阅读说明：本技术 丁苯橡胶及其制备方法 (Butadiene-styrene rubber and preparation method thereof ) 是由 石捷强 殷兰 庞建勋 王秀芝 李永茹 侯军 郭睿达 孙继德 于 2018-05-24 设计创作，主要内容包括：本发明提供了一种丁苯橡胶及其制备方法。本发明制备丁苯橡胶的方法包括如下步骤：1)将丁二烯、苯乙烯、乳化剂、电解质、除氧剂、活化剂、氧化剂、调节剂、脱盐水进行混合,然后进行乳液聚合反应；待反应结束后,将反应体系进行脱气后加入防老剂,得到胶乳,其中该氧化剂为过氧化氢蒎烷；2)将该胶乳加入到含有絮凝剂和浓硫酸的水中并进行搅拌,待该胶乳凝聚后,过滤干燥,得到丁苯生胶,其中该浓硫酸为质量分数大于或等于70％的硫酸溶液；3)将该丁苯生胶与炭黑、硫磺混合并进行硫化,得到丁苯橡胶。该制备方法能够有效缩短聚合时间,减少调节剂用量,降低能耗；并且使用该制备方法可以制备出不同的丁苯胶乳,并制备出合格的丁苯橡胶制品。(The present invention provides a kind of butadiene-styrene rubber and preparation method thereof.The method that the present invention prepares butadiene-styrene rubber includes the following steps: 1) to mix butadiene, styrene, emulsifier, electrolyte, oxygen scavenger, activator, oxidant, regulator, desalted water, then carries out emulsion polymerization；To which anti-aging agent is added after after reaction, reaction system is de-gassed, latex is obtained, wherein the oxidant is di isopropyl benzene hydroperoxide；2) latex is added in the water containing flocculant and the concentrated sulfuric acid and is stirred, after the emulsion condensation, filtration drying obtains butylbenzene raw rubber, and wherein the concentrated sulfuric acid is the sulfuric acid solution that mass fraction is greater than or equal to 70%；3) the butylbenzene raw rubber is mixed and is vulcanized with carbon black, sulphur, obtain butadiene-styrene rubber.The preparation method can effectively shorten polymerization time, reduce regulator dosage, reduce energy consumption；And different styrene-butadiene latexes can be prepared using the preparation method, and prepares qualified butadiene-styrene rubber product.)

1. a kind of method for preparing butadiene-styrene rubber, which is characterized in that described method includes following steps:

1) butadiene, styrene, emulsifier, electrolyte, oxygen scavenger, activator, oxidant, regulator, desalted water are mixed It closes, then carries out emulsion polymerization；To which anti-aging agent is added after after reaction, reaction system is de-gassed, latex is obtained, Wherein the oxidant is di isopropyl benzene hydroperoxide；

2) latex is added in the water containing flocculant and the concentrated sulfuric acid and is stirred, after the emulsion condensation, mistake It is filtered dry dry, obtains butylbenzene raw rubber, wherein the concentrated sulfuric acid is the sulfuric acid solution that mass fraction is greater than or equal to 70%；

3) the butylbenzene raw rubber is mixed and is vulcanized with carbon black, sulphur, obtain the butadiene-styrene rubber.

2. the method according to claim 1, wherein by weight, the butadiene in step 1) is 30 ~70 parts, the styrene be 10~40 parts, the emulsifier is 1~10 part, the electrolyte is 0.1~10 part, described is removed Oxygen agent is 0.01~0.1 part, the activator is 0.01~0.1 part, the oxidant is 0.01~0.1 part, the regulator For 0.1~0.3 part, the desalted water be 100~200 parts and the anti-aging agent is 0.1~10 part.

3. method according to claim 1 or 2, which is characterized in that in step 1), the reaction temperature of the emulsion polymerization Degree is 0~20 DEG C, and the reaction time is 3~10 hours；It is preferred that the reaction temperature of the emulsion polymerization is 5~10 DEG C, reaction Time is 4~10 hours；The reaction temperature of the more preferable emulsion polymerization is 5~7 DEG C, and the reaction time is 5~9 hours.

4. the method according to claim 1, wherein the temperature of the stirring in step 2) is controlled 40~90 Between DEG C, the time is 5~20 minutes；Preferably, the temperature of the stirring controls between 60~80 DEG C, and the time is 5~15 points Clock；It is highly preferred that the temperature control of the stirring is 65 DEG C, the time is 10 minutes.

5. method according to claim 1 or 4, which is characterized in that by weight, described in step 2) contains flocculation In the water of agent and the concentrated sulfuric acid, the flocculant is 1~10 part, and the concentrated sulfuric acid is 1~10 part, and water is 100 parts；Preferably, institute Stating flocculant is one of polyacrylamide, polymer alumina and bodied ferric sulfate or a variety of.

6. the method according to any one of claims 1 to 5, which is characterized in that the activator be NaFeEDTA sodium salt and/ Or rongalite；Preferably, the weight of the NaFeEDTA sodium salt and the rongalite in the activator Amount is than being 90~110:30.

7. the method according to any one of claims 1 to 5, which is characterized in that the emulsifier be single emulsifier or Blended emulsifier；Preferably, the single emulsifier is isproportionated potassium rosinate；Preferably, the blended emulsifier is disproportionation The mixture of rosin acid potash soap and fatty acid sodium soap；Preferably, isproportionated potassium rosinate described in the blended emulsifier and institute The weight ratio for stating fatty acid sodium soap is 1.1~0.9:1.

8. the method according to any one of claims 1 to 5, which is characterized in that the electrolyte is phosphoric acid, hydroxide One of potassium, tetrasodium salt of EDTA and methine sodium dinaphthalenesulfonate are a variety of；Preferably, in the electrolyte The phosphoric acid, the potassium hydroxide, the tetrasodium salt of EDTA and it is described between methine sodium dinaphthalenesulfonate Weight ratio be 2.5~1.5:3.5~2.5:0.2~0.3:1.

9. the method according to any one of claims 1 to 5, which is characterized in that the oxygen scavenger is sodium dithionite.

10. the method according to any one of claims 1 to 5, which is characterized in that the regulator is dodecyl sulphur Alcohol.

11. the method according to any one of claims 1 to 5, which is characterized in that the anti-aging agent is ethyoxyl -2 6-, 2,4- trimethyl -1,2- dihyaroquinoline, N- phenyl-α-aniline, N- phenyl-β-naphthylamine, p-phenylenediamine, N- phenyl-N '-isopropyl One of base-p-phenylenediamine, N-N '-diphenyl-p-phenylenediamine are a variety of.

12. the butadiene-styrene rubber of the preparation of a kind of method described in any one of claims 1 to 11.

Technical field

The present invention relates to synthetic rubber fields, in particular to a kind of butadiene-styrene rubber and preparation method thereof.

Background technique

Butadiene-styrene rubber (SBR) is the thermo-setting elastomer as made of butadiene, styrene monomer copolymerization, is in synthetic rubber One of important rubber clone.In order to improve the performance and processing performance of butadiene-styrene rubber product, at present mainly to tie benzene amount 23.5- Based on styrene-butadiene latex based on 40%, or filling out for small part amount 300-600 or so is mixed in the glue of knot benzene amount 23.5-40% Oil-filled, mixing latex obtained, cohesion obtains unvulcanized raw rubber, then blends carbon black, sulfur cross-linking, obtains vulcanized rubber, i.e., Prepare butadiene-styrene rubber elastomer.Butadiene-styrene rubber preparation method in the prior art mainly has the defect of following several respects:

Defect one: polymerization reaction time is long；Shortening polymerization reaction time can make conversion ratio decline to be met The butadiene-styrene rubber product of performance requirement.

Defect two: the power consumption of consersion unit is high.

Defect three: the required regulator dosage of polymerization reaction is big.

Based on the above reasons, need further to study butadiene-styrene rubber preparation method, with solve its polymerization time it is long, The problem that energy consumption is high and regulator dosage is big.

Summary of the invention

The main purpose of the present invention is to provide a kind of butadiene-styrene rubber and preparation method thereof, to solve fourth in the prior art The problem that benzene method for preparing rubber polymerization time is long, energy consumption is high and regulator dosage is big.

To achieve the goals above, according to an aspect of the invention, there is provided a kind of method for preparing butadiene-styrene rubber, is somebody's turn to do Method include the following steps: 1) by butadiene, styrene, emulsifier, electrolyte, oxygen scavenger, activator, oxidant, regulator, Desalted water is mixed, and emulsion polymerization is then carried out；It is anti-old to be added after reaction, after reaction system is de-gassed Agent obtains latex, and wherein the oxidant is di isopropyl benzene hydroperoxide；2) latex is added to the water containing flocculant and the concentrated sulfuric acid In and be stirred, after the emulsion condensation, filtration drying obtains butylbenzene raw rubber, and wherein the concentrated sulfuric acid is greater than for mass fraction Or the sulfuric acid solution equal to 70%；3) the butylbenzene raw rubber is mixed and is vulcanized with carbon black, sulphur, obtain the butadiene-styrene rubber.

Further, by weight, the butadiene in step 1) is 30~70 parts, the styrene is 10~40 parts, The emulsifier is 1~10 part, the electrolyte is 0.1~10 part, the oxygen scavenger is 0.01~0.1 part, the activator be 0.01~ 0.1 part, the oxidant be 0.01~0.1 part, the regulator is 0.1~0.3 part, the desalted water is 100~200 parts and this is anti-old Agent is 0.1~10 part.

Further, in step 1), the reaction temperature of the emulsion polymerization is 0~20 DEG C, and the reaction time is 3~10 small When.

Further, in step 1), the reaction temperature of the emulsion polymerization is 5~10 DEG C, and the reaction time is 4~10 small When.

Further, in step 1), the reaction temperature of the emulsion polymerization is 5~7 DEG C, and the reaction time is 5~9 small When.

Further, the temperature of the stirring in step 2) controls between 40~90 DEG C, and the time is 5~20 minutes.

Further, the temperature of the stirring in step 2) controls between 60~80 DEG C, and the time is 5~15 minutes.

Further, the temperature control of the stirring in step 2) is 65 DEG C, and the time is 10 minutes.

Further, by weight, being somebody's turn to do in the water containing flocculant and the concentrated sulfuric acid in step 2), the flocculant are 1 ~10 parts, which is 1~10 part, and water is 100 parts.

Further, which is one of polyacrylamide, polymer alumina and bodied ferric sulfate or a variety of.

Further, which is NaFeEDTA sodium salt and/or rongalite.

Further, the weight ratio of the NaFeEDTA sodium salt in the activator and the rongalite is 90~110: 30。

Further, which is single emulsifier or blended emulsifier.

Further, which is isproportionated potassium rosinate.

Further, which is the mixture of isproportionated potassium rosinate and fatty acid sodium soap.

Further, the weight ratio of isproportionated potassium rosinate described in the blended emulsifier and the fatty acid sodium soap is 1.1~0.9:1.

Further, which is phosphoric acid, two naphthalene sulfonic acids of potassium hydroxide, tetrasodium salt of EDTA and methine One of sodium is a variety of.

Further, the phosphoric acid in the electrolyte, the potassium hydroxide, the tetrasodium salt of EDTA and time first between this Weight ratio between base sodium dinaphthalenesulfonate is 2.5~1.5:3.5~2.5:0.2~0.3:1.

Further, which is sodium dithionite.

Further, which is lauryl mercaptan.

Further, which is 6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinoline, N- phenyl-α-benzene Amine, N- phenyl-β-naphthylamine, p-phenylenediamine, N- phenyl-N '-isopropyl-p-phenylenediamine, in N-N '-diphenyl-p-phenylenediamine It is one or more.

According to another aspect of the present invention, the preparation of a kind of method described in any one of claims 1 to 12 is provided Butadiene-styrene rubber.

It applies the technical scheme of the present invention, 1) method for preparing butadiene-styrene rubber includes the following steps: butadiene, benzene second Alkene, emulsifier, electrolyte, oxygen scavenger, activator, oxidant, regulator, desalted water are mixed, and emulsion polymerization is then carried out Reaction；To which anti-aging agent is added after after reaction, reaction system is de-gassed, latex is obtained, wherein the oxidant is peroxide Change hydrogen pinane；2) latex is added in the water containing flocculant and the concentrated sulfuric acid and is stirred, after the emulsion condensation, mistake It is filtered dry dry, obtains butylbenzene raw rubber, wherein the concentrated sulfuric acid is the sulfuric acid solution that mass fraction is greater than or equal to 70%；3) by the butylbenzene Raw rubber mixes and is vulcanized with carbon black, sulphur, obtains butadiene-styrene rubber.The preparation method can effectively shorten polymerization time, subtract Few regulator dosage, reduces energy consumption；And different styrene-butadiene latexes can be prepared using the preparation method, and prepares qualification Butadiene-styrene rubber product.

Specific embodiment

It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.

The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally Apply for range claimed.

As described in background technology part, there are polymerization time length, energy consumption are high for existing butadiene-styrene rubber preparation method And the problem that regulator dosage is big.To solve the above-mentioned problems, the present invention provides a kind of methods for preparing butadiene-styrene rubber, should Method includes the following steps:

1) by butadiene, styrene, emulsifier, electrolyte, oxygen scavenger, activator, oxidant, regulator, desalted water into Row mixing, then carries out emulsion polymerization；To which anti-aging agent is added after after reaction, reaction system is de-gassed, obtain Latex, wherein the oxidant is di isopropyl benzene hydroperoxide；

2) latex is added in the water containing flocculant and the concentrated sulfuric acid and is stirred, after the emulsion condensation, mistake It is filtered dry dry, obtains butylbenzene raw rubber, wherein the concentrated sulfuric acid is the sulfuric acid solution that mass fraction is greater than or equal to 70%；

3) the butylbenzene raw rubber is mixed and is vulcanized with carbon black, sulphur, obtain the butadiene-styrene rubber.

The preparation method can effectively shorten polymerization time, reduce regulator dosage, reduce energy consumption；And use the preparation Method can prepare different styrene-butadiene latexes, and prepare qualified butadiene-styrene rubber product.

In order to further balance the effect of each component and more give full play to synergistic effect between each component, it is a kind of preferably Embodiment in, by weight, the butadiene in step 1) is 30~70 parts, the styrene is 10~40 parts, the cream Agent is 1~10 part, the electrolyte is 0.1~10 part, the oxygen scavenger is 0.01~0.1 part, the activator is 0.01~0.1 Part, the oxidant are 0.01~0.1 part, the regulator is 0.1~0.3 part, the desalted water is 100~200 parts and the anti-aging agent It is 0.1~10 part.

In a preferred embodiment, in step 1), the reaction temperature of the emulsion polymerization is 0~20 DEG C, instead It is 3~10 hours between seasonable.Compared to other reaction temperatures and reaction time, the application's has above-mentioned reaction temperature and reaction The emulsion polymerization of time can be obviously improved SBR of emulsion polymerization branching crosslinking situation, improve the property such as stress at definite elongation Energy.

In a preferred embodiment, in step 1), the reaction temperature of the emulsion polymerization is 5~10 DEG C, instead It is 4~10 hours between seasonable.Compared to other reaction temperatures and reaction time, the application's has above-mentioned reaction temperature and reaction The emulsion polymerization of time can be obviously improved SBR of emulsion polymerization branching crosslinking situation, improve the property such as stress at definite elongation Energy.

In a preferred embodiment, in step 1), the reaction temperature of the emulsion polymerization is 5~7 DEG C, reaction Time is 5~9 hours.Compared to other reaction temperatures and reaction time, when there is above-mentioned reaction temperature and reaction of the application Between emulsion polymerization can be obviously improved SBR of emulsion polymerization branching crosslinking situation, improve the performances such as stress at definite elongation.

In a preferred embodiment, the temperature of the stirring in step 2) controls the time between 40~90 DEG C It is 5~20 minutes.Compared to other whipping temps and time, the application's has above-mentioned whipping temp and the stirring of time can It is obviously promoted gathering for latex.

In a preferred embodiment, the temperature of the stirring in step 2) controls the time between 60~80 DEG C It is 5~15 minutes.Compared to other whipping temps and time, the application's has above-mentioned whipping temp and the stirring of time can It is obviously promoted gathering for latex.

In a preferred embodiment, the temperature control of the stirring in step 2) is 65 DEG C, and the time is 10 minutes. Compared to other whipping temps and time, the application's there is above-mentioned whipping temp and the stirring of time can be obviously promoted latex Gather.

In order to further balance the effect between each component, in a preferred embodiment, by weight, step 2) being somebody's turn to do in the water containing flocculant and the concentrated sulfuric acid in, the flocculant are 1~10 part, which is 1~10 part, water 100 Part.

In a preferred embodiment, which is in polyacrylamide, polymer alumina and bodied ferric sulfate It is one or more.Compared to other flocculants, flocculant used in this application will more promptly can hang in solution The aggregation of floating glue lactoconium, which is coupled, forms coarse cotton-shaped granule or agglomerate.

In a preferred embodiment, which is NaFeEDTA sodium salt and/or rongalite.Compared to Other activators, activator used in this application had both prevented macromolecular chain further occurrence autocatalysis oxidative degradation, simultaneously Again prevent macromolecular chain free radical recombine or attack chain on double bond, reduce energy consumption, improve production efficiency, improve The other performances such as the mechanical strength of latex.

In order to further balance the effect between each component, in a preferred embodiment, being somebody's turn to do in the activator The weight ratio of NaFeEDTA sodium salt and the rongalite is 90~110:30.

In a preferred embodiment, which is single emulsifier or blended emulsifier.Use the application's Single emulsifier or blended emulsifier can prepare two different styrene-butadiene latexes.

In a preferred embodiment, which is isproportionated potassium rosinate.Compared to other emulsifiers, Single emulsifier used in this application can form micella in polymerization water phase, emulsify the monomer being dispersed in water phase, shape Polymer particle coalescing is prevented at stable monomer droplet to protect established latex granule.

In a preferred embodiment, which is the mixing of isproportionated potassium rosinate and fatty acid sodium soap Object.Compared to other emulsifiers, blended emulsifier used in this application more efficiently can form glue in polymerization water phase Beam emulsifies the monomer being dispersed in water phase, forms more stable monomer droplet, to protect established latex granule, more It is effectively prevented polymer particle coalescing.

In order to further balance the effect between each component, in a preferred embodiment, in the blended emulsifier The weight ratio of the isproportionated potassium rosinate and the fatty acid sodium soap is 1.1~0.9:1.

In a preferred embodiment, the electrolyte be phosphoric acid, potassium hydroxide, tetrasodium salt of EDTA and One of methine sodium dinaphthalenesulfonate is a variety of.Compared to other electrolyte, electrolyte used in this application has good Extension, foamability is low, can be mixed with other activating agents.

In order to further balance the effect between each component, in a preferred embodiment, being somebody's turn to do in the electrolyte Phosphoric acid, the potassium hydroxide, the tetrasodium salt of EDTA and the weight ratio between this between methine sodium dinaphthalenesulfonate are 2.5~1.5:3.5~2.5:0.2~0.3:1.

In a preferred embodiment, which is sodium dithionite.Compared to other oxygen scavengers, the application Used oxygen scavenger can effectively remove the oxygen in oxidation system, so that polymerization activity is improved, polymerization reaction speed Rate tends to reasonably stability, to ensure that the stabilization of polymerisation conversion and rubber cement Mooney.

In a preferred embodiment, which is lauryl mercaptan.Compared to other regulators, the application Used regulator can effectively prevent excessive functional group from being crosslinked, and keep polymer cohesive force appropriate, dosage directly affects Polymer molecular weight size leads to the superiority and inferiority of polymer physics mechanical property.

In a preferred embodiment, which is 6- ethyoxyl -2,2,4- trimethyl -1,2- dihydro quinoline Quinoline, N- phenyl-α-aniline, N- phenyl-β-naphthylamine, p-phenylenediamine, N- phenyl-N '-isopropyl-p-phenylenediamine, N-N '-hexichol One of base-p-phenylenediamine is a variety of.Compared to other anti-aging agents, anti-aging agent used in this application can effectively improve rubber Glue and its preparation for heat, oxygen, ozone, variable valency metal ions, mechanical stress, light, high-energy ray destruction resistance energy Power delays or inhibits ageing process, to extend storage period and the service life of rubber and its product.

According to another aspect of the present invention, a kind of butadiene-styrene rubber of above-mentioned method preparation is provided.The preparation of the application Butadiene-styrene rubber prepared by method can fully meet the performance requirement of general trade mark butadiene-styrene rubber.

The preparation method can effectively shorten polymerization time, reduce regulator dosage, reduce energy consumption；And use the preparation Method can prepare different styrene-butadiene latexes, and prepare qualified butadiene-styrene rubber product.

Beneficial effects of the present invention are further illustrated by the following examples: