CN102633936A - Thermoexpandable thermoplastic microspheres - Google Patents
Thermoexpandable thermoplastic microspheres Download PDFInfo
- Publication number
- CN102633936A CN102633936A CN2012101093023A CN201210109302A CN102633936A CN 102633936 A CN102633936 A CN 102633936A CN 2012101093023 A CN2012101093023 A CN 2012101093023A CN 201210109302 A CN201210109302 A CN 201210109302A CN 102633936 A CN102633936 A CN 102633936A
- Authority
- CN
- China
- Prior art keywords
- heat
- thermoplastic microspheres
- monomer
- straight
- swellable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 44
- 239000004005 microsphere Substances 0.000 title claims abstract description 36
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 239000000126 substance Substances 0.000 claims abstract description 25
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 19
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- -1 acrylic ester Chemical class 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 20
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 19
- 238000002156 mixing Methods 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000002612 dispersion medium Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002512 suppressor factor Substances 0.000 description 4
- 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 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920000103 Expandable microsphere Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- ZAJYARZMPOEGLK-UHFFFAOYSA-N 1-ethyl-2-propan-2-ylbenzene Chemical compound CCC1=CC=CC=C1C(C)C ZAJYARZMPOEGLK-UHFFFAOYSA-N 0.000 description 1
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- HZNQSWJZTWOTKM-UHFFFAOYSA-N 2,3,4-trimethoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C(OC)=C1OC HZNQSWJZTWOTKM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical class OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- SKEYBVJYVVGWPE-UHFFFAOYSA-N C(=C)OCC(=S)OCCO Chemical compound C(=C)OCC(=S)OCCO SKEYBVJYVVGWPE-UHFFFAOYSA-N 0.000 description 1
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- NGMNTLCQDNNBNT-UHFFFAOYSA-N C(C=C)(=O)OC.C(CS)(=O)OCCOC(CS)=O Chemical compound C(C=C)(=O)OC.C(CS)(=O)OCCOC(CS)=O NGMNTLCQDNNBNT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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- 108010010803 Gelatin Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- LYSXNLOXFRNJFD-UHFFFAOYSA-N [O].OC(=O)C=C Chemical compound [O].OC(=O)C=C LYSXNLOXFRNJFD-UHFFFAOYSA-N 0.000 description 1
- LCJHLOJKAAQLQW-UHFFFAOYSA-N acetic acid;ethane Chemical compound CC.CC(O)=O LCJHLOJKAAQLQW-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N alpha-isobutyric acid Natural products CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- FEIXNIOTSKFSAZ-UHFFFAOYSA-L azane;dihydroxy(dioxo)chromium Chemical class N.N.O[Cr](O)(=O)=O FEIXNIOTSKFSAZ-UHFFFAOYSA-L 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium 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
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- UFFSXJKVKBQEHC-UHFFFAOYSA-N heptafluorobutyric anhydride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OC(=O)C(F)(F)C(F)(F)C(F)(F)F UFFSXJKVKBQEHC-UHFFFAOYSA-N 0.000 description 1
- NQUPKCJGWCPODR-UHFFFAOYSA-N hexaneperoxoic acid Chemical group CCCCCC(=O)OO NQUPKCJGWCPODR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical class [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical class O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- CPTIBDHUFVHUJK-NZYDNVMFSA-N mitopodozide Chemical compound C1([C@@H]2C3=CC=4OCOC=4C=C3[C@H](O)[C@@H](CO)[C@@H]2C(=O)NNCC)=CC(OC)=C(OC)C(OC)=C1 CPTIBDHUFVHUJK-NZYDNVMFSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000001702 nutmeg Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to thermoexpandable thermoplastic microspheres which are mainly prepared by carrying out suspension polymerization on olefine polymerizable monomers and expandable substances. The thermoexpandable thermoplastic microspheres have a core-shell structure which uses the thermoplastic polymers as the shell and the expandable substances as the cure. The invention is characterized in that on the basis of 100 wt% as the total weight of the olefine polymerizable monomers, the olefine polymerizable monomers are composed of 30-90 wt% of acrylonitrile, 5-50 wt% of methacrylate monomers, 1-20 wt% of acrylamide monomers, 0.01-1.0 wt% of fluorine-containing acrylate monomers and 0-40 wt% of acrylic monomers. The start T of the thermoexpandable thermoplastic microspheres is 160-200 DEG C.
Description
Technical field
The present invention relates to a kind of thermoplastic microspheres of heat-swellable.
Background technology
The thermoplastic microspheres of heat-swellable is a kind of mainly by being shell with the thermoplastic polymer and being the microsphere with nucleocapsid structure that nuclear constituted with the expandable substance.In this type of microsphere, expandable substance normally boiling point is not higher than the liquid of the softening temperature of thermoplastic polymer (shell).Meet heat, said liquid evaporation and increase interior pressure, meanwhile, said thermoplastic polymer (shell) is softening, (the temperature brief note when microballoon begins to expand is T thereby cause said microballoon to expand
Beginning, and the temperature brief note when realizing maximum swelling is T
Maximum).
In some Application Areass, the user hopes that the thermoplastic microspheres of the heat-swellable that supplier provides has higher T
Beginning(generally at 160 ℃-200 ℃).Yet, have a higher T existing
BeginningThe thermoplastic microspheres of heat-swellable in; Methacrylonitrile becomes the necessary component that constitutes thermoplastic polymer (shell) (methacrylonitrile complex manufacturing and cost an arm and a leg); Do not having under the condition of methacrylonitrile, the performance of the thermoplastic microspheres of the heat-swellable that makes (mainly is T
BeginningAnd swelling capacity) still can not make the user satisfied.
Therefore, provide a kind of that do not contain methacrylonitrile and have a higher T
Beginning(generally at 160 ℃-200 ℃) and the heat-swellable thermoplastic microspheres of higher swelling capacity become the technical issues that need to address of the present invention.
Summary of the invention
The objective of the invention is to, provide a kind of that do not contain methacrylonitrile and have a higher T
BeginningThe heat-swellable thermoplastic microspheres of (generally at 160 ℃-200 ℃) and higher swelling capacity.
Heat-swellable thermoplastic microspheres provided by the present invention; It mainly can gather monomer by olefinic and expandable substance obtains through suspension polymerization; Resulting heat-swellable thermoplastic microspheres is to be shell with the thermoplastic polymer and to be the microballoon with nucleocapsid structure of nuclear with the expandable substance; It is characterized in that wherein said olefinic can gather monomer and be made up of vinyl cyanide, acrylic ester monomer, acrylamide monomers, acrylate containing fluorine monomer and acrylic monomer, can gather monomeric gross weight with said olefinic is that 100wt% calculates benchmark; Can gather in the monomer at described olefinic; Vinyl cyanide accounts for 30wt%～90wt%, and the methyl acrylic ester monomer accounts for 5wt%～50wt%, and acrylamide monomers accounts for 1wt%～20wt%; The acrylate containing fluorine monomer accounts for 0.01wt%～1.0wt%, and acrylic monomer accounts for 0wt%～40wt% (preferred 1wt%～30wt%);
Wherein, Said acrylic ester monomer is selected from: mixture a kind of or that (contain two kinds) more than two kinds in the said compound of the formula I family; Said acrylamide monomers is selected from: mixture a kind of or that (contain two kinds) more than two kinds in the said compound of the formula II family; Said acrylate containing fluorine monomer is selected from: mixture a kind of or that (contain two kinds) more than two kinds in the said compound of the formula III family, and said acrylic monomer is that vinylformic acid is or/and methylacrylic acid;
In the formula, R
1Be C
1～C
10Straight chain, side chain or cyclic alkyl, R
2And R
3Independently be selected from respectively: H, C
1～C
6The substituted C of straight or branched alkyl or hydroxyl
1～C
6A kind of in the straight or branched alkyl, R
4Be C
1～C
6Straight or branched contain fluoroalkyl, R
5Be H or methyl.
The present invention mainly substitutes methacrylonitrile (monomer) in the prior art with acrylamide monomers and acrylate containing fluorine monomer, has obtained to have higher T
BeginningThe heat-swellable thermoplastic microspheres of (generally at 160 ℃-200 ℃) and higher swelling capacity reaches intended purposes of the present invention.
Embodiment
The thermoplastic microspheres for preparing heat-swellable according to the invention can adopt existing suspension polymerization.In described suspension polymerization, expandable substance keeps suspended state with the polymerizable compound that comprises polymerisable monomer through continuously stirring or interpolation dispersion stabilizer (like Marinco H or colloid silica etc.).Through suspension polymerization, polymkeric substance can form sphere.
In the present invention, to initiator used in used expandable substance and the suspension polymerization and linking agent and have no special requirements.
For the selection of expandable substance, as long as satisfy the softening temperature that the boiling point of selecteed expandable substance is not higher than the prepared thermoplastic polymer of the present invention (shell).The present invention recommends to use C
5～C
12The aliphatic hydrocarbon compounds, preferred expandable substance is C
5～C
12The straight or branched saturated hydrocarbons compound, further preferred expandable substance is C
5～C
8The straight or branched saturated hydrocarbons compound.
For the selection of linking agent, be fit to linking agent of the present invention and be to contain a kind of compound of or the bridging property official group that (contains two kinds) more than two kinds, concrete linking agent is selected from a kind of or mixture that (contains two kinds) more than two kinds in the following compounds:
Vinylstyrene, ethylene glycol bisthioglycolate (methyl) propenoate, two (terepthaloyl moietie) two (methyl) propenoate, triethylene glycol two (methyl) propenoate, Ucar 35 two (methyl) propenoate, 1; 4-butyleneglycol two (methyl) propenoate, 1; 6-pinakon two (methyl) propenoate, glycerine two (methyl) propenoate, 1; 3-butyleneglycol two (methyl) propenoate, NSC 6366 two (methyl) propenoate, decamethylene-glycol two (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, Dipentaerythritol six (methyl) propenoate, triallyl formal three (methyl) propenoate, allyl methacrylate(AMA), trimethylolpropane tris (methyl) propenoate, three butyleneglycol two (methyl) propenoate, PEG#200 two (methyl) propenoate, PEG#400 two (methyl) propenoate, PEG#600 two (methyl) propenoate, 3 acrylic acid oxygen base glycol mono acrylic ester, three acyl group formals, triallyl isocyanate, cyanacrylate, divinyl ether, ethylene glycol bisthioglycolate vinyl ether, Diethylene Glycol divinyl ether, triethylene glycol divinyl ether or TEG divinyl ether etc.
The consumption of linking agent is the 0.1wt%～10wt% of the total monomer weight that is used to prepare thermoplastic polymer (shell), and its preferred consumption is the 0.1wt%～3wt% of the total monomer weight that is used to prepare thermoplastic polymer (shell).
For the selection of initiator, the existing initiator (like organic superoxide or azo compound etc.) that is used for radical polymerization all is fit to the present invention, and concrete initiator is selected from a kind of or mixture that (contains two kinds) more than two kinds in the following compounds:
Two (hexadecyl) peroxy dicarbonate, two (4-tert-butylcyclohexyl) peroxy dicarbonate, peroxo-are two sad, diphenyl peroxide formic acid, peroxo-two LAURIC ACID 99 MIN, peroxo-two capric acid, tertiary butyl peroxy acetic acid ester, the tertiary butyl are crossed laurate, tert butyl peroxy benzoate, t-butyl hydroperoxide, cumene hydroperoxide, ethyl cumene peroxide, di-isopropyl hydroxydicarboxylic acid ester, 2; 2 '-azo two ((2; The 4-methyl pentane nitrile), 2; 2 '-azo two (isopropyl cyanide), 1; 1 '-azo two (hexanaphthene-1-nitrile), dimethyl-2; 2 ,-azo two (2 Methylpropionic acid ester) or 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl)-propionic acid amide] etc.
Can decide according to the kind of used initiator as for described suspension polymerization temperatures, the suspension polymerization temperatures that the present invention recommends is 40 ℃～100 ℃, and preferred suspension polymerization temperatures is 45 ℃～90 ℃, and preferred suspension polymerization temperatures is 50 ℃～85 ℃.
For polymerization initial stage pressure, preferred gauge pressure is 0-5.0MPa, and then preferred 0.1-3.0MPa, preferred especially 0.2-2.0MPa.
In addition, preferably make in its aqueous dispersion medium that is containing dispersion stabilizer and/or stably dispersing auxiliary agent in the present invention and carry out suspension polymerization.Usage quantity for described aqueous dispersion medium does not have special qualification, with respect to the polymerizable components (can gather the monomer total amount) of 100 weight parts, preferably uses the aqueous dispersion medium of 100 weight part to 1000 weight parts.
Wherein said dispersion stabilizer can be that colloid silica, colloid lime carbonate, Marinco H, calcium phosphate, white lake, ironic hydroxide, calcium sulfate, sodium sulfate, caoxalate, lime carbonate, barium carbonate, magnesiumcarbonate are or/and alumina sol etc.The consumption of dispersion stabilizer is preferably the 0.1wt%～20wt% of polymerizable components (can gather the monomer total amount) gross weight.
Further; Above-mentioned stably dispersing auxiliary agent can be selected from: the stably dispersing auxiliary agent of polymers such as the condensation resultant of diethylolamine and aliphatic dicarboxylic acid, gelatin, Vinylpyrrolidone polymer, methylcellulose gum, polyethylene oxide, Z 150PH; Cats products such as alkyltrimethylammonium chloride or chlorination dialkyl dimethyl ammonium; ASs such as sodium alkyl sulfate, various emulsifying agents such as zwitterionics such as alkyl dimethyl aminoacetic acid trimethyl-glycine, alkyl dihydroxy ethyl aminoacetic acid trimethyl-glycine.The consumption of stably dispersing auxiliary agent is preferably the 0.001wt%～2.0wt% of polymerizable components (can gather the monomer total amount) gross weight.
The pH of the aqueous dispersion medium during polymerization suitably determines according to the kind of the dispersion stabilizer that uses.For example; If dispersion stabilizer is selected from: the salt of metal Ca, Mg, Ba, Zn, Ni and Mn, oxide compound or oxyhydroxide are (concrete like calcium phosphate, lime carbonate, Marinco H, Natural manganese dioxide, permanent white, caoxalate; With a kind of in the oxyhydroxide of zinc, nickel or manganese or the mixture that (contains two kinds) more than two kinds); The then preferred 5-12 of pH value, more preferably 6-10; If dispersion stabilizer is selected from: the oxide compound or the oxyhydroxide of starch, methylcellulose gum, Vltra tears, carboxyl methylcellulose, glue agar, colloid silica, colloidal clays or aluminium or iron, the then preferred 1-6 of pH value, more preferably 3-5.
In addition, in aqueous dispersion medium, also can contain water-soluble radical suppressor factor, to suppress the generation of the cohesion microballoon in the polymerization.As water-soluble radical suppressor factor, can be nitrite alkali metal-salt (Sodium Nitrite and/or potassium nitrite etc.), dichromate (ammonium dichromate (two ammonium chromates), sodium dichromate 99 (two Sodium chromate-51Crs) and/or SRM 935a (two potassiumchromates) etc.); Tin protochloride; Tin chloride, iron protochloride, iron(ic)chloride; Ferrous sulfate, radical suppressor factor such as water-soluble xitix class and verivate thereof.Aspect the stability water, preferred nitrite alkali metal-salt.Per 100 parts by weight polymerizable components (can gather the monomer total amount), the consumption of water-soluble radical suppressor factor is the 0.0001-1 parts by weight, preferred 0.0003-0.1 parts by weight.
In the used aqueous dispersion medium of the present invention, also can contain ionogen.Do not have special qualification for ionogen, as being selected from: lithium chloride, sodium-chlor, Repone K, magnesium chloride, calcium chloride, sodium hydrogencarbonate, Lithium Sulphate, sodium sulfate, vitriolate of tartar, sal epsom, sulfuric acid are a kind of or (contain two kinds) more than two kinds by, yellow soda ash or TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. etc.With respect to the aqueous dispersion medium of 100 parts by weight, electrolytical consumption is advisable with the 0.1-50 parts by weight.
The mean diameter of heat-swellable microballoon provided by the present invention is 5 μ m～100 μ m, and preferred mean diameter is 10 μ m～100 μ m, further preferred mean diameter 10 μ m～60 μ m.
In addition; With the heat-swellable microballoon gross weight that is provided is that 100wt% calculates benchmark, and expandable substance accounts for 5wt%～50wt%, and preferred content is 10wt%～50wt%; Further preferred content is 10wt%～40wt%, and the optimum content of expandable substance is 10wt%～35wt%.
In another optimized technical scheme of the present invention, R
1Be C
1～C
6The straight or branched alkyl, preferred R
1Be C
1～C
3The straight or branched alkyl, best R
1Be methyl.
In another optimized technical scheme of the present invention, R
2And R
3Independently be selected from respectively: H, C
1～C
3The substituted C of straight or branched alkyl or hydroxyl
1～C
3A kind of in the straight or branched alkyl, preferred R
2And R
3Independently be selected from respectively: a kind of in H, methyl or the methylol, compound is acrylic amide, N hydroxymethyl acrylamide or N shown in the best formula II, the N-DMAA.
In another optimized technical scheme of the present invention, R
4Be C
2～C
4Straight or branched contain fluoroalkyl, best R
4Be trifluoroethyl or hexafluoro butyl.
When polymerization is accomplished basically, can obtain the microballoon of water paste or dispersion-s, they can in statu quo use or obtain so-called wet cake through any ordinary method (for example bed filter, press filtration, leaf filter, commentaries on classics filter, band filter or centrifugal the dehydration).Yet, also can be through any ordinary method (for example spraying drying, support drying, tunnel drying, Rotary drying, drum dried, air seasoning, turbine support are dry, disk is dry or fluidised bed drying etc.), with this microspheres drying.
But also attaching surface properties-correcting agent, the further raising that realization is dispersed or mobile further improvement of outside surface at heat-swellable property microballoon provided by the present invention.
The surface-modifying agent that is adhered to can for organic system or inorganic be a kind of or mixture that (contains two kinds) more than two kinds in the properties-correcting agent,
Said organic system properties-correcting agent is like (but being not limited to): metallic soap classes such as Magnesium Stearate, calcium stearate, Zinic stearas, barium stearate, lithium stearates; Polyethylene wax, LAURIC ACID 99 MIN acid amide, nutmeg acid acid amides, palm fibre are put synthetic wax classes such as sour acid amides, stearylamide, hardened castor oil; SEPIGEL 305, polyimide, nylon, poly-methyl methacrylate vinegar, Vilaterm or tetrafluoroethylene etc.
Said inorganic be properties-correcting agent, like (but being not limited to): talcum, mica, wilkinite, sericite, carbon black, curing aluminium, tungsten disulfide, fluorographite, Calcium Fluoride (Fluorspan), SP 1, silicon-dioxide, aluminum oxide, mica, lime carbonate, calcium hydroxide, calcium phosphate, Marinco H, trimagnesium phosphate, permanent white, titanium dioxide are admired, zinc oxide, ceramic bead, granulated glass sphere or crystal pearl etc.
Do not limit the adhesion amount (attached to heat-swellable property microsphere surface) of said surface-modifying agent is special.If but consider the function that to bring into play surface-modifying agent fully etc.; Heat-swellable property microballoon gross weight not adhere to is 100 parts by weight; The adhesion amount of said surface-modifying agent is the 0.1-95 parts by weight; Be preferably the 0.5-60 parts by weight, further be preferably the 5-50 parts by weight, most preferably be the 8-30 parts by weight.
Adhering to of surface-modifying agent can be carried out through mixing the heat-swellable property microballoon and the surface-modifying agent that do not adhere to.For mixing, not special the qualification can be carried out in having the container of whipping appts.In addition, also can use and to carry out the common powder mixing machine that shakes or stir.As the powder mixing machine, for example can enumerate zonate frond type mixing machine, vertical spin type mixing machine etc. and can shake the powder mixing machine that stirs or stir.In addition, also can use is super mixing machine and high-speed mixer, SV mixing machine etc. through the higher multi-functional powder mixing machine of efficient that makes up whipping appts in recent years.
Heat-swellable microballoon provided by the present invention can be used for papermaking, printing-ink (for example water-based inks, solvent-based ink, plastisol, uv curing ink etc.), putty, sealing agent; The ultralight clay, base coat, tackiness agent; Coming unstuck of tackiness agent, leatheroid, corium; Paint, nonwoven fabric material, paper and plate; The coating (like nonskidcoating etc.) that is used for various materials such as paper, plate, plastics, metal and fabric, explosive substance, cable insulation; Thermoplastics (for example Vilaterm, SE and ethane-acetic acid ethyenyl ester) or thermoplastic elastomer (for example styrene-ethylene-butylene-styrene multipolymer, styrene-butadiene-styrene multipolymer, thermoplastic polyurethane and TPO), styrene-butadiene rubber(SBR), tree elastomer; Vulcanized rubber, silicone rubber, thermosetting polymer fields such as (for example epoxy resin, urethane and polyester).
Through embodiment the present invention is done further elaboration below.In listed embodiment, except as otherwise noted, all umbers and percentage are meant by weight umber and percentage among the embodiment, and following method and instrument are adopted in the analysis of heat-swellable property microballoon:
(1) size distribution specificity analysis:
The size distribution of microballoon is to measure through the size distribution laser diffraction analysis appearance LS13320 that Bekman coulter company produces.Mean diameter is measured as volume average particle size, and size distribution is calculated as C.V. value (standard deviation/mean diameter) X100.
(2) foaming character analysis:
The characteristic of heat-expandable microsphere is measured through the thermomechanical analyzer TMA Q-400 that TA Instrument company produces.
The 1.0mg heat-expandable microsphere that holds in the aluminium dish by diameter 6.7mm and degree of depth 4.5mm prepares sample.Then, said aluminium dish is with the aluminium dish sealing of diameter 6.5mm and degree of depth 4.0mm.According to TMA expanding probe type, sample temperature is increased to 230 ℃ with the heat-up rate of 50 ℃/min from envrionment temperature, and applies the power of 0.5N by probe.Analysis is carried out through the measuring sonde vertical translation.
-expansion initial temperature (Tstart): the temperature when the probe displacement begins to increase (℃).
-foaming top temperature (Tmax): the temperature when the probe displacement reaches maximum (℃).
-maximum foaming displacement ((Dmax): the displacement (μ m) when the probe displacement reaches maximum.
Embodiment 1
Through mixing 140 gram vinyl cyanide, 20 gram N; N-DMAA, 40 gram TEB 3Ks, 0.1 gram methylacrylic acid-2; 2,2-trifluoro ethyl ester, 0.4 gram trimethylolpropane trimethacrylate, 4 gram Lucidols and 50 gram octane-iso obtain the oil phase of suspension polymerization.
In No. 1 beaker, add 280 gram deionized waters, 30 gram sodium hydroxide, 40 gram sodium-chlor and 0.2 gram sodium lauryl sulphate are fully dissolved; In No. 2 beakers, add 280 gram deionized waters, 85 gram Magnesium dichloride hexahydrates, 30 gram sodium-chlor, the Sodium Nitrite of 0.01 gram fully dissolves; Earlier the solution in No. 1 beaker is poured in 2.5 liters of there-necked flasks that have stirring rake, stirred down at the 1200rpm rotating speed then, the more slow solution in No. 2 beakers of adding in this there-necked flask.Fully stirred again 15 minutes after adding, obtain the water of suspension polymerization.
Disperseed oil phase and water in 2 minutes through under 7000rpm, stirring with the intimate mixing machine, thus the preparation aaerosol solution.At once aaerosol solution is injected 1 and raises and press reaction kettle, logical nitrogen replacement air, and to the reaction kettle supercharging to reach the original pressure of 0.3MPa.Then, under 69-71 ℃, carried out polyreaction 20 hours.Polymerization obtains target compound (heat-swellable property microballoon of the present invention) through filtration, washing, drying after accomplishing.The performance of target compound is seen table 2.
Embodiment 2
Through mixing 40 gram vinyl cyanide, 2 gram N; N-DMAA, 3 gram TEB 3Ks, 4 gram methyl acrylates; 0.1 gram methylacrylic acid-2; 2,2-trifluoro ethyl ester, 0.5 gram methylacrylic acid, 0.1 gram vinylformic acid, 0.4 gram trimethylolpropane trimethacrylate, 1 gram Diisopropyl azodicarboxylate, 12 gram octane-iso and 3 gram iso-pentane obtain the oil phase of suspension polymerization.
In 200 weight part ion exchanged waters; Add 23 weight part sodium-chlor, 10 weight parts (effective constituent amount: 20 weight %) colloid silica, 0.1 weight account polyethylene pyrrolidone and 0.01 weight part Sodium Nitrite; Then with pH regulator to 2.4; Mix equably, with it as aqueous dispersion medium.
Disperseed oil phase and water in 3 minutes through under 6000rpm, stirring with the intimate mixing machine, thus the preparation aaerosol solution.At once aaerosol solution is injected 1 and raises and press reaction kettle, logical nitrogen replacement air, and to the reaction kettle supercharging to reach the original pressure of 0.3MPa.Then, under 60-61 ℃, carried out polyreaction 20 hours.Polymerization obtains target compound (heat-swellable property microballoon of the present invention) through filtration, washing, drying after accomplishing.The performance of target compound is seen table 2.
Embodiment 3-6
Except that the kind and consumption and polymer temperature that change used monomer, linking agent, initiator and expandable substance (specifically referring to table 1), other condition is identical with embodiment 1, makes different heat-swellable property microballoons, and its performance is seen table 2.
Table 1
In the table 1, AN: vinyl cyanide, MMA: TEB 3K, DMAA:N; The N-DMAA, AM: acrylic amide, HMAA:N-NMA, TFEMA: trifluoroethyl methacrylate; HFBA: vinylformic acid hexafluoro butyl ester, TMPDMA: trimethylolpropane trimethacrylate, EGDMA: TGM 1, DEGDE: Diethylene Glycol divinyl ether; BPO: Lucidol, AIBN: Diisopropyl azodicarboxylate, LPO: lauroyl peroxide, DCPD: peroxo-carbonic acid two cyclohexyls; IO: octane-iso, NH: normal hexane, IP: iso-pentane.
Table 2
Comparative example 1～3
Except that the kind and consumption and polymer temperature that change used monomer, linking agent, initiator and expandable substance (specifically referring to table 1), other condition is identical with embodiment 1, makes different heat-swellable property microballoons, and its performance is seen table 2.
Can know that by table 1 and table 2 1-3 compares with comparative example, comprise N, the foaming character that the embodiment 1-6 performance of the monomer mixture of N-DMAA (DMAA) and trifluoroethyl methacrylate significantly improves, and have narrow size distribution.
Comparative examples 1 and 2, when with DMAA instead of part AN as monomer, and not during methylate vinylformic acid trifluoro ethyl ester, T
Open BeginningAnd T
MaximumObviously improve, but the obvious broad of size distribution.
In addition, do not add the comparative example 3 of DMAA for only using trifluoroethyl methacrylate, though size distribution narrows down T
BeginningAnd T
MaximumObviously do not improve.
The method given according to above-mentioned explanation, those skilled in the art can expect multiple modification of the present invention and other embodiments.Therefore, should be appreciated that the embodiment that protection scope of the present invention is not limited to disclose, protection scope of the present invention is set forth in claim.
Claims (15)
1. heat-swellable thermoplastic microspheres; It mainly can gather monomer by olefinic and expandable substance obtains through suspension polymerization, and resulting heat-swellable thermoplastic microspheres is to be shell with the thermoplastic polymer and to be the microballoon with nucleocapsid structure of nuclear with the expandable substance, it is characterized in that; Wherein said olefinic can gather monomer and be made up of vinyl cyanide, acrylic ester monomer, acrylamide monomers, acrylate containing fluorine monomer and acrylic monomer; Can gather monomeric gross weight with said olefinic is that 100wt% calculates benchmark, can gather in the monomer at described olefinic, and vinyl cyanide accounts for 30wt%～90wt%; The methyl acrylic ester monomer accounts for 5wt%～50wt%; Acrylamide monomers accounts for 1wt%～20wt%, and the acrylate containing fluorine monomer accounts for 0.01wt%～1.0wt%, and acrylic monomer accounts for 0wt%～40wt%;
Wherein, Said methyl acrylic ester monomer is selected from: a kind of or mixture more than two kinds in the said compound of the formula I family; Said acrylamide monomers is selected from: a kind of or mixture more than two kinds in the said compound of the formula II family; Said acrylate containing fluorine monomer is selected from: a kind of or mixture more than two kinds in the said compound of the formula III family, said acrylic monomer are that vinylformic acid is or/and methylacrylic acid
The boiling point of said expandable substance is not higher than the softening temperature of prepared thermoplastic polymer,
The polymerization temperature of said suspension polymerization is 40 ℃～100 ℃, and the polymerization gauge pressure of said suspension polymerization is 0.1MPa～3.0MPa,
In the formula, R
1Be C
1～C
10Straight chain, side chain or cyclic alkyl, R
2And R
3Independently be selected from respectively: H, C
1～C
6The substituted C of straight or branched alkyl or hydroxyl
1～C
6A kind of in the straight or branched alkyl, R
4Be C
1～C
6Straight or branched contain fluoroalkyl, R
5Be H or methyl.
2. heat-swellable thermoplastic microspheres as claimed in claim 1 is characterized in that wherein said acrylic monomer accounts for 1wt%～30wt%.
3. according to claim 1 or claim 2 heat-swellable thermoplastic microspheres is characterized in that, is that 100wt% calculates benchmark with said heat-swellable microballoon gross weight, and expandable substance accounts for 5wt%～50wt%.
4. heat-swellable thermoplastic microspheres as claimed in claim 3 is characterized in that wherein expandable substance accounts for 10wt%～35wt%.
5. heat-swellable thermoplastic microspheres as claimed in claim 4 is characterized in that, wherein said expandable substance C
5～C
12The aliphatic hydrocarbon compounds.
6. heat-swellable thermoplastic microspheres as claimed in claim 5 is characterized in that wherein said expandable substance is C
5～C
8The straight or branched saturated hydrocarbons compound.
7. like claim 1,2 or 6 described heat-swellable thermoplastic microspheres, it is characterized in that, wherein R
1Be C
1～C
6The straight or branched alkyl.
8. heat-swellable thermoplastic microspheres as claimed in claim 7 is characterized in that, wherein R
1Be C
1～C
3The straight or branched alkyl.
9. heat-swellable thermoplastic microspheres as claimed in claim 8 is characterized in that, wherein R
1Be methyl.
10. like claim 1,2 or 6 described heat-swellable thermoplastic microspheres, it is characterized in that, wherein R
2And R
3Independently be selected from respectively: H, C
1～C
3The substituted C of straight or branched alkyl or hydroxyl
1～C
3A kind of in the straight or branched alkyl.
11. heat-swellable thermoplastic microspheres as claimed in claim 10 is characterized in that, wherein R
2And R
3Independently be selected from respectively: a kind of in H, methyl or the methylol.
12. heat-swellable thermoplastic microspheres as claimed in claim 11 is characterized in that, wherein used acrylamide monomers is acrylic amide, N hydroxymethyl acrylamide or/and N, the N-DMAA.
13., it is characterized in that, wherein R like claim 1,2 or 6 described heat-swellable thermoplastic microspheres
4Be C
2～C
4Straight or branched contain fluoroalkyl.
14. heat-swellable thermoplastic microspheres as claimed in claim 13 is characterized in that, wherein R
4Be trifluoroethyl or hexafluoro butyl.
15. like any described heat-swellable thermoplastic microspheres in the claim 1～14, it is characterized in that wherein the polymerization temperature of suspension polymerization is 50 ℃～85 ℃, the polymerization gauge pressure of suspension polymerization is 0.2MPa～2.0MPa.
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Denomination of invention: Thermoexpandable thermoplastic microsphere Effective date of registration: 20221027 Granted publication date: 20160608 Pledgee: Industrial Bank Co.,Ltd. Shanghai Lujiazui sub branch Pledgor: NANOSPHERE (SHANGHAI) Co.,Ltd. Registration number: Y2022310000301 |
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Date of cancellation: 20231225 Granted publication date: 20160608 Pledgee: Industrial Bank Co.,Ltd. Shanghai Lujiazui sub branch Pledgor: NANOSPHERE (SHANGHAI) Co.,Ltd. Registration number: Y2022310000301 |
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Denomination of invention: Thermoexpandable thermoplastic microspheres Effective date of registration: 20231229 Granted publication date: 20160608 Pledgee: Industrial Bank Co.,Ltd. Shanghai Lujiazui sub branch Pledgor: NANOSPHERE (SHANGHAI) Co.,Ltd. Registration number: Y2023310000947 |