such as distilled water, dodecyl sodium sulfate, sodium bicarbonate are added using acrylic acid, methacrylic acid as monomer in the present invention Matter continues to add epoxidized soybean oil, initiator after heating stirring is reacted, and adjusts pH again by cross-linking reaction with ammonium hydroxide, obtains To acrylate latex, ethylene-vinyl acetate copolymer, phenyl silicone oil, fumed silica are mixed to get rheology filler, Rheology filler, vermiculite power, acrylate latex are mixed to get stream penetration enhancer by certain mass ratio, by poly-vinyl alcohol solution and positive fourth Aldehyde, which is placed in condensation reaction kettle, to react, and upper layer waste liquid is removed after layering, and stream penetration enhancer, inorganic bond filler, bonding reinforcing agent is added, Insulated and stirred processing, obtains rubber tackifier, the present invention intersects polycondensation by using polyvinyl alcohol and n-butanal, urges using acidity Agent benzene sulfonic acid prepares the polyvinyl butyral that can be dissolved each other with acrylate, flows the vermiculite power in penetration enhancer, can make to gather Vinyl alcohol and the intermolecular intersolubility of n-butanal increase, and improve reaction conversion ratio, and the porous structure of vermiculite power can inhibit poly- Vinyl butyral crystallizes the curing time for being hardened and extending acrylate, enables prepared rubber tackifier in rubber Sufficiently stream seeps in raw material, improves rubber lasting adhesiveness；

(2) using polyvinyl butyral as carry plasticising cementation in rubber in the present invention, additionally it is possible to improve rubber Flexibility and rubber to the adhesiveness of metal, so that it is bad to most of metal substrate adhesion property to solve rubber tackifier The problem of, biggish steric hindrance can be generated in rubber using inorganic bond filler in the present invention, be conducive to improve in rubber The dispersion performance of bonding component such as acrylate and polyvinyl butyral makes rubber cement keep uniform close in rubber Degree, by the way that bonding reinforcing agent is prepared by the beta-cyclodextrin cationic etherificate of 2,3- epoxypropyltrimethylchloride chloride progress, Electrostatic attraction effect is generated between the bonding reinforcing agent energy and the acrylate for the electronics that is easy to get, which acts on so that rubber Association can be generated in polymeric groups and in strand, elastomeric polymer molecule is caused to shrink, keeps tackifier viscous in ground Settled density increases at junction interface, improves the lasting adhesive property between rubber and ground, has broad application prospects.

Specific embodiment

According to parts by weight, 20~30 parts of epoxidized soybean oils, 50~60 parts of distilled water, 10~15 are added into three-necked flask Part dodecyl sodium sulfate, 4~5 parts of sodium bicarbonates, 40~45 parts of acrylic acid and 20~30 parts of methacrylic acids, then leaked with dropping liquid It struggles against and 1~3 part of potassium peroxydisulfate, after being added dropwise, insulation reaction 30 is added dropwise with the drop rate of 3~5mL/min into four-hole boiling flask ~40min continues to be heated to 90~100 DEG C, 45~55min of insulation reaction, is cooled to 55~60 DEG C, is with mass fraction It is 6.0~7.0 that 20% ammonium hydroxide, which adjusts pH, and discharging obtains acrylate latex, spare；According to the mass fraction, to high speed dispersion Be added in machine the sierozem power of 25~30 part of 300 mesh, the talcum powder of 8~10 part of 400 mesh, 50~55 parts of pulverized limestones, 30~40 parts it is white Marble, 100~120 parts of polyvinyl alcohol, 2~3h of high speed dispersion under 3000~4000r/min revolving speed obtain inorganic bond and fill out Material, it is spare；It takes vermiculite to be put into 30~40min of ball milling in ball mill, crosses 400 meshes and obtain vermiculite power, vermiculite power, rheology are filled out Material, spare acrylate latex are 1 ︰, 4 ︰ 10 mixing in mass ratio, obtain stream penetration enhancer, the rheology filler is by EVA resin, benzene Base silicone oil, fumed silica are that 3 ︰, 2 ︰ 1 is mixed to get with mass ratio, and wherein vinyl acetate mass content is 25 in EVA resin ~30%；The sodium hydroxide solution that 70~75g beta-cyclodextrin and 100~130mL mass fraction are 50%, room temperature are added into beaker After 10~15min of lower stirring, 5~10g2 is added, 3- epoxypropyltrimethylchloride chloride places the beaker in water-bath, adds Heat is warming up to 50~55 DEG C, 3~4h of insulation reaction, and filtering removal filtrate obtains bonding reinforcing agent, spare；According to parts by weight, The poly-vinyl alcohol solution that 60~70 parts of mass fractions are 40% is squeezed into condensation reaction kettle through filter and is cooled down, is cooled to 40~50 parts of n-butanals, 4~5 parts of benzene sulfonic acids are sequentially added after 10~15 DEG C, are added after reacting 40~50min into condensation reaction kettle Enter 40~50 parts of stream penetration enhancers, the reaction was continued is mutually layered until reacting in condensation reaction kettle；To react phase in above-mentioned condensation reaction kettle It is continuously heating to 55~60 DEG C after layering, reacts 10~15h, is separated by filtration removal upper layer waste liquid, continues into condensation reaction kettle It is added 70~80 parts of stream penetration enhancers, 10~12 parts of spare inorganic bond fillers, 20~25 parts of spare bonding reinforcing agents, it is warming up to 70~ 78 DEG C, insulated and stirred handles 45~50min, obtains rubber tackifier.