CN111234294A - Preparation method of thermal expansion microspheres - Google Patents
Preparation method of thermal expansion microspheres Download PDFInfo
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- CN111234294A CN111234294A CN202010085026.6A CN202010085026A CN111234294A CN 111234294 A CN111234294 A CN 111234294A CN 202010085026 A CN202010085026 A CN 202010085026A CN 111234294 A CN111234294 A CN 111234294A
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- China
- Prior art keywords
- methacrylate
- weight
- parts
- thermally expandable
- expandable microspheres
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- 239000004005 microsphere Substances 0.000 title claims description 34
- 238000002360 preparation method Methods 0.000 title claims description 29
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920000103 Expandable microsphere Polymers 0.000 claims abstract description 14
- 239000004088 foaming agent Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 9
- 239000002612 dispersion medium Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000012071 phase Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 26
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 20
- 239000000725 suspension Substances 0.000 claims description 19
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 13
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 10
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004604 Blowing Agent Substances 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkali metal nitrite Chemical class 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 claims description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 3
- COXCGWKSEPPDAA-UHFFFAOYSA-N 2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)C#N COXCGWKSEPPDAA-UHFFFAOYSA-N 0.000 claims description 3
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 3
- HTWRFCRQSLVESJ-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOC(=O)C(C)=C HTWRFCRQSLVESJ-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 3
- 150000001451 organic peroxides Chemical group 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract description 2
- 230000009477 glass transition Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 26
- 239000007788 liquid Substances 0.000 description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 235000010288 sodium nitrite Nutrition 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 4
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010558 suspension polymerization method Methods 0.000 description 4
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/20—Making expandable particles by suspension polymerisation in the presence of the blowing agent
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention provides a method for producing thermally expandable microspheres comprising a thermoplastic resin shell and a foaming agent encapsulated in the shell and having a boiling point not higher than the softening point of the thermoplastic resin, the method comprising the steps of: in an aqueous dispersion medium, a polymerizable component is subjected to suspension polymerization in the presence of a water-soluble composition, an acrylic monomer composition is adopted as a main monomer of the polymerizable component, a shell with high barrier property and high glass transition temperature is formed after polymerization, and a virulent acrylonitrile monomer is not adopted, so that the comprehensive cost of monomer raw materials is reduced, the safety in the production operation process is improved, and the potential pollution risk of the production environment is reduced.
Description
Technical Field
The invention relates to a preparation method of thermal expansion microspheres, belonging to the technical field of preparation of thermal expansion microspheres by a suspension polymerization method.
Background
The great expansion capacity of the thermally expandable microspheres makes them useful in a wide variety of fields, for example, to reduce the mass of products, to change the properties of products (such as thermal, acoustic and electrical insulation properties) and to save the amount of materials used; the thermal expansion microsphere also has the advantages of excellent solvent resistance, wear resistance, good mechanical property, no toxicity, no pollution and the like. At present, the thermal expansion microspheres are prepared by a suspension polymerization method which is a common method for synthesizing functional polymer microspheres at home and abroad, and a plurality of monomers and foaming agents are copolymerized in liquid drops and are precipitated on the surfaces of the liquid drops by the suspension polymerization method to obtain the thermal expansion microspheres with a core-shell structure. And the suspension polymerization method for preparing the thermal expansion microspheres at home and abroad at present basically adopts virulent acrylonitrile as a main monomer, and has the advantages of low operation safety, strict environmental protection requirement, high cost and complex process control.
Therefore, there is a need for a novel method for preparing thermally expandable microspheres.
Disclosure of Invention
The invention aims to solve the defects of high toxicity, low operation safety and high environmental protection requirement in the prior art and provide a monomer composition for replacing acrylonitrile monomers.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
the present invention provides a method for producing thermally expandable microspheres comprising a thermoplastic resin shell and a foaming agent encapsulated in the shell and having a boiling point not higher than the softening point of the thermoplastic resin, wherein the method comprises the steps of:
(1) preparation of oil phase: mixing 80-200 parts by weight of foaming agent, 100 parts by weight of polymerization combined monomer composition, 0.05-5 parts by weight of cross-linking agent and 0.01-10 parts by weight of initiator to prepare oil phase;
(2) preparation of the aqueous phase: mixing 0.001-2 parts by weight of a water-soluble composition, 100-800 parts by weight of an aqueous dispersion medium, 5-50 parts by weight of a dispersion stabilizer and 0.005-0.03 parts by weight of an alkali metal nitrite inhibitor to prepare an aqueous phase;
(3) preparation of thermally expanded microspheres: and (3) mixing the oil phase in the step (1) with the water phase in the step (2) to prepare a suspension, then transferring the suspension into a reaction kettle, heating to 35-105 ℃ in the atmosphere of nitrogen, reacting for 8-20h, and drying to obtain the thermal expansion microspheres.
In a preferred embodiment of the invention, the blowing agent is one or more of isobutane, isopentane, n-pentane, isohexane, isooctane, or n-octane, preferably isopentane or isooctane.
In a preferred embodiment of the present invention, the polymeric combination monomer composition comprises one or more of methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, methyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, N dimethylacrylamide or poly (ethylene glycol) methyl methacrylate, preferably comprises methyl methacrylate, N dimethylacrylamide, poly (ethylene glycol) methyl methacrylate, isobornyl methacrylate and hexafluorobutyl methacrylate.
In a more preferred embodiment of the invention, the weight ratio of methyl methacrylate, N dimethylacrylamide, poly (ethylene glycol) methyl methacrylate, isobornyl methacrylate, and hexafluorobutyl methacrylate is 8: 2.5: 0.2: 1: 0.5.
in a preferred embodiment of the present invention, the crosslinking agent is one or more of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triallyl cyanurate, 1, 3-propanediol dimethacrylate or 1, 4-butanediol dimethacrylate.
In a preferred embodiment of the present invention, the water-soluble composition comprises polyvinylpyrrolidone and sodium lauryl sulfate.
In a preferred embodiment of the present invention, the blowing agent is present in an amount of 23 to 32 parts by weight.
In a preferred embodiment of the present invention, the initiator is an organic peroxide or azo compound, preferably one or more of dibenzoyl peroxide, dilauryl peroxide, didecanoic acid peroxide, tert-butyl peracetate, tert-butyl peraurate or azobisisobutyronitrile, 2 '-azobis, (2, 4-dimethylpentanenitrile) and 1, 1' -azobis (cyclohexane-1-carbonitrile).
In a preferred embodiment of the present invention, the aqueous dispersion medium is water containing an electrolyte.
In a preferred embodiment of the present invention, the oil phase prepared in step (1) and the water phase prepared in step (2) are made into a suspension by stirring mechanical shearing, wherein the rotation speed of the stirring mechanical shearing is 3000-8000rpm for 5-45 min.
Detailed Description
The invention aims to solve the defects of high toxicity, low operation safety and high environmental protection requirement in the prior art and provide a monomer composition for replacing acrylonitrile monomers.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
the present invention provides a method for producing thermally expandable microspheres comprising a thermoplastic resin shell and a foaming agent encapsulated in the shell and having a boiling point not higher than the softening point of the thermoplastic resin, wherein the method comprises the steps of:
(1) preparation of oil phase: mixing 80-200 parts by weight of foaming agent, 100 parts by weight of polymerization combined monomer composition, 0.05-5 parts by weight of cross-linking agent and 0.01-10 parts by weight of initiator to prepare oil phase;
(2) preparation of the aqueous phase: mixing 0.001-2 parts by weight of a water-soluble composition, 100-800 parts by weight of an aqueous dispersion medium, 5-50 parts by weight of a dispersion stabilizer and 0.005-0.03 parts by weight of an alkali metal nitrite inhibitor to prepare an aqueous phase;
(3) preparation of thermally expanded microspheres: and (3) mixing the oil phase in the step (1) with the water phase in the step (2) to prepare a suspension, then transferring the suspension into a reaction kettle, heating to 35-105 ℃ in a nitrogen atmosphere, reacting for 8-20h, performing suction filtration and deionized water washing on milky white liquid obtained after reaction, and drying to obtain the thermal expansion microspheres.
In a preferred embodiment of the invention, the blowing agent is one or more of isobutane, isopentane, n-pentane, isohexane, isooctane, or n-octane, preferably isopentane or isooctane.
In a preferred embodiment of the present invention, the polymeric combination monomer composition comprises one or more of methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, methyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, N dimethylacrylamide or poly (ethylene glycol) methyl methacrylate, preferably comprises methyl methacrylate, N dimethylacrylamide, poly (ethylene glycol) methyl methacrylate, isobornyl methacrylate and hexafluorobutyl methacrylate. The polymerization combination monomer composition is used for polymerization to form a shell of a thermoplastic resin.
In a more preferred embodiment of the invention, the weight ratio of methyl methacrylate, N dimethylacrylamide, poly (ethylene glycol) methyl methacrylate, isobornyl methacrylate, and hexafluorobutyl methacrylate is 8: 2.5: 0.2: 1: 0.5.
in a preferred embodiment of the present invention, the crosslinking agent is one or more of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triallyl cyanurate, 1, 3-propanediol dimethacrylate, or 1, 4-butanediol dimethacrylate, etc.
In a preferred embodiment of the present invention, the water-soluble composition comprises polyvinylpyrrolidone and sodium lauryl sulfate.
In a preferred embodiment of the present invention, the blowing agent is present in an amount of 23 to 32 parts by weight.
In a preferred embodiment of the present invention, the initiator is an organic peroxide or azo compound, preferably one or more of dibenzoyl peroxide, dilauryl peroxide, didecanoic acid peroxide, tert-butyl peracetate, tert-butyl peraurate or azobisisobutyronitrile, 2 '-azobis, (2, 4-dimethylpentanenitrile) and 1, 1' -azobis (cyclohexane-1-carbonitrile).
In a preferred embodiment of the present invention, the aqueous dispersion medium is water containing an electrolyte.
In a preferred embodiment of the present invention, the oil phase prepared in step (1) and the water phase prepared in step (2) are made into a suspension by stirring mechanical shearing, wherein the rotation speed of the stirring mechanical shearing is 3000-8000rpm for 5-45 min.
The initiator and the crosslinking agent used in the suspension polymerization of the present invention are not particularly required, and those skilled in the art can select suitable materials and auxiliaries depending on the progress of the reaction and the intended result.
The diameter of the prepared thermal expansion microsphere before unexpanded is 15-25 mu m, and the content of the foaming agent is 23-32%.
The dispersing medium adopted by the invention is water containing electrolyte, the pH value is controlled to be 3-5, the electrolyte is not particularly limited, the selection can be carried out by a person skilled in the art, one or more of sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium sulfate and potassium sulfate is preferred in the invention, sodium chloride or potassium chloride is more preferred, the dosage of the electrolyte is preferably 10-30 parts, and in addition, the commonly used colloidal silica dispersion stabilizer and alkali nitrite salt inhibitor such as sodium nitrite are selected.
After the water phase and the oil phase are dispersed into suspension in the step (2), the suspension polymerization is initiated by adopting an oil-soluble initiator preferentially, and the thermal expansion microspheres are prepared after the polymerization reaction is carried out for 8-20 hours. The suspension polymerization temperature may be determined depending on the kind of the initiator used, and the suspension polymerization temperature recommended in the present invention is 35 to 105 ℃. The process of dispersing the oil phase and the water phase into the suspension in the step (2) can be carried out by a stirring method such as a homogenizer, an electric stirrer and the like, and the rotating speed of the stirring high-speed mechanical shearing is 3000-8000rpm for 5-45 min.
The preparation method comprises the following steps: in an aqueous dispersion medium, a polymerizable component is subjected to suspension polymerization in the presence of a water-soluble composition, an acrylic monomer composition is adopted as a main monomer of the polymerizable component, a shell with high barrier property and high glass transition temperature is formed after polymerization, and a virulent acrylonitrile monomer is not adopted, so that the comprehensive cost of monomer raw materials is reduced, the safety in the production operation process is improved, and the potential pollution risk of the production environment is reduced.
The preparation process of the thermal expansion microsphere is simple, and the prepared thermal expansion microsphere has excellent performance and can be widely applied to the fields of textile, shoe industry, building, industry and the like. And acrylonitrile type highly toxic monomers are not adopted in the preparation process of the thermal expansion microspheres. The preparation of the thermal expansion microsphere adopts the monomer composition, and has safe operation and low environmental protection requirement.
Examples
The following are more specific examples to develop the present invention, but the present invention is not limited to the scope of these examples. Ratios, proportions, parts, percentages herein are by weight and all temperature units are in degrees Celsius unless otherwise indicated.
Example 1
(1) Preparation of oil phase: mixing 6g of isopentane, 6g of isooctane, 8g of methyl methacrylate, 2.5g N, N-dimethylacrylamide, 0.2g of poly (ethylene glycol) methyl methacrylate, 1g of isobornyl methacrylate, 0.5g of hexafluorobutyl methacrylate, 0.05g of triallyl cyanurate and 0.05g of azobisisobutyronitrile at 25 ℃ for 10-15min to form a uniform oil phase;
(2) preparation of the aqueous phase: dissolving 20g of sodium chloride in 100g of deionized water, then adding 20g of a 25% colloidal silica solution, adding 4g of a 1% polyvinylpyrrolidone aqueous solution and 0.1g of sodium dodecyl sulfate, then adding 1.8g of a 1% sodium nitrite aqueous solution, uniformly stirring, and then continuously adding hydrochloric acid to adjust the pH value to 3, wherein the formed solution is a water phase;
(3) homogenizing the water phase and the oil phase: pouring the oil phase into the water phase, and dispersing the mixed liquid in a homomixer at 6000rpm for 10min to prepare suspension;
(4) preparation of thermally expanded microspheres: the suspension is transferred into a reaction kettle and is heated to 65 ℃ in the atmosphere of nitrogen to react for 20 h. And filtering the milky white liquid obtained after the reaction, washing the milky white liquid with deionized water, and drying the milky white liquid to obtain the thermal expansion microspheres, wherein the average particle size of the thermal expansion microspheres is 15 microns, the content of the foaming agent is 28 percent, and the average expansion ratio is 50 times.
Example 2
(1) Preparation of oil phase: mixing 6g of isopentane, 7g of isooctane, 8g of methyl methacrylate, 3g of N, N-dimethylacrylamide, 0.5g of poly (ethylene glycol) methyl methacrylate, 1.2g of isobornyl methacrylate, 0.6g of hexafluorobutyl methacrylate, 0.06g of triallyl cyanurate and 0.04g of benzoyl peroxide at 25 ℃ and stirring for 10min-15min to form a uniform oil phase;
(2) preparation of the aqueous phase: dissolving 20g of sodium chloride in 100g of deionized water, then adding 20g of a colloidal silicon dioxide solution with the mass concentration of 25%, adding 5g of a 1% polyvinylpyrrolidone aqueous solution and 0.1g of sodium dodecyl sulfate, then adding 2g of a 1% sodium nitrite aqueous solution, stirring uniformly, and then continuously adding hydrochloric acid to adjust the pH value to 3, wherein the formed solution is a water phase;
(3) homogenizing the water phase and the oil phase: pouring the oil phase into the water phase, and dispersing the mixed liquid in a homomixer at 6000rpm for 15min to prepare suspension;
(4) preparation of thermally expanded microspheres: the suspension is transferred into a reaction kettle and heated to 80 ℃ in the atmosphere of nitrogen to react for 16 h. And filtering the milky white liquid obtained after the reaction, washing the milky white liquid with deionized water, and drying the milky white liquid to obtain the thermal expansion microspheres, wherein the average particle size of the thermal expansion microspheres is 20 microns, the content of the foaming agent is 26%, and the average expansion ratio is 45 times.
Example 3
(1) Preparation of oil phase: 5g of isopentane, 7g of isooctane, 8g of methyl methacrylate, 2.5g of N, N dimethylacrylamide, 0.2g of poly (ethylene glycol) methyl methacrylate, 1g of isobornyl methacrylate, 0.5g of hexafluorobutyl methacrylate, 0.07g of ethylene glycol dimethacrylate and 0.04g of azobisisobutyronitrile are mixed and stirred at 25 ℃ for 10min to 15min to form a uniform oil phase;
(2) preparation of the aqueous phase: dissolving 20g of sodium chloride in 100g of deionized water, then adding 20g of a colloidal silicon dioxide solution with the mass concentration of 25%, adding 3.5g of a 1% polyvinylpyrrolidone aqueous solution and 0.2g of sodium dodecyl sulfate, then adding 1.8g of a 1% sodium nitrite aqueous solution, uniformly stirring, and then continuously adding hydrochloric acid to adjust the pH value to 3, wherein the formed solution is a water phase;
(3) homogenizing the water phase and the oil phase: pouring the oil phase into the water phase, and dispersing the mixed liquid in a homomixer at 6000rpm for 10min to prepare suspension;
(4) preparation of thermally expanded microspheres: the suspension is transferred into a reaction kettle and is heated to 65 ℃ in the atmosphere of nitrogen to react for 20 h. And filtering the milky white liquid obtained after the reaction, washing the milky white liquid with deionized water, and drying the milky white liquid to obtain the thermal expansion microspheres, wherein the average particle size of the thermal expansion microspheres is 21 microns, the content of the foaming agent is 25%, and the average expansion ratio is 40 times.
Example 4
(1) Preparation of oil phase: mixing 6g of isopentane, 6g of isooctane, 8g of methyl methacrylate, 2.5g of N, N dimethylacrylamide, 0.2g of poly (ethylene glycol) methyl methacrylate, 1g of isobornyl methacrylate, 0.5g of hexafluorobutyl methacrylate, 0.04g of 1, 4-butanediol dimethacrylate and 0.05g of dibenzoyl peroxide at 25 ℃ and stirring for 10min to 15min to form a uniform oil phase;
(2) preparation of the aqueous phase: dissolving 20g of sodium chloride in 100g of deionized water, then adding 20g of a colloidal silicon dioxide solution with the mass concentration of 25%, adding 3.5g of a 1% polyvinylpyrrolidone aqueous solution and 0.15g of sodium dodecyl sulfate, then adding 1.8g of a 1% sodium nitrite aqueous solution, uniformly stirring, and then continuously adding hydrochloric acid to adjust the pH value to 3, wherein the formed solution is a water phase;
(3) homogenizing the water phase and the oil phase: pouring the oil phase into the water phase, and dispersing the mixed liquid in a homomixer at 7500rpm for 15min to obtain suspension;
(4) preparation of thermally expanded microspheres: the suspension is transferred into a reaction kettle and is heated to 65 ℃ in the atmosphere of nitrogen to react for 20 h. And filtering the milky white liquid obtained after the reaction, washing the milky white liquid with deionized water, and drying the milky white liquid to obtain the thermal expansion microspheres, wherein the average particle size of the thermal expansion microspheres is 25 microns, the content of the foaming agent is 30%, and the average expansion ratio is 50 times.
Claims (10)
1. A method for producing thermally-expanded microspheres comprising a thermoplastic resin shell and a foaming agent having a boiling point not higher than the softening point of the thermoplastic resin encapsulated in the shell, wherein the method comprises the steps of:
(1) preparation of oil phase: mixing 80-200 parts by weight of foaming agent, 100 parts by weight of polymerization combined monomer composition, 0.05-5 parts by weight of cross-linking agent and 0.01-10 parts by weight of initiator to prepare oil phase;
(2) preparation of the aqueous phase: mixing 0.001-2 parts by weight of a water-soluble composition, 100-800 parts by weight of an aqueous dispersion medium, 5-50 parts by weight of a dispersion stabilizer and 0.005-0.03 parts by weight of an alkali metal nitrite inhibitor to prepare an aqueous phase;
(3) preparation of thermally expanded microspheres: and (3) mixing the oil phase in the step (1) with the water phase in the step (2) to prepare a suspension, then transferring the suspension into a reaction kettle, heating to 35-105 ℃ in the atmosphere of nitrogen, reacting for 8-20h, and drying to obtain the thermal expansion microspheres.
2. The method for producing thermally expandable microspheres according to claim 1, wherein the blowing agent is one or more selected from isobutane, isopentane, n-pentane, isohexane, isooctane and n-octane, preferably isopentane or isooctane.
3. The method for preparing thermally expandable microspheres according to claim 1, wherein the polymeric combination monomer composition comprises one or more of methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, methyl acrylate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, N dimethylacrylamide or poly (ethylene glycol) methyl methacrylate, preferably comprises methyl methacrylate, N dimethylacrylamide, poly (ethylene glycol) methyl methacrylate, isobornyl methacrylate and hexafluorobutyl methacrylate.
4. The process for producing thermally expandable microspheres according to claim 3, wherein the weight ratio of methyl methacrylate, N-dimethylacrylamide, poly (ethylene glycol) methyl methacrylate, isobornyl methacrylate and hexafluorobutyl methacrylate is 8: 2.5: 0.2: 1: 0.5.
5. the method of producing thermally expandable microspheres according to claim 1, wherein the crosslinking agent is one or more of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triallyl cyanurate, 1, 3-propanediol dimethacrylate, and 1, 4-butanediol dimethacrylate.
6. The method for producing thermally expandable microspheres according to claim 1, wherein the water-soluble composition comprises polyvinylpyrrolidone and sodium lauryl sulfate.
7. The method for producing thermally expandable microspheres according to claim 1, wherein the blowing agent is used in an amount of 23 to 32 parts by weight.
8. The method for preparing thermally expandable microspheres according to claim 1, wherein the initiator is an organic peroxide or an azo compound, preferably one or more of dibenzoyl peroxide, dilauryl peroxide, didecanoic acid peroxide, t-butyl peracetate, t-butyl peraurate or azobisisobutyronitrile, 2 '-azobis, (2, 4-dimethylpentanenitrile) and 1, 1' -azobis (cyclohexane-1-carbonitrile).
9. The method for producing thermally expandable microspheres according to claim 1, wherein the aqueous dispersion medium is water containing an electrolyte.
10. The method for preparing thermally expandable microspheres according to claim 1, wherein the oil phase prepared in step (1) and the aqueous phase prepared in step (2) are subjected to stirring mechanical shearing to prepare a suspension, wherein the rotation speed of the stirring mechanical shearing is 3000-8000rpm for 5-45 min.
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