CN102190741A - Method for coagulating rubber latex - Google Patents

Method for coagulating rubber latex Download PDF

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Publication number
CN102190741A
CN102190741A CN 201010130406 CN201010130406A CN102190741A CN 102190741 A CN102190741 A CN 102190741A CN 201010130406 CN201010130406 CN 201010130406 CN 201010130406 A CN201010130406 A CN 201010130406A CN 102190741 A CN102190741 A CN 102190741A
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latex
arm
rubber latex
add
rubber
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CN102190741B (en
Inventor
张元寿
赵继忠
梁滔
钟启林
于奎
桂强
徐典宏
孙红霞
董万卓
吴宇
张志强
李炳泉
朱晶
武爱军
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Petrochina Co Ltd
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Petrochina Co Ltd
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Abstract

The invention relates to a method for continuously coagulating latex with low energy consumption and high production efficiency, which adopts a tubular static mixer, rubber latex is added into a main pipe, coagulant or other auxiliary agents are added into a branch pipe in a parallel flow manner, one or more nozzles are arranged in the main pipe, and the branch pipe is preferably arranged behind the nozzles. The branch pipes can be one or more, and are respectively used as adding pipelines of coagulant or other auxiliary agents, and the branch pipes are arranged behind the spray nozzles, so that the latex and the coagulant are continuously mixed at a certain temperature and time, and the latex is continuously coagulated into a suspension mixture of solid rubber particles and coagulated mother liquor in a turbulent flow state. The rubber particles prepared by the latex coagulation method are uniform, the impurity content is low, the coagulation time is short, and the production efficiency is high. Can be suitable for synthetic rubber latex and natural rubber latex which contain gel, have no gel, have high Mooney viscosity, low Mooney viscosity, have polar groups and the like and have strong adhesiveness.

Description

A kind of method of rubber latex cohesion
Technical field
The present invention relates to a kind of condensing method of rubber latex, in more detail, is a kind of continuous condensing method of rubber latex.
Background technology
At present, the condensing method of relevant latex is existing multiple, as with latex being the positive coacervation that raw material adds flocculation agent; With the flocculation agent is the anti-coacervation that raw material adds latex; It with latex, glue convection drying coacervation of raw material etc.
Positive coacervation:
Directly coacervation is meant under agitation condition, segmentation adds flocculation agent in latex, or latex is directly joined in the flocculation agent method of cohesion rubber, though can obtain well behaved rubber, using this method is intermittently preparation, and production efficiency is low, the energy consumption height, cohesion back rubber form is irregular, and body is bigger, needs the compression moulding packing.
The preparation method of acrylonitrile-butadiene rubber powder among the patent CN93101142.6, it is the positive coacervation batch process for preparing of a kind of employing, be that segmentation adds monovalence and divalent metal salt brine solution in nitrile rubber, through pre-coagulate, flocculation, micelle sclerosis equal segments cohesion complex process, several steps is finished in corresponding several separate mixing tank, therefore exist production efficiency low, shortcoming such as energy consumption, material consumption are big.
Anti-coacervation:
Latex is directly joined the anti-method of coagulating for preparing rubber in the flocculation agent, instead is mutation process with fixed attention, and pool time is extremely short, original stable latex is destroyed in moment, easily forms sealing coat, generally, form the bag slurry, flocculating result is relatively poor, only is adapted to resin emulsion at present and becomes powder.
All there be the problem of cleaning cohesion with equipment in above method, and nonproductive consumption rate is bigger on raw material, production time, plant factor.
US4265939 discloses a kind of method of continuous production of rubber powder, latex is mixed with flocculation agent, to condense latex again and deliver in the extra heavy pipe and mixed with polymers as coating-forming agent, cohesion can make tube wall produce on deleterious deposition or the wall to lump in tubule.
CN1117117C discloses a kind of method that is used for making continuously the rubber powder that contains filler, wherein, and with liquid-phase mixing filler suspension and rubber latex.Liquid form mixt is carried by a pipe, mixes the rubber powder that contains filler with a kind of condensing agent and precipitation in pipe at least.Liquid form mixt is carried by the throttle position that at least one is arranged in the pipe, and the latter has variable throttling cross section; The characteristics of this method are to mix throttling more earlier, promptly are to make rubber latex and filler be mixed into suspension to mix through throttling, add behind condensing agent or the coating-forming agent more further throttling again and mix, and this method amount of filler is big, and efficient is not high, and it is bigger to produce consumption rate.
Need a kind of condensing method of exploitation at present badly, adopt the successive method, can be with the direct condensation powdering of all kinds latex, it is even to produce rubber particles, and pool time is short, and cohesion equipment does not need cleaning, the method for the continuous cohesion latex that energy consumption is low, production efficiency is high substantially.
Summary of the invention
The object of the present invention is to provide the method for the continuous cohesion rubber latex that a kind of energy consumption is low, production efficiency is high.
The condensing method of rubber latex of the present invention is rubber latex to be fed tubular static mixer condense continuously, tubular static mixer contains to be responsible for and arm, in the person in charge, add rubber latex, arm and stream add flocculation agent or and other auxiliary agent, one or more nozzles are arranged in the person in charge, arm is located at the nozzle rear, and the auxiliary agent that is added to the person in charge by arm mixes with it under rubber latex turbulent flows state; Condensation temperature is 25~45 ℃, pool time 0.5~10min.
0.4~3 millimeter of rubber grain particle diameter after condensing method cohesion of the present invention, product after the cohesion obtains difform rubber product through different subsequent handlings again, as obtaining powdered rubber product or granulated rubber product through chemistry or physical isolation processing; Also can make sheet rubber by press filtration, washing through fourdrinier wire.
Arm can be one or more, respectively as flocculation agent or and the adding pipeline of other auxiliary agent, arm is located at the nozzle rear, makes latex and flocculation agent that latex is mixed continuously and is condensed into the suspended mixture that contains solid rubber small-particle and cohesion back mother liquor.The present invention does not get rid of and uses other auxiliary agent, as thinner, separant, coating etc., and also special requirement and flow addition sequence not.In the arm also can in establish nozzle, turbulization when its material being entered be responsible for to mix is mixed more abundant.
The present invention also condensing method of a kind of rubber latex of special recommendation is rubber latex to be fed tubular static mixer condense continuously, tubular static mixer contains to be responsible for and three arms, in the person in charge, add rubber latex, add univalent metal salt solution in first arm, adding two and/or trivalent metal salts solution add entry or separant, coating solution in the 3rd arm in second arm.The dried glue weight of latex is 100 parts of weight meters, preferably 25~30 parts of the amounts of the univalent metal salt that adds in first arm, preferably 10~15 parts of the amounts of the monovalence that adds in second arm, divalence and/or trivalent metal salt add preferably 8~12 parts of the amounts of entry or separant, coating in the 3rd arm.
Built-in nozzle form the present invention is not limited especially in the pipe, be preferably conical, the person in charge can be that straight tube also can be an adapter bonnet, difference according to institute's coagel dairy products kind, select suitable caliber and shape, as being chosen in the nozzle position, expanding with arm connecting portion caliber, caliber after the expansion is 1.3~1.5 times of the preceding caliber of expansion, make it enough big space and obtain best turbulent flow mixed effect, finish chemical phase transition process in physical mixing processes, promptly Ye Tai latex changes solid-state rubber particles into.
The method of special recommendation of the present invention is to have among the rubber latex person in charge in conveying, add flocculation agent (univalent metal salt or two, trivalent metal salts solution) by arm, it is mixed in the turbulent flows state and be condensed into short grained process, latex is condensed with fine granularity.
Characteristics of the present invention are to adopt the tubular type equipment of simple built-in nozzle to realize the continuity that rubber latex condenses.
Rubber latex among the present invention can be a natural rubber latex, it also can be synthetic latex, particularly used the emulsion polymerization latex of negatively charged ion or nonionic emulsifying agent, the independent polymkeric substance-content of polybutadiene rubber latex of conjugated diolefine hydrocarbon compound that polymerization makes as conventional emulsion, chloroprene rubber latex etc.; The binary of vinyl compounds such as conjugated diolefine hydrocarbon compound and vinylbenzene, vinyl cyanide, vinylformic acid, methacrylic acid or terpolymer-styrene butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, carboxylic styrene-butadiene rubber latex etc.
The used flocculation agent of the present invention is univalent metal salt, divalent metal salt, also can be trivalent metal salt, needs to select different flocculation agent for use according to different latex, can be NaCl, KCl, CaCl 2, K 2SO 4, H 2SO 4, MgSO 4, Zn 2SO 4, in the alum etc. one or more.
These flocculation agent---univalent metal salt, divalence, trivalent metal salt are 100 parts of weight in the dried glue weight of latex, and addition is preferably 1~40 part; It uses with aqueous solution form, and concentration is the general mass percent concentration of this technical field, is preferably 2%~25%.The flocculation agent consumption is relevant with the kind of latex, the flocculation agent consumption or (with) the concentration deficiency, latex is difficult for breakdown of emulsion, or forms oversize particle and block; If consumption is too big, though can form particle, can increase the flocculation agent consumption, increase product cost.The present invention does not do unqualified to the pH value of rubber latex.The present invention does not get rid of the use of other auxiliary agent that is suitable for condensing yet.
Condensation temperature is 25~45 ℃ among the present invention, because rubber latex uses tubular static mixer of the present invention to condense continuously, therefore on the operational condition with prior art in the cohesion of still formula different, pool time is shorter, therefore the condensation temperature of special recommendation of the present invention is 35~45 ℃, crosses the low or too high form that all can influence aggregated particle.
Pool time is short among the present invention, generally is preferably in 0.5~10min, but the too short form that also can influence aggregated particle of pool time.
The rubber particles that uses the method for emulsion condensation of the present invention to make is even, and foreign matter content is few, and pool time is short, the production efficiency height.Can be adapted to contain gel, gel-free, high Mooney viscosity, low mooney viscosity and have strong synthetic rubber latex and the natural rubber latexes of cementability such as polar group.
Description of drawings
Fig. 1 is an example of the method for application emulsion condensation of the present invention.
Among the figure:
A-represents the monovalent salt mixing solutions
B-represents the divalent salts mixing solutions
C-represents two, the trivalent mixed salt solution
L-represents the direction of latex and adding
M-represents to be condensed into the suspended mixture of solid rubber small-particle and cohesion back mother liquor
1,2,3,4,5,6-represents built-in nozzle
Fig. 2 is built-in nozzle section synoptic diagram in being responsible for.
Fig. 3, Fig. 4, Fig. 5 are responsible for for the method for using emulsion condensation of the present invention and are the example of adapter bonnet.
Embodiment
Below illustrate that with embodiment but the present invention is not limited to these embodiment.Unless outside specializing among the embodiment, " part ", " % " all refer to mass percent.Mixed liquor A is a univalent metal salt solution, and mixed liquid B is the divalent metal salts solution, and mixed solution C is two, the trivalent metal salts solution, and concentration is respectively 15%, 12%, 18%.A, B, C are added to the person in charge by different arms respectively.
Rubber latex among the embodiment is as described below:
1. paracril latex (to call NBR in the following text)
The nitrile rubber that CNPC's Lanzhou Petrochemical is produced.
2. styrene-butadiene latex (to call SBR in the following text)
Styrene butadiene rubber latex SBR-1500, XSBR, SBR-1712 that CNPC's Lanzhou Petrochemical is produced.
3. content of polybutadiene rubber latex (to call BR in the following text)
The polybutadiene latex that CNPC Lanzhou Petrochemical synthetic rubber plant produces.
4. carboxylic acrylonitrile butadiene rubber latex, the commercially available prod.
What the emulsion condensation device used is device shown in Figure 1.
Embodiment 1
What the emulsion condensation device used is device shown in Figure 1, and wherein the diameter of Zhu Guaning is DN125, and the diameter of arm is DN100.Condensation temperature is 35 ℃, pool time 2min.(pool time is meant from latex and flocculation agent and begins to add the timed interval of cohesion pipe to condensation product inflow receiving pit that following examples together.)
First step: saturated nacl aqueous solution mixes with soft water, forms mixed liquor A;
Second step: by storage tank with pump through filter, NBR latex is delivered to the emulsion condensation device---cohesion is responsible for, and the mixed liquor A of delivering to first arm in first nozzle (its add-on be latex solid content 25%) is mixed the formation throw out;
Third step: the mixed liquid B that the second step gained throw out is delivered to second arm in second nozzle (its add-on be latex solid content 8%) is mixed, and forms condensation product; Mixed liquid B is MgSO 4The aqueous solution.
The 4th step: the mixed solution C that is delivered to the 3rd arm in the 3rd nozzle by third step gained condensation product mixes (its add-on be latex solid content 3%), in condensation product added receiving pit before the filter screen along pipeline, fourdrinier wire forms adhesive tape on the equal then uniform flow, the elimination whey liquid, through washing, press filtration, vacuum and drying, be packaged into product.Mixed solution C is CaCl 2The aqueous solution.
The condensation product particle grain size distribution is :≤2.5mm accounts for 85%, and≤2.0mm accounts for 75%.
Embodiment 2
What the emulsion condensation device used is device shown in Figure 1, and wherein the diameter of Zhu Guaning is DN125, and the diameter of arm is DN100.Condensation temperature is 40 ℃, pool time 4min.
First step: saturated nacl aqueous solution mixes with soft water, forms mixed liquor A;
Second step: by storage tank with pump through filter, deliver to the NBR latex of cohesion pipe, in first nozzle, mixes the formation throw out with mixed liquor A (its add-on be latex solid content 18%);
Third step: with the second step gained throw out in second nozzle with mixed liquid B (MgSO 4The aqueous solution, add-on be the latex solid content 12%) mix, form condensation product;
The 4th step: in the 3rd nozzle, mix with water by third step gained condensation product, condensation product is added the slurry receiver successively along pipeline, in groove, add separant potassium stearate soap lye (add-on be in the groove rubber solid content 10%, soap lye concentration is 15%), through surperficial slaking and effective isolation processing, after sending into the dehydration of precession horizontal centrifuge, dry and screening operation obtains qualified powdered rubber product by vacuum pneumatic, and the condensation product particle grain size distribution is :≤1.25mm account for 95% ,≤1.0mm account for 75% ,≤0.5mm account for 55%.
Embodiment 3
What the emulsion condensation device used is device shown in Figure 1, and wherein the diameter of Zhu Guaning is DN125, and the diameter of arm is DN100.Condensation temperature is 35 ℃, pool time 5min.
First step: saturated nacl aqueous solution mixes with soft water, forms mixed liquor A;
Second step: by storage tank with pump through filter, deliver to the NBR latex of cohesion pipe, in first nozzle, mixes the formation throw out with mixed liquor A (its add-on be latex solid content 25%);
Third step: the second step gained throw out is mixed with mixed liquid B (its add-on be latex solid content 8~9%) in second nozzle, form condensation product; B is ZnSO 4The aqueous solution.
The 4th step: mix with water in the 3rd nozzle by third step gained condensation product, condensation product is added receiving pit before the filter screen along pipeline in, then all on the uniform flow fourdrinier wire form adhesive tape, the elimination whey liquid through washing, press filtration, vacuum and drying, is packaged into product.The condensation product particle grain size distribution is :≤1.0mm account for 95% ,≤0.5mm account for 45%.
Embodiment 4
What the emulsion condensation device used is device shown in Figure 1, and wherein the diameter of Zhu Guaning is DN125, and the diameter of arm is DN100.Condensation temperature is 30 ℃, pool time 6min.
First step: saturated nacl aqueous solution mixes with soft water, forms mixed liquor A;
Second step: by storage tank with pump through filter, deliver to the SBR latex of cohesion pipe, in first nozzle, mixes the formation throw out with mixed liquor A (its add-on be latex solid content 30%);
Third step: the second step gained throw out is mixed with mixed liquid B (its add-on be latex solid content 5%) in second nozzle, form condensation product; B is the sodium chloride-containing aqueous solution.
The 4th step: mix with water in the 3rd nozzle by third step gained condensation product, condensation product is added receiving pit before the filter screen along pipeline in, all the uniform flow upper filter screen forms blob of viscose then, the elimination whey liquid through washing, vacuum, drying and briquetting, is packaged into product.The condensation product particle grain size distribution is :≤1.25mm account for 99% ,≤1.0mm account for 89% ,≤0.5mm account for 75%.
Embodiment 5
What the emulsion condensation device used is device shown in Figure 1, and wherein the diameter of Zhu Guaning is DN125, and the diameter of arm is DN100, and condensation temperature is 30~35 ℃, pool time 2min.
First step: saturated nacl aqueous solution mixes with soft water, forms mixed liquor A;
Second step: by storage tank with pump through filter, deliver to the content of polybutadiene rubber latex of cohesion pipe, in first nozzle, mixes the formation throw out with mixed solution (its add-on be latex solid content 12%) A;
Third step: the second step gained throw out is mixed with mixed liquid B (its add-on be latex solid content 5%) in second nozzle, form condensation product; B is MgSO 4The aqueous solution.
The 4th step: in the 3rd nozzle, mix with mixed solution C (its add-on be latex solid content 5%) by third step gained condensation product, in condensation product added receiving pit before the filter screen along pipeline, fourdrinier wire forms adhesive tape on the equal then uniform flow, the elimination whey liquid, through washing, press filtration, vacuum and drying, be packaged into product.Mixed solution C is an alum solution.
The condensation product particle grain size distribution is :≤1.25mm account for 98% ,≤1.0mm account for 95% ,≤0.5mm account for 65%.
Embodiment 6
What the emulsion condensation device used is device shown in Figure 1, and wherein the diameter of Zhu Guaning is DN125, and the diameter of arm is DN100.Condensation temperature is 40 ℃, pool time 2min.
First step: saturated nacl aqueous solution mixes with soft water, forms mixed liquor A;
Second step: by storage tank with pump through filter, deliver to the carboxy nitrile rubber latex of cohesion pipe, in first nozzle, mixes the formation throw out with mixed liquor A (its add-on be latex solid content 18%);
Third step: with the second step gained throw out in second nozzle and K 2SO 4Aqueous solution forms condensation product, K 2SO 4Add-on is 17% of a latex solid content;
The 4th step: condensation product is added the slurry receiver successively along pipeline, in groove, add the separant Magnesium Stearate, through surperficial slaking and isolation processing, send into the dehydration of precession horizontal centrifuge after, dry and screening operation obtains qualified powdered rubber product by vacuum pneumatic.The condensation product particle grain size distribution is :≤1.25mm account for 97% ,≤1.0mm account for 95% ,≤0.5mm account for 75%.
The product salient features:
Product mainly is powder and sheet, niggerhead, its leading indicator be rubber become content in 97% above moisture content below 1.0%, saltiness is below 1.5%.
Comparative Examples 1:
According to the identical condition of embodiment, only be to change cohesion equipment, the arm entry position is re-established as the place ahead of being responsible for nozzle, its flocculating result is not good at the rear of being responsible for nozzle, cause the turbulent flow mixed effect poor, cohesion back particle is inhomogeneous, and it is big and irregular that particle diameter becomes, even can cause line clogging.
According to the condition of embodiment 1, the arm entry position is re-established as the place ahead of being responsible for nozzle, condensation temperature is 35 ℃, its flocculating result is not good at the rear of being responsible for nozzle, the condensation product particle grain size distribution is :≤3.0mm accounts for 95%, and≤2.0mm accounts for 25%, and≤1.0mm accounts for 5%, it is big that flocculated particle obviously becomes, and forming bulk easily, blocking pipeline also forms the coherent packet slurry easily, cause cohesion not exclusively, be difficult for dry.

Claims (10)

1. the method for an emulsion condensation, it is characterized in that rubber latex is fed tubular static mixer to be condensed continuously, tubular static mixer contains to be responsible for and arm, in the person in charge, add rubber latex, arm and stream add flocculation agent or and other auxiliary agent, one or more nozzles are arranged in the person in charge, and arm is located at the nozzle rear, and the auxiliary agent that is added to the person in charge by arm mixes with it under rubber latex turbulent flows state; Condensation temperature is 25~45 ℃, pool time 0.5~10min.
2. method according to claim 1, it is characterized in that being responsible for is adapter bonnet, expands at the nozzle position and/or with arm connecting portion caliber.
3. method according to claim 1 is characterized in that arm is one or more, respectively as flocculation agent or/and the adding pipeline of other auxiliary agent.
4. method according to claim 1 is characterized in that establishing in the arm nozzle.
5. method according to claim 3, it is characterized in that rubber latex is fed tubular static mixer to be condensed continuously, tubular static mixer contains to be responsible for and three arms, in the person in charge, add rubber latex, add univalent metal salt solution in first arm, in second arm, add monovalence, two and/or the trivalent metal salts solution, in the 3rd arm, add entry, separant and/or coating solution.
6. method according to claim 5, it is characterized in that the dried glue weight of latex is 100 parts of weight meters, the amount of the univalent metal salt that adds in first arm is 25~30 parts, the amount of the monovalence that adds in second arm, divalence and/or trivalent metal salt is 10~15 parts, and the amount that adds entry or separant, coating in the 3rd arm is 8~12 parts.
7. method according to claim 1 is characterized in that rubber latex is a natural rubber latex, or the synthetic latex of letex polymerization.
8. method according to claim 7 is characterized in that synthetic latex is content of polybutadiene rubber latex, chloroprene rubber latex, styrene butadiene rubber latex, paracril latex, carboxy nitrile rubber latex or carboxylic styrene-butadiene rubber latex.
9. method according to claim 1 is characterized in that flocculation agent is NaCl, KCl, CaCl 2, K 2SO 4, H 2SO 4, MgSO 4, Zn 2SO 4, in the alum one or more.
10. method according to claim 1 is characterized in that flocculation agent is 100 parts of weight in the dried glue weight of latex, and addition is 1~40 part.
CN 201010130406 2010-03-19 2010-03-19 Method for coagulating rubber latex Active CN102190741B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103804735A (en) * 2012-11-14 2014-05-21 中国石油天然气股份有限公司 Preparation method of modified oil-extended powder styrene-butadiene rubber
CN103864963A (en) * 2014-03-25 2014-06-18 北京化工大学 Preparation method for low-heat productivity natural rubber
CN104292369A (en) * 2014-11-03 2015-01-21 上海三爱富新材料股份有限公司 Continuous condensation method of perfluorinated ethylene propylene emulsion
CN104558257A (en) * 2013-10-17 2015-04-29 海南大学 Quick granulation device for natural latex
CN104710547A (en) * 2013-12-17 2015-06-17 北方华锦化学工业集团有限公司 Agglomeration method of polybutadiene latex used for acrylonitrile butadiene styrene (ABS) resin
CN110272511A (en) * 2018-03-13 2019-09-24 中国石油天然气股份有限公司 Process for recovering polymer from polymer emulsion

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US4446309A (en) * 1981-03-05 1984-05-01 Japan Synthetic Rubber Co., Ltd. Method and apparatus for continuously coagulating a rubbery polymer latex
CN1198758A (en) * 1996-06-03 1998-11-11 埃勒夫阿托化学有限公司 Method for producing coagulated polymer latex particles
CN1569906A (en) * 2003-07-17 2005-01-26 中国石油天然气股份有限公司 Method for preparing powdered rubber through continuous coagulation

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US4446309A (en) * 1981-03-05 1984-05-01 Japan Synthetic Rubber Co., Ltd. Method and apparatus for continuously coagulating a rubbery polymer latex
CN1198758A (en) * 1996-06-03 1998-11-11 埃勒夫阿托化学有限公司 Method for producing coagulated polymer latex particles
CN1569906A (en) * 2003-07-17 2005-01-26 中国石油天然气股份有限公司 Method for preparing powdered rubber through continuous coagulation

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103804735A (en) * 2012-11-14 2014-05-21 中国石油天然气股份有限公司 Preparation method of modified oil-extended powder styrene-butadiene rubber
CN103804735B (en) * 2012-11-14 2016-06-08 中国石油天然气股份有限公司 Preparation method of modified oil-extended powder styrene-butadiene rubber
CN104558257A (en) * 2013-10-17 2015-04-29 海南大学 Quick granulation device for natural latex
CN104558257B (en) * 2013-10-17 2016-05-04 海南大学 The device of the quick granulation of a kind of Heveatex
CN104710547A (en) * 2013-12-17 2015-06-17 北方华锦化学工业集团有限公司 Agglomeration method of polybutadiene latex used for acrylonitrile butadiene styrene (ABS) resin
CN103864963A (en) * 2014-03-25 2014-06-18 北京化工大学 Preparation method for low-heat productivity natural rubber
CN103864963B (en) * 2014-03-25 2015-12-09 北京化工大学 A kind of preparation method of low-heat-generation natural rubber
CN104292369A (en) * 2014-11-03 2015-01-21 上海三爱富新材料股份有限公司 Continuous condensation method of perfluorinated ethylene propylene emulsion
CN110272511A (en) * 2018-03-13 2019-09-24 中国石油天然气股份有限公司 Process for recovering polymer from polymer emulsion
CN110272511B (en) * 2018-03-13 2022-03-29 中国石油天然气股份有限公司 Process for recovering polymer from polymer emulsion

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