CN115057956B - High-solid-content narrow-distribution polybutadiene latex agglomeration method and application thereof - Google Patents
High-solid-content narrow-distribution polybutadiene latex agglomeration method and application thereof Download PDFInfo
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- CN115057956B CN115057956B CN202210749684.XA CN202210749684A CN115057956B CN 115057956 B CN115057956 B CN 115057956B CN 202210749684 A CN202210749684 A CN 202210749684A CN 115057956 B CN115057956 B CN 115057956B
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- 239000004816 latex Substances 0.000 title claims abstract description 97
- 229920000126 latex Polymers 0.000 title claims abstract description 97
- 238000005054 agglomeration Methods 0.000 title claims abstract description 65
- 230000002776 aggregation Effects 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 58
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 48
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 46
- 238000009826 distribution Methods 0.000 title abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 27
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 32
- 239000000839 emulsion Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 17
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 10
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 8
- 229960003237 betaine Drugs 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- -1 betaine compound Chemical class 0.000 claims description 5
- 229940096992 potassium oleate Drugs 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001339 alkali metal compounds Chemical group 0.000 claims description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229940114930 potassium stearate Drugs 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- RZMWTGFSAMRLQH-UHFFFAOYSA-L disodium;2,2-dihexyl-3-sulfobutanedioate Chemical group [Na+].[Na+].CCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCC RZMWTGFSAMRLQH-UHFFFAOYSA-L 0.000 claims 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical group [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229940043266 rosin Drugs 0.000 claims 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001687 destabilization Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- NVJCKICOBXMJIJ-UHFFFAOYSA-M potassium;1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [K+].C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C([O-])=O NVJCKICOBXMJIJ-UHFFFAOYSA-M 0.000 description 3
- WVFDILODTFJAPA-UHFFFAOYSA-M sodium;1,4-dihexoxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CCCCCCOC(=O)CC(S([O-])(=O)=O)C(=O)OCCCCCC WVFDILODTFJAPA-UHFFFAOYSA-M 0.000 description 3
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 description 2
- 239000005870 Ziram Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000417 polynaphthalene Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 2
- VJWGHGJYLCJIEK-UHFFFAOYSA-N 1,4-bis(6-methylheptoxy)-1,4-dioxobutane-2-sulfonic acid Chemical compound CC(C)CCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCC(C)C VJWGHGJYLCJIEK-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000001987 Pyrus communis Species 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MQKXWEJVDDRQKK-UHFFFAOYSA-N bis(6-methylheptyl) butanedioate Chemical compound CC(C)CCCCCOC(=O)CCC(=O)OCCCCCC(C)C MQKXWEJVDDRQKK-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- GUYXXEXGKVKXAW-UHFFFAOYSA-N prop-2-enenitrile Chemical compound C=CC#N.C=CC#N GUYXXEXGKVKXAW-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009288 screen filtration Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/18—Increasing the size of the dispersed particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a high-solid-content narrow-distribution polybutadiene latex agglomeration method and application thereof. The invention introduces a mixed dispersing agent with double ions in the chemical agglomeration process, improves the stability of the agglomeration process, and the product latex has narrower particle size distribution range and better performance of the finished resin. The method has simple process, solves the problem of poor stability of the latex system in the chemical agglomeration process of the polybutadiene latex, can reduce the dosage of the agglomerating agent and the stabilizing agent, has high solid content and high productivity of the product latex, and is suitable for mass production of ABS resin.
Description
Technical Field
The invention belongs to the technical field of ABS (Acrylonitrile butadiene styrene) resin, and particularly relates to a high-solid-content narrow-distribution polybutadiene latex agglomeration method and application thereof.
Background
Polybutadiene latex is generally used as a rubber phase for providing toughness to the resin during the synthesis of ABS resin. As is well known, the polybutadiene rubber has the best toughening effect when the particle diameter is about 300nm, and the production process can be divided into a one-step method and a two-step method according to different production modes, and compared with the one-step method, the polybutadiene rubber has longer reaction time; the two-step process adopts emulsion polymerization to generate 100nm small-particle-size latex, and then utilizes a physical/chemical agglomeration mode to prepare 300-350nm polybutadiene latex emulsion, so that the polymerization reaction period of the polybutadiene latex is shortened from about 28 hours to 14 hours, and the production capacity of the device is effectively improved.
The traditional agglomeration technology can be divided into four types of freezing agglomeration, mechanical agglomeration, pressure agglomeration and chemical agglomeration, and as described in patent CN113493530A, the various methods have advantages and disadvantages, wherein the chemical agglomeration has the characteristics of controllable product particle size and good performance of the finished ABS resin, and is commonly selected for large-scale industrial production; because of the destabilization to re-stabilization process of the latex in the chemical agglomeration process (the pH value of the emulsion is usually adjusted by adopting an acidic agglomerating agent so as to destroy the double-electronic-layer structure on the surface of the latex, and the latex particles are mutually polymerized and grown into large-particle-size particles under stirring), the operation window is narrow in the actual production, and the destabilization latex is extremely easy to generate a large amount of gumming residues in the process due to the problems of local shearing or uneven addition of the agglomerating agent.
In the prior art, the technical schemes of agglomeration agent multi-point feeding, low-shear strong mixing maximum energy stirrer and the like are adopted, but the problems of poor stability and difficult control still exist; to further improve this process, patent US20170073476a and JP07157501a both propose adding an additional anionic surfactant to the agglomerating agent, which is still active under acidic conditions, and which can achieve protection of part of the two-electron layer during agglomeration, thus widening the process window and reducing the slag discharge under the destabilization regulation of the latex; however, this technique also has a broad agglomeration window, broadens the particle size distribution of the agglomerated latex, and lowers the product performance.
Therefore, there is a need to develop an agglomeration technique for the production of large particle size polybutadiene latex that combines a narrow particle size distribution with a high stability of the process.
Disclosure of Invention
The invention aims to provide an agglomeration process method of polybutadiene latex, which can conveniently and efficiently prepare large-particle-size polybutadiene latex by continuous agglomeration, and the prepared large-particle-size polybutadiene latex has narrower particle size distribution and lower process slag content.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A process for agglomerating polybutadiene latex, said process comprising the steps of:
s1: introducing raw material polybutadiene latex into a reaction vessel, adding a dispersing agent and stirring;
s2: adding an agglomeration agent into the S1 mixture, and stirring to obtain target polybutadiene latex;
S3: adding a stabilizer into the S2 latex, stirring and storing for subsequent emulsion grafting reaction;
Wherein the dispersant of S1 is a mixture of two structural compounds, wherein R 1、R2、R3 is one or more of C6-C16 alkyl:
According to the invention, the dispersing agent with double ions is added into the latex before agglomeration reaction, so that on one hand, the stabilizing system can be realized when the pH value is changed from alkaline to acidic in the agglomeration process; on the other hand, the double-electron layer which can partially neutralize the surface of the latex particles is added before agglomeration due to the double ions, so that agglomeration is more rapid, and the particle size distribution of the produced large-particle-size polybutadiene latex is narrower. Particularly, after the dispersing agent is added, the agglomeration process can be stably implemented under higher solid content index, and meanwhile, the method has the characteristic of lower dosage of the process agglomeration agent, and meets the environment-friendly industrialization requirement of the process.
In the present invention, the dispersant A of S1 is preferably a betaine compound, more preferably alkyl dimethyl betaine; the dispersing agent B is preferably an alkali metal sulfonate, more preferably dihexyl sulfosuccinate sodium salt and/or dioctyl sodium sulfosuccinate; preferably, the ratio of dispersant A to dispersant B is from 0.2 to 5:1, preferably 1-3:1, a step of; preferably, the dispersant is added in an amount of from 20 to 500ppm, preferably from 50 to 300ppm, based on the dry weight of the starting polybutadiene latex;
in the present invention, the particle size of the raw material polybutadiene latex of S1 is 50-150nm, preferably 80-120nm.
In the present invention, the agglomeration temperature of S1 is 5℃to 60℃and preferably 20℃to 50 ℃.
In the present invention, the agglomeration agent S2 is carboxylic acid and/or carboxylic anhydride, preferably acetic acid and/or acetic anhydride; preferably, the agglomerating agent is added in an amount of 0.3 to 3 parts, preferably 0.5 to 2 parts, based on 100 parts of dry weight of the raw polybutadiene latex.
In the invention, the particle size of the target polybutadiene latex of S2 is 250-600nm.
In the invention, the stabilizer S3 is an alkali metal compound, preferably one or more of KOH, naOH, disproportionated potassium abietate, potassium oleate and potassium stearate; preferably, the stabilizer is added in an amount of 0.3 to 3 parts, preferably 0.5 to 2 parts, based on 100 parts of dry weight of the raw polybutadiene latex.
It is another object of the present invention to provide a polybutadiene agglomerated latex.
A polybutadiene agglomerated latex prepared by the agglomeration process described above, said latex having a solids content of >35%, a dispersion index PDI <0.15, and a process slag content <200ppm.
It is a further object of the present invention to provide the use of polybutadiene agglomerated latex.
The use of a polybutadiene agglomerated latex, obtained by the agglomeration process described above, or of a latex as described above, for the emulsion grafting of ABS high-rubber powders, and thus of ABS resins.
In one embodiment, the prepared latex is grafted with acrylonitrile and styrene to prepare grafted powder, and the grafted powder is mixed with SAN according to a fixed proportion to obtain ABS resin slices. The preparation process is as follows:
Agglomerating latex grafting: adding FeSO 4 into the agglomerated latex emulsion, uniformly stirring, gradually heating a reaction system, gradually adding cumene hydroperoxide, styrene, acrylonitrile, tertiary dodecyl mercaptan, potassium oleate and ionized water into the reaction system, continuously adding the materials, and continuously reacting after the addition is completed to obtain grafted latex emulsion;
Coagulation/drying: adding the obtained grafting latex emulsion into a reaction kettle, heating, gradually adding MgSO 4 and deionized water into the reaction kettle, keeping the temperature, uniformly stirring and reacting, filtering the obtained condensed emulsion by adopting stainless steel filter cloth to obtain wet grafting powder, and drying by adopting a vacuum drum dryer to obtain grafting powder;
blending: and (3) adopting a double-screw extruder, adding SAN phase for blending, and cooling and granulating to obtain ABS resin finished product slices.
The invention has the beneficial effects that:
(1) The special composite dispersing agent is adopted in the scheme to improve the problem of wide stability-particle size distribution in the chemical agglomeration process, the ABS resin product has better performance, the strength of a clear kettle can be obviously reduced in batch production, and the automation level of the device is improved.
(2) The use of the dispersing agent also obviously improves the solid content of the latex, reduces the using amount of the agglomerating agent, obviously improves the production capacity of the device, and simultaneously reduces the corrosiveness of a reaction system and the COD of wastewater.
Drawings
FIG. 1 is a graph showing the particle size distribution of the target polybutadiene latex obtained in example 1;
FIG. 2 is a graph showing the particle size distribution of the target polybutadiene latex obtained in comparative example 1.
Detailed description of the preferred embodiments
The invention is further illustrated by the following examples and comparative examples, which, however, do not limit the scope of the invention as claimed.
Raw material specification:
| raw materials/Specification | Manufacturer' s | Specification of specification |
| Glacial acetic acid | Chemical engineering of Xilong | 99.8％ |
| Acetic anhydride | Chemical engineering of Xilong | 98.5％ |
| Dioctyl sulfosuccinate sodium salt | Sortv | >50％ |
| N-dodecyl-N, N-dimethyl betaine | Merck | >97％ |
| N-tetradecyl-N, N-dimethyl betaine | Merck | 98.9％ |
| N-hexadecyl-N, N-dimethyl betaine | Merck | 99.2％ |
| Dihexylsulfosuccinate sodium salt | Shandong Liotai biotechnology | 50％ |
| Diisooctyl sulfosuccinate sodium sulfonate | solvey | 50％ |
| Polynaphthalene formaldehyde sulfonate sodium salt | Flower king | 98.5％ |
| KOH | Alatine | 50％ |
| Oleic acid potassium salt | Qingdao Rueno chemical industry | Technical grade, 35% |
| Disproportionated potassium abietate | Shandong Qianbei chemical industry | Technical grade, 50% |
| Ferrous sulfate heptahydrate | Inock | 99.5％ |
| Cumene hydroperoxide | Nori-on | 85％ |
| Styrene | Wanhua chemistry | 99.5％ |
| Acrylonitrile (Acrylonitrile) | Sierban chemistry | 98.5％ |
| Tert-dodecyl mercaptan | Korean pear tree | >98％ |
| Magnesium sulfate heptahydrate | Chinese medicine | >99.5％ |
| SAN resins | Taiwan Qimei | PN118 |
Experimental facilities:
| Apparatus and method for controlling the operation of a device | Manufacturer' s | Model number |
| Stainless steel reaction kettle | Wisea chemical machinery plant | 5L |
Latex particle size testing: 1g of latex was mixed with 100g of deionized water, and the average particle diameter and dispersibility index were measured according to the dynamic laser scattering method using Malvern Mastersizer laser granulometry.
The prepared latex is grafted by acrylonitrile and styrene to prepare grafted powder, and is mixed with SAN according to a fixed proportion, so that ABS resin slices for performance test can be obtained. The preparation process is as follows:
Agglomerating latex grafting: 100g of latex emulsion obtained by agglomeration is taken, 0.001g of FeSO 4 is added into the latex emulsion, the mixture is uniformly stirred, after the reaction system is gradually heated to 70 ℃, 0.1g of cumene hydroperoxide, 11.7g of styrene, 4.6g of acrylonitrile, 0.2g of tertiary dodecyl mercaptan, 0.3g of potassium oleate and 10g of deionized water are gradually added into the mixture, the continuous feeding time is 3h, and the reaction is continued for 3h after the feeding is completed, so that grafted latex emulsion with the grafting rate of 40%;
Coagulation/drying: 100g of the obtained grafting latex emulsion is added into a reaction kettle, heated to 95 ℃, 4g of MgSO 4 and 40g of deionized water are gradually added into the reaction kettle, the temperature is kept, the uniform stirring reaction is carried out for 1h, the obtained condensed emulsion is filtered by adopting 200-mesh stainless steel filter cloth, wet grafting powder is obtained, and the wet grafting powder is dried for 4h at 60 ℃ under 2KPaA by adopting a vacuum drum dryer, so that grafting powder with the water content of less than 1% is obtained;
Blending: using a twin screw extruder (ZSK 26p 10.6 family of plon), at 210 ℃, taking ziram PN118 as the blended SAN phase, according to PN118: the above grafted powder = 75:25, and cooling and granulating to obtain the ABS resin finished product slice.
Impact properties: and (3) adopting the ABS resin slice obtained by blending, and carrying out sample preparation and impact performance test (a pendulum impact tester Zwick/HIT25 PPlus) according to a GB/T1043 rigid plastic simply supported beam impact test method.
Example 1
3000G of 113.5nm raw material polybutadiene latex (solid content 41.3%, PDI 0.123) was added to a 5L agglomeration reactor, 0.124g N-dodecyl-N, N-dimethyl betaine as a dispersing agent was added thereto, 0.248g of 50% emulsion of diisooctyl succinate sodium sulfonate was added thereto, stirring was started for 5 minutes, and heating was started to a constant temperature at 40 ℃.
Adding 140g of 5% HAc aqueous solution into the mixed latex, uniformly stirring to perform agglomeration reaction, stopping stirring and aging reaction for 8min, adding 110g of 7wt% KOH into the reaction kettle again, uniformly stirring, sampling and testing, wherein the solid content of the agglomerated latex is 35.35%, the average particle size is 303.4nm,PDI 0.095, and the latex slag content is 25ppm (filtering by a 325-mesh filter screen);
Adding 3000g of the latex emulsion obtained by agglomeration into a 5L glass flask, adding 0.03g of FeSO 4 into the glass flask, uniformly stirring, heating to 70 ℃, continuously adding pre-emulsified mixed liquid (containing 3g of cumene hydroperoxide, 482g of styrene, 187g of acrylonitrile, 6g of tertiary dodecyl mercaptan, 9g of potassium oleate and 300g of deionized water) into the glass flask, continuously adding for 3 hours, maintaining the reaction temperature at 70 ℃ for continuous reaction for 3 hours after the addition is finished, and obtaining the grafted latex emulsion, wherein the conversion rate of styrene and acrylonitrile monomers is 93.2% by headspace gas phase analysis, and the grafting rate is 41.89%;
3500g of the obtained grafting latex emulsion is added into a reaction kettle, heated to 95 ℃,600 g of 10wt% MgSO 4 and 1404g of deionized water are gradually added into the reaction kettle, the temperature is kept, the uniform stirring reaction is carried out for 1h, the obtained condensed emulsion is filtered by adopting 200-mesh stainless steel filter cloth, the moisture content is 32.4%, and the obtained condensed emulsion is dried for 12h at 60 ℃ under 2KPaA by adopting a vacuum drum dryer, so as to obtain 1418g of grafting powder with the water content less than 1%;
Using a twin screw extruder (ZSK 26p 10.6 family of plon), at 210 ℃, taking ziram PN118 as the blended SAN phase, according to PN118: the above grafted powder = 75:25, and cooling and granulating to obtain the ABS resin finished product slice. The impact strength of the ABS resin obtained by the analysis was 19.6J/m.
Example 2
3000G of a 108.9nm raw material polybutadiene latex (solid content: 42.3%, PDI: 0.097) was charged into a 5L agglomeration reactor, 0.190g N-tetradecyl-N, N-dimethyl betaine as a dispersant was added thereto, 0.380g of 50% emulsion of dihexyl sodium sulfosuccinate was added thereto, stirring was started for 5 minutes, and heating was started to 30℃at constant temperature.
Adding 155g of 5% HAc aqueous solution into the mixed latex, uniformly stirring to perform agglomeration reaction, stopping stirring and aging reaction for 8min, adding 90g of 10wt% NaOH into the reaction kettle again, uniformly stirring, sampling and testing, wherein the solid content of the agglomerated latex is 36.56%, the average particle size is 285.2nm,PDI 0.089, and the latex slag content is 53ppm (filtering by a 325-mesh filter screen);
The latex obtained by agglomeration is further grafted to prepare graft powder by the method of the example 1, and is mixed by a double screw extruder, and the ABS resin finished product slice is obtained by pelleting. The ABS resin obtained by the analysis was found to have an impact strength of 18.9J/m.
Example 3
3000G of 90.3nm raw material polybutadiene latex (solid content 40.58%, PDI 0.105) was added to a 5L agglomeration reactor, 0.091g N-hexadecyl-N, N-dimethyl betaine as a dispersing agent was added thereto, 0.061g of dioctyl sodium sulfosuccinate 50% emulsion was added thereto, stirring was started for 5 minutes, and heating was started to a constant temperature at 50 ℃.
Adding 180g of 10% acetic anhydride aqueous solution into the mixed latex, uniformly stirring to perform agglomeration reaction, stopping stirring and aging reaction for 20min, adding 50g of 25wt% disproportionated potassium abietate aqueous solution into a reaction kettle again, uniformly stirring, sampling and testing, wherein the solid content of the agglomerated latex is 36.24%, the average particle size is 479.2nm,PDI 0.118, and the latex slag content is 82ppm (325 mesh filter screen filtration);
The latex obtained by agglomeration is further grafted to prepare graft powder by the method of the example 1, and is mixed by a double screw extruder, and the ABS resin finished product slice is obtained by pelleting. The ABS resin obtained by the analysis was found to have an impact strength of 20.7J/m.
Comparative example 1
In comparison with example 1, the dispersant proposed in the present invention was not used.
3000G of 113.5nm polybutadiene latex (solid content 41.3%, PDI 0.123) was added to a 5L agglomeration reactor, and heating was started after stirring for 5min, and the temperature was kept constant when heating to 40 ℃.
Adding 370g of 5% HAc aqueous solution into the mixed latex, uniformly stirring to perform agglomeration reaction, stopping stirring and aging reaction for 8min, adding 300g of 7% KOH into the reaction kettle again, uniformly stirring, sampling and testing, wherein the solid content of the agglomerated latex is 28.87%, the average particle size is 302.7nm,PDI 0.205, and the latex slag content is 373ppm (filtering by a 325-mesh filter screen);
further, the preparation of the graft powder and the ABS resin was carried out by the method described in example 1, and the impact strength of the prepared ABS resin was 16.7J/m.
Comparative example 2
In comparison with example 1, only anionic dispersants are used.
3000G of 113.5nm raw material polybutadiene latex (solid content: 41.3%, PDI: 0.123) was charged into a 5L agglomeration reactor, to which 0.248g of polynaphthalene formaldehyde sulfonate sodium salt was added, and stirring was started for 5 minutes, and heating was continued to a constant temperature of 40 ℃.
Adding 248g of 5% HAc aqueous solution into the mixed latex, uniformly stirring to perform agglomeration reaction, stopping stirring and aging reaction for 8min, adding 210g of 7% KOH into the reaction kettle again, uniformly stirring, sampling and testing, wherein the solid content of the agglomerated latex is 31.75%, the average particle size is 295.9nm,PDI 0.286, and the latex slag content is 234ppm (filtering by a 325-mesh filter screen);
Further, the preparation of the graft powder and the ABS resin was carried out by the method described in example 1, and the impact strength of the prepared ABS resin was 16.3J/m.
From the results, the agglomeration process is more stable after adding trace amounts of agglomeration auxiliary agents, slag can be effectively reduced by about one order of magnitude in the agglomeration process, agglomerated latex has narrower particle size distribution, and the product resin performance is better; the special agglomeration process can be carried out under higher solid content, the consumption of the agglomerating agent and the stabilizing agent is obviously reduced, and the three-waste discharge amount is reduced in the industrialized implementation process.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (11)
1. A process for agglomerating polybutadiene latex, characterized in that it comprises the following steps:
s1: introducing raw material polybutadiene latex into a reaction vessel, adding a dispersing agent and stirring;
s2: adding an agglomeration agent into the S1 mixture, and stirring to obtain target polybutadiene latex;
S3: adding a stabilizer into the S2 latex, stirring and storing for subsequent emulsion grafting reaction;
wherein the dispersant of S1 is a mixture of a dispersant A and a dispersant B containing two structural compounds, wherein R 1、R2、R3 is one or more of C4-C16 alkyl:
Wherein the ratio of the dispersing agent A to the dispersing agent B is 0.2-5:1, a step of;
Wherein the dispersant is added in an amount of 20 to 500ppm based on the dry weight of the raw polybutadiene latex.
2. The agglomeration process according to claim 1, wherein S1 said dispersant a is a betaine compound; the dispersant B is sulfonate of alkali metal;
the ratio of the dispersing agent A to the dispersing agent B is 1-3:1, a step of;
the addition amount of the dispersing agent is 50-300ppm based on the dry weight of the raw material polybutadiene latex;
and/or, the particle size of the raw material polybutadiene latex of S1 is 50-150nm;
And/or, the agglomeration temperature of S1 is 5-60 ℃.
3. Agglomeration process according to claim 2, characterized in that S1 the dispersant a is an alkyl dimethyl betaine; the dispersing agent B is sodium dihexyl sulfosuccinate and/or sodium dioctyl sulfosuccinate;
And/or, the particle size of the raw material polybutadiene latex of S1 is 80-120nm;
and/or, the agglomeration temperature of S1 is 20-50 ℃.
4. Agglomeration process according to claim 1 or 2, characterized in that the agglomerating agent S2 is a carboxylic acid and/or carboxylic anhydride;
and/or, the particle size of the target polybutadiene latex of S2 is 250-600nm.
5. The agglomeration process according to claim 4, characterized in that S2 said agglomerating agent is acetic acid and/or acetic anhydride;
the agglomeration agent is added in an amount of 0.3 to 3 parts based on 100 parts of the dry weight of the raw polybutadiene latex.
6. The agglomeration process according to claim 5, wherein the agglomerating agent S2 is added in an amount of 0.5 to 2 parts based on 100 parts of dry weight of the raw polybutadiene latex.
7. The agglomeration process according to claim 1, wherein S3 said stabilizer is an alkali metal compound.
8. The agglomeration process according to claim 7, wherein S3 said stabilizer is one or more of KOH, naOH, disproportionated potassium rosin, potassium oleate and potassium stearate;
The stabilizer is added in an amount of 0.3 to 3 parts based on 100 parts of the dry weight of the raw polybutadiene latex.
9. Agglomeration process according to claim 8, characterized in that the stabilizer is added in an amount of 0.5 to 2 parts, based on 100 parts of dry weight of the starting polybutadiene latex.
10. Polybutadiene agglomerated latex, prepared by the agglomeration process according to any of claims 1 to 9, characterized in that it has a solids content of >35%, a dispersity index PDI <0.15 and a process slag content <200ppm.
11. Use of a polybutadiene agglomerated latex obtained by the agglomeration process according to any of claims 1 to 9, or according to claim 10, for the preparation of ABS high-powder, and therefore ABS resins, by emulsion grafting.
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| CN112940204A (en) * | 2021-02-04 | 2021-06-11 | 万华化学(四川)有限公司 | Preparation method of polybutadiene latex for agglomeration and prepared ABS resin |
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| CN1048504C (en) * | 1991-10-31 | 2000-01-19 | 武田药品工业株式会社 | Production of copolymer latices |
| JP3248978B2 (en) * | 1993-05-13 | 2002-01-21 | 花王株式会社 | Stabilizer for deproteinized natural rubber latex and method for producing stabilized deproteinized natural rubber latex using the same |
| US5455315A (en) * | 1994-06-06 | 1995-10-03 | Xerox Corporation | Emulsion polymerization processes and toners thereof |
| GB2364260A (en) * | 2000-06-30 | 2002-01-23 | Great Lakes Chemical Corp | Flame retardant dispersible powders on a wax,polymer or organic carrier |
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| CN104327281B (en) * | 2014-11-03 | 2017-11-14 | 天津大沽化工股份有限公司 | A kind of preparation method of the polybutadiene latex of Unimodal Distribution |
| CN109517286A (en) * | 2017-09-18 | 2019-03-26 | 中国石油天然气股份有限公司 | ABS resin and preparation method thereof |
| CN112194764B (en) * | 2019-07-08 | 2022-03-08 | 万华化学集团股份有限公司 | Preparation method of polybutadiene latex |
| CN113493529B (en) * | 2020-04-07 | 2022-09-20 | 万华化学集团股份有限公司 | Preparation method of polybutadiene latex with double particle size distribution |
| CN113651903B (en) * | 2021-08-10 | 2023-05-26 | 上海中化科技有限公司 | Method for preparing large-particle-size polybutadiene latex based on high molecular agglomeration technology |
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