CN100575373C - A kind of preparation method of high styrene rubber - Google Patents
A kind of preparation method of high styrene rubber Download PDFInfo
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- CN100575373C CN100575373C CN200510071104A CN200510071104A CN100575373C CN 100575373 C CN100575373 C CN 100575373C CN 200510071104 A CN200510071104 A CN 200510071104A CN 200510071104 A CN200510071104 A CN 200510071104A CN 100575373 C CN100575373 C CN 100575373C
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Abstract
The present invention relates to a kind of preparation method of high styrene rubber, adopt the multistage polymeric mode of normal temperature emulsion, with vinylbenzene and divinyl is polymerization single polymerization monomer, add water, activation phase, molecular weight regulator, deionized water, adding initiator initiated polymerization, polymerization is added monomer and molecular weight regulator after generating SBR emulsion or high styrene resin emulsion, continues reaction, directly synthetic high styrene rubber emulsion, emulsion makes high styrene rubber through cohesion, drying.This method flow is brief, simple to operate, process is controlled easily, and product can improve characteristics such as the rigidity, hardness, wear resistance, reduction shrinking percentage of rubber item in using the course of processing.
Description
Technical field
A kind of preparation method of high styrene rubber particularly relates to a kind of preparation method who directly synthesizes high styrene rubber.
Background technology
The multipolymer that high-phenylethylene is made up of divinyl and vinylbenzene if combined styrene content increases, will obtain little and the resin copolymer that plasticity is bigger of elasticity; Otherwise, then obtain the big less rubbery copolymer of plasticity of elasticity.Usually vinylbenzene binding capacity person between 45～70% in the molecular structure, be called high styrene rubber, and combined styrene content 70% above person, be called high styrene resin.The distinguishing feature of high styrene rubber is that hardness height own, intensity are good, and the physicals that has rubber again, with multiple synthetic rubber or natural rubber and time spent, can improve the performance such as rigidity, hardness, wear resistance, reduction shrinking percentage of rubber item, can be widely used in shoemaking industry, tire industry, Printing industry and other industry, and extremely pay attention to.
The synthetic method of high styrene rubber has three kinds: emulsion coagulation method, mechanical mixing method and direct polymerization method.The performance of the high styrene rubber of being produced owing to the emulsion coagulation method was better than the direct polymerization method in the past and was commonly used, and mechanical mixing method, because of its energy consumption height, product performance relatively poor, existing to eliminate.The present domestic trade mark that uses more Japanese Geon company to produce is the HS-860 high styrene rubber, adopts the manufacturing of emulsion coagulation method.Because technology does not pass a test before the direct polymerization method, the high styrene rubber product performance of being produced also seldom adopt, even are abandoned not as good as the emulsion coagulation method.
" China Synthetic Rubber Industry " 1998 the 2nd phases of volume have been delivered " development of high styrene rubber and application " literary composition.This article adopts organic synthesis factory of Ji Hua company to introduce butylbenzene 1502 prescriptions of JSR company, after high benzene resin emulsion mixes by a certain percentage, adds without pollution anti-aging agent styrenated phenol or three nonyl phenyl phosphites, with NaCl and H
2SO
4The aqueous solution is made flocculation agent and is produced high styrene rubber.
US4519431 is the patent of Japanese bridge stone tire company and Japan SYnthetic Rubber Co. Ltd's co-applications.It discloses a kind of butylbenzene copolymer preparation method of high-phenylethylene content.This polymkeric substance in conjunction with styrene content greater than 25m%, less than 60m%.This patent is to adopt the synthetic high-phenylethylene of solution polymerization process.
" chemical engineering design " (Technology that high styrene rubber is produced introduced in 1995,5 (3)-4-8) " high styrene rubbers " literary compositions, and the polymerization formula of high styrene resin emulsion, styrene-butadiene rubber(SBR)-1502 latex, technical process, operational condition etc.
" orchidization science and technology " (1998,12 (16)-4) a kind of single stage method directly polymerization process and the major influence factors of synthetic high styrene rubber, the comparison of its result of study and products obtained therefrom and co-agglomeration introduced in " research of the synthetic high styrene rubber of single stage method " literary composition.
CN1224733 has announced a kind of " graft-blending high-phenylethylene rubber and manufacture method thereof ".This subject content is that to adopt waste polystyrene foam and styrene-butadiene rubber(SBR) or cis-1,4-polybutadiene rubber be main raw material, and blend graft under effects such as linking agent, initiator forms high styrene rubber.The present invention compared with prior art, have cost low, improve environmental pollution, advantage such as manufacturing process is simple.
" production method of high-phenylethylene " this patent of CN1271740, its product high-phenylethylene is a kind of rubber and plastic product, as elastomeric strengthening agent, can with the various synthetic rubber except that isoprene-isobutylene rubber, natural rubber is also used, improve the tensile strength of rubber, tear strength, improve the hardness of rubber, wear resistance and electrical insulating property are used to make high rigidity, the goods that relative density is little, the high styrene resin emulsion is got through letex polymerization by divinyl, vinylbenzene, and itself and SBR-1502 latex are carried out common cohesion, dehydration, granulation by the combined styrene content requirement.Advantages such as this product has the hardness height, and mooney viscosity is big, the production technology operation of this invention, control easily.
" preparation method of high styrene rubber " this patent of CN1544522 is a kind of preparation method of high styrene rubber, with Rcoome, and rosinMe, Roso
3Me, Rso
3Me is an emulsifying agent, is initiator with the superoxide, is conditioning agent with mercaptan, add ionogen commonly used, under 40～80 ℃ of temperature, make 5～25% divinyl and 75～95% styrene emulsion copolymerization, in 5～12h, the high benzene resin of preparation under the condition of transformation efficiency＞98.5%; Use the high benzene resin emulsion of aforesaid method synthetic again, with the SBR-1502 latex that contains vinylbenzene 23.5 ± 1% or SBR-1500 latex blending, cohesion altogether, the preparation high styrene rubber, adopt synthetic SBR-1500 latex of quick high transformation technology or SBR-1502 latex polymerization novel process, and middle temperature letex polymerization, monomer conversion reach the high benzene synthetic technology of resins more than 98%, and it is short to have the reaction times, control easily, constant product quality, distinguishing feature such as energy consumption is low.
" preparation technology of the emulsion polymerized styrene butadiene rubber of different combined styrene content " this patent of CN1425701, introduced the preparation technology of the emulsion polymerized styrene butadiene rubber of different combined styrene content, it is the emulsion polymerization that carries out at low temperatures by divinyl and vinylbenzene, it is characterized in that adjusting vinylbenzene and quality of butadiene percentage ratio is respectively: vinylbenzene is 20～60% (are 100% in the monomer total amount), divinyl is 40～80% (are 100% in the monomer total amount), the consumption of the molecular weight regulator that adds is 0.12～0.25% of a monomer total amount for oil-filled glue.The present invention can utilize common styrene-butadiene rubber(SBR) production equipment, produces and prepare the oil-filled and non-oil-extended styrene-butadiene rubber of various combined styrene content, satisfies the needs of the different purposes of rubber.
Emulsion coagulation method production technology is generally adopted in the production of high styrene rubber at present, and this technological process can access the high styrene rubber of better performances, but the subject matter that this method exists is:
At first on technology, need synthetic respectively earlier SBR-1500 or SBR-1502 latex and high benzene resin emulsion, mix again by a certain percentage analyzing two kinds of qualified emulsions, obtain high styrene rubber through condensing drying then, its technical process is relatively than synthesis procedures such as the preparation of growing twice water of needs, oil phase, initiator and the degassings; Secondly on production cost, because synthetic SBR-1500 or SBR-1502 latex monomer transformation efficiency only 70%, unreacted monomer accounts for 30%, and this part monomer is difficult to reclaim in the production equipment of middle and small scale, causes production cost is higher and polymerization process is required equipment, auxiliary material, personnel, time, the energy more relatively; On the production cycle, because the synthesis temperature of high benzene resin emulsion is high temperature polymerization, polymeric kettle inner structure gel is more in addition, and used polymeric kettle carries out once clear still operation at 10～15 batches of needs of production usually, so plant factor is lower.
From result for retrieval,, all adopt latex condensation technique altogether though it is more to produce the document patent of high styrene rubber both at home and abroad.The present invention adopts that SBR emulsion (SBR-1500 or SBR-1502) or high benzene resin emulsion are synthetic in advance to be added monomer methods by one or many again and directly prepare the high styrene rubber emulsion, the back with polymeric flocculant condense, the technology of dry preparation high styrene rubber.This technology is domestic to be had only, and " research of the synthetic high styrene rubber of single stage method " has relevant report, its polymerization is to carry out in the 500ml vial, 10～25 ℃ of polymerization temperatures, its process is at first to feed intake with the ratio of m (Bd)/m (St)=70/30 and amount of auxiliary and the feeding manner thereof suitable with synthetic common SBR, treat that polymerisation conversion reaches at 70～80% o'clock, the St of additional demand amount, mercaptan and second emulsifying agent continue to be blended into transformation efficiency 98% discharging when above, through cohesion, dry product.Its technology synthetic technology is very imperfect, particularly condenses drying process and industrialization technology and differs bigger, and its technical target of the product, processing characteristics and product appearance and coagulation method have certain gap, and these goods are in Application Areas not approval as yet.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high styrene rubber.Adopt the multistage polymeric mode of normal temperature emulsion, carry out SBR emulsion (SBR-1500 or SBR-1502) or high styrene resin emulsion earlier pre-synthetic to add the directly synthetic combined styrene content that contains of monomer methods by one or many again be 60 ± 5% high styrene rubber emulsion, the back with polymeric flocculant condense, the technology of dry preparation high styrene rubber.
The present invention is a polymerization single polymerization monomer with vinylbenzene and divinyl, add water, activation phase, molecular weight regulator, deionized water, initiator, after polymerization generates SBR emulsion or high styrene resin emulsion, add monomer and molecular weight regulator, continue reaction, directly synthetic high styrene rubber emulsion, through cohesion, dry preparation high styrene rubber, wherein the parts by weight of reactant are:
Water 54.2～91.4
Activation phase 5.2～11
Molecular weight regulator 0.2～0.65
Initiator 0.03～0.05
Vinylbenzene 59～64
Divinyl 36～41
Deionized water 100～140
Described molecular weight mediator agent is a tert-dodecyl mercaptan, initiator be di-isopropylbenzene hydroperoxide or hydrogen peroxide to alkane in the Meng, the component of water and parts by weight are:
Deionized water 50～85
Emulsifying agent 4～6
Diffusant 0.1～0.2
Ionogen 0.1～0.2;
Emulsifying agent is the mixture of nilox resin acid potash soap, fatty acid potassium soap or above-claimed cpd, and diffusant is a naphthalenesulfonic acid-formaldehyde condensate, and ionogen is Repone K, potassiumphosphate, salt of wormwood, and the component and the parts by weight of activation phase are:
Deionized water 5～10
Sodium sulfoxylate formaldehyde 0.1～0.2
Disodium ethylene diamine tetraacetate 0.02～0.03
Sytron 0.01～0.02
Describedly comprise step by the synthetic high styrene rubber emulsion of SBR emulsion:
A) add reactant, reactant and parts by weight are: deionized water 100～140, the part water that accounts for water gross weight 2/3～4/5, vinylbenzene 16～17, divinyl 37～40, all activate phase, account for the part molecular weight mediator agent of molecular weight mediator agent gross weight 25%, stir, add initiator, initiation reaction;
B) when the transformation efficiency of divinyl reaches 25～35%, add the part molecular weight mediator agent that accounts for molecular weight mediator agent gross weight 10%, continue reaction;
C) when the transformation efficiency of divinyl reaches 55～65%, adding parts by weight is 43～47 vinylbenzene, remaining water and molecular weight mediator agent, continues reaction;
D) when the transformation efficiency of divinyl reaches 98%, termination reaction obtains the high styrene rubber emulsion, obtains high styrene rubber through cohesion, drying.
Describedly comprise step by the synthetic high styrene rubber emulsion of high styrene resin emulsion:
E) add reactant, reactant and parts by weight are: deionized water 100～140, the part water that accounts for water gross weight 2/3～4/5, vinylbenzene 60～63, divinyl 10.5～11.5, all activate phase, account for the part molecular weight mediator agent of molecular weight mediator agent gross weight 25%, stir, add initiator, initiation reaction;
F) when cinnamic transformation efficiency reaches 25～35%, add the part molecular weight mediator agent that accounts for molecular weight mediator agent gross weight 10%, continue reaction;
G) when cinnamic transformation efficiency reaches 70～80%, adding parts by weight is 25.5～29.5 divinyl, remaining water and molecular weight mediator agent, continues reaction;
H) when cinnamic transformation efficiency reaches 98%, termination reaction obtains the high styrene rubber emulsion, obtains high styrene rubber through cohesion, drying.
This method flow is brief, simple to operate, process is controlled easily, through the degassing, cohesion, washing, extruding, dehydration, granulation and make high styrene rubber, product can improve characteristics such as the rigidity, hardness, wear resistance, reduction shrinking percentage of rubber item in using the course of processing, every performance reaches international like product (HS-860) level.
Embodiment
Embodiment 1～4: step 1: the preparation water
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Deionized water | 50 | 60 | 70 | 85 |
| Emulsifying agent | (5.25 the mass ratio of fatty acid potassium soap-nilox resin acid potash soap is 2: 1) 4 | 4 (fatty acid potassium soaps) | 5 (nilox resin acid potash soaps) | 6 (nilox resin acid potash soaps) |
| Diffusant (naphthalenesulfonic acid-formaldehyde condensate) | 0.15 | 0.1 | 0.1 | 0.2 |
| Ionogen | (0.2 Repone K) | (0.1 potassiumphosphate) | (0.1 salt of wormwood) | (0.2 salt of wormwood) |
Step 2: preparation activation phase
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Deionized water | 5 | 6 | 8 | 10 |
| Sodium sulfoxylate formaldehyde | 0.1 | 0.1 | 0.2 | 0.2 |
| Disodium ethylene diamine tetraacetate | 0.02 | 0.02 | 0.03 | 0.03 |
| Sytron | 0.01 | 0.01 | 0.02 | 0.02 |
Step 3: synthetic SBR emulsion
At first to a 12M
3Polymeric kettle vacuumizes, and drops into the reactant of following weight ratio example successively, and stirs
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Deionized water | 140 | 130 | 120 | 100 |
| The part water | 4/5 of water | 2/3 of water | 4/5 of water | 11/15 of water |
| The activation phase | All | All | All | All |
| Vinylbenzene | 16 | 16 | 17 | 17 |
| Divinyl | 37 | 38 | 39 | 40 |
| Tert-dodecyl mercaptan | 25% (total amount is 0.65) of total amount | 25% (total amount is 0.2) of total amount | 25% (total amount is 0.3) of total amount | 25% (total amount is 0.5) of total amount |
| Initiator | (0.03 hydrogen peroxide is to alkane in the Meng) | (0.04 di-isopropylbenzene hydroperoxide) | (0.05 hydrogen peroxide is to alkane in the Meng) | (0.05 di-isopropylbenzene hydroperoxide) |
After adding initiator, initiated polymerization, control reaction temperature adds secondary material, following table at 15～35 ℃ when butadiene conversion reaches 25～35%
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Tert-dodecyl mercaptan | 10% (total amount is 0.65) of total amount | 10% (total amount is 0.2) of total amount | 10% (total amount is 0.3) of total amount | 10% (total amount is 0.5) of total amount |
When butadiene conversion reaches 55～65%, add three materials, comprise remaining water and molecular weight mediator agent and vinylbenzene (amount of adding such as following table), continue reaction
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Vinylbenzene | 43 | 44 | 45 | 47 |
Continue to keep reaction after adding material.Water carries out temperature control as refrigerant, and temperature of reaction is no more than 35 ℃, when butadiene conversion reaches 98.0% when above, termination reaction.After polyreaction is finished, the high styrene rubber emulsion is sent into the method for using coupling vacuum stripping after the degassing still flash distillation again, use saturated wetting vapour directly to feed and remove unreacted monomer in the emulsion.Sampling analysis dry solid content, mooney viscosity, residual styrene content.
Embodiment 5～8
Step 1: preparation water (the same)
Step 2: preparation activation phase (the same)
Step 3: synthetic high styrene resin emulsion
At first to a 12M
3Polymeric kettle vacuumizes, and drops into the reactant of following weight ratio example successively, and stirs
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Deionized water | 140 | 130 | 120 | 100 |
| The part water | 4/5 of water | 2/3 of water | 4/5 of water | 11/15 of water |
| Vinylbenzene | 60 | 61 | 62 | 63 |
| Divinyl | 10.5 | 11 | 11 | 11.5 |
| Tert-dodecyl mercaptan | 25% (total amount is 0.65) of total amount | 25% (total amount is 0.2) of total amount | 25% (total amount is 0.3) of total amount | 25% (total amount is 0.5) of total amount |
| The activation phase | All | All | All | All |
| Initiator | (0.03 hydrogen peroxide is to alkane in the Meng) | (0.04 di-isopropylbenzene hydroperoxide) | (0.05 hydrogen peroxide is to alkane in the Meng) | (0.05 di-isopropylbenzene hydroperoxide) |
After adding initiator, initiated polymerization, control reaction temperature adds secondary material, as following table at 15～35 ℃ when the styrene conversion rate reaches 25～35%
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Tert-dodecyl mercaptan | 10% (total amount is 0.65) of total amount | 10% (total amount is 0.2) of total amount | 10% (total amount is 0.3) of total amount | 10% (total amount is 0.5) of total amount |
When the styrene conversion rate reaches 70～80%, add three materials, comprise and divinyl (amount of adding such as following table) and remaining water, molecular weight mediator agent, continue to react
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Divinyl | 25.5 | 26.5 | 27.5 | 29.5 |
Continue to keep reaction after adding material.Water carries out temperature control as refrigerant, and temperature of reaction is no more than 35 ℃, when the styrene conversion rate reaches 98.0% when above, termination reaction.After polyreaction is finished, the high styrene rubber emulsion is sent into the method for using coupling vacuum stripping after the degassing still flash distillation again, use saturated wetting vapour directly to feed and remove unreacted monomer in the emulsion.Sampling analysis dry solid content, mooney viscosity, residual styrene content.
Gained high styrene rubber emulsion index is as follows among the embodiment 1～8:
Solid content: 〉=34%; PH value :～8.8;
Mooney viscosity (ML
1+4 100 ℃) :～54; Combined styrene:＞60%
Emulsion obtains the product high styrene rubber after cohesion, drying, gained high styrene rubber index is as follows:
| Combined styrene, % | ～60 | Mooney viscosity (ML 1+4 100℃) | ～53 | 300% stress at definite elongation, Mpa | ～18.6 |
| Tensile strength at yield, Mpa | ～22.9 | Elongation at break, % | ～345 | 105 ℃ of fugitive constituents, % | ～0.6 |
| Hardness Shao Shi, A | ～84 |
Claims (6)
1. the preparation method of a high styrene rubber, it is characterized in that with vinylbenzene and divinyl be polymerization single polymerization monomer, after adding water, activation phase, molecular weight regulator, deionized water, initiator, polymerization generation SBR emulsion or high styrene resin emulsion, add monomer and molecular weight regulator, continue reaction, directly synthetic high styrene rubber emulsion is through cohesion, dry preparation high styrene rubber; Described SBR emulsion refers to SBR emulsion; Described high styrene resin emulsion refers to that combined styrene content is at 70% above polymer emulsion; Described high styrene rubber emulsion refers to the polymer emulsion of vinylbenzene binding capacity between 40～70%; The component of its reactant and parts by weight are:
Water 54.2～91.4
Activation phase 5.2～11
Tert-dodecyl mercaptan 0.2～0.65 as molecular weight regulator
Initiator 0.03～0.05
Vinylbenzene 59～64
Divinyl 36～41
Deionized water 100～140
Above the component of described water and parts by weight are:
Deionized water 50～85
Emulsifying agent 4～6
Naphthalenesulfonic acid-formaldehyde condensate 0.1～0.2 as diffusant
Ionogen 0.1～0.2
Above described ionogen is Repone K, potassiumphosphate or salt of wormwood.
2. the preparation method of a kind of high styrene rubber according to claim 1 is characterized in that described initiator is that di-isopropylbenzene hydroperoxide or hydrogen peroxide are to alkane in the Meng.
3. the preparation method of a kind of high styrene rubber according to claim 1 is characterized in that described emulsifying agent is the mixture of nilox resin acid potash soap, fatty acid potassium soap or above-claimed cpd.
4. the preparation method of a kind of high styrene rubber according to claim 1 is characterized in that the component of described activation phase and parts by weight are:
Deionized water 5～10
Sodium sulfoxylate formaldehyde 0.1～0.2
Disodium ethylene diamine tetraacetate 0.02～0.03
Sytron 0.01～0.02.
5. the preparation method of a kind of high styrene rubber according to claim 1 is characterized in that describedly comprising step by the synthetic high styrene rubber emulsion of SBR emulsion:
A) add reactant: reactant and parts by weight are, deionized water 100～140, the part water that accounts for water total amount 2/3～4/5, vinylbenzene 16～17, divinyl 37～40, all activate phase, account for the part molecular weight regulator of molecular weight regulator total amount 25%, stir, add initiator, initiation reaction;
B) when the transformation efficiency of divinyl reaches 25～35%, add the part molecular weight regulator that accounts for molecular weight regulator total amount 10%, continue reaction;
C) when the transformation efficiency of divinyl reaches 55～65%, adding parts by weight is 43～47 vinylbenzene, remaining water and molecular weight regulator, continues reaction;
D) when the transformation efficiency of divinyl reaches 98%, termination reaction obtains the high styrene rubber emulsion, obtains high styrene rubber through condensing drying.
6. the preparation method of a kind of high styrene rubber according to claim 1, it is characterized in that described by
The synthetic high styrene rubber emulsion of high styrene resin emulsion comprises step:
A) add reactant: reactant and parts by weight are, deionized water 100～140, the part water that accounts for water total amount 2/3～4/5, vinylbenzene 60～63, divinyl 10.5～11.5, all activate phase, account for the part molecular weight regulator of molecular weight regulator gross weight 25%, stir, add initiator, initiation reaction;
B) when cinnamic transformation efficiency reaches 25～35%, add the part molecular weight regulator that accounts for molecular weight regulator total amount 10%, continue reaction;
C) when cinnamic transformation efficiency reaches 70～80%, adding parts by weight is 25.5～29.5 divinyl, remaining water and molecular weight regulator, continues reaction;
D) when the transformation efficiency of divinyl reaches 98%, termination reaction obtains the high styrene rubber emulsion, obtains high styrene rubber through condensing drying.
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| EP2567985B1 (en) | 2011-09-07 | 2016-11-09 | Trinseo Europe GmbH | Polymer latex with improved mechanical properties and process for preparing said polymer latex |
| CN103254359A (en) * | 2013-01-28 | 2013-08-21 | 安庆华兰科技有限公司 | Production method of powder acrylonitrile butadiene rubber for oil resistance product and soft friction material modification |
| CN104788601B (en) * | 2015-03-17 | 2018-02-13 | 上海强盛化工有限公司 | A kind of latex product fortified SB latex and preparation method thereof |
| CN107337763B (en) * | 2017-09-18 | 2020-03-17 | 烟台世缘橡胶有限公司 | Production process of high styrene rubber |
| CN111019205B (en) * | 2018-10-10 | 2022-03-29 | 中国石油天然气股份有限公司 | Preparation method of polyurethane modified emulsion polymerized styrene butadiene rubber |
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Non-Patent Citations (2)
| Title |
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| 一步法合成高苯橡胶的研究. 米普科，王兴亚.兰化科技，第16卷第4期. 1998 |
| 一步法合成高苯橡胶的研究. 米普科，王兴亚.兰化科技，第16卷第4期. 1998 * |
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