CN102633936B - Heat-swellable thermoplastic microspheres - Google Patents
Heat-swellable thermoplastic microspheres Download PDFInfo
- Publication number
- CN102633936B CN102633936B CN201210109302.3A CN201210109302A CN102633936B CN 102633936 B CN102633936 B CN 102633936B CN 201210109302 A CN201210109302 A CN 201210109302A CN 102633936 B CN102633936 B CN 102633936B
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- CN
- China
- Prior art keywords
- heat
- monomer
- thermoplastic microspheres
- swellable thermoplastic
- accounts
- 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.)
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- 239000004005 microsphere Substances 0.000 title claims abstract description 52
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 44
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 60
- -1 acrylic ester Chemical class 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229920000103 Expandable microsphere Polymers 0.000 claims description 6
- 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
- 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
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000002612 dispersion medium Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003431 cross linking reagent Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 6
- 238000006073 displacement reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 238000010557 suspension polymerization reaction Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003112 inhibitor Substances 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 235000012254 magnesium hydroxide Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 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 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 238000004458 analytical method Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 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
- 229920000642 polymer Polymers 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate 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
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical class C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-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
- 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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 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
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 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
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 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
- 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
- 239000000463 material Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 229910052759 nickel 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
- 229920000573 polyethylene Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 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
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- DEQJNIVTRAWAMD-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl prop-2-enoate Chemical compound FC(F)(F)CC(F)C(F)(F)OC(=O)C=C DEQJNIVTRAWAMD-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
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 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
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NVZWSDYYWDDQAN-UHFFFAOYSA-N 2-amino-4,4-dihydroxybutanoic acid Chemical compound OC(=O)C(N)CC(O)O NVZWSDYYWDDQAN-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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- YCSFWTRTUSYTIO-UHFFFAOYSA-N C(=O)O.C1(=CC=CC=C1)OOC1=CC=CC=C1 Chemical compound C(=O)O.C1(=CC=CC=C1)OOC1=CC=CC=C1 YCSFWTRTUSYTIO-UHFFFAOYSA-N 0.000 description 1
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000498779 Myristica Species 0.000 description 1
- 235000009421 Myristica fragrans Nutrition 0.000 description 1
- HSHXDCVZWHOWCS-UHFFFAOYSA-N N'-hexadecylthiophene-2-carbohydrazide Chemical compound CCCCCCCCCCCCCCCCNNC(=O)c1cccs1 HSHXDCVZWHOWCS-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 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
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- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003289 ascorbyl group Chemical class [H]O[C@@]([H])(C([H])([H])O*)[C@@]1([H])OC(=O)C(O*)=C1O* 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
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 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
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- 150000001559 benzoic acids Chemical class 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 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
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
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- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
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- 239000003292 glue Substances 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
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 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
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 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
- 229940070765 laurate Drugs 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical class [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 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
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- GTDHYNXLIKNVTJ-UHFFFAOYSA-N n-(1-hydroxy-2-methylpropan-2-yl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC(C)(C)CO GTDHYNXLIKNVTJ-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint 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
- 229950000845 politef Drugs 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- XMXNVYPJWBTAHN-UHFFFAOYSA-N potassium chromate Chemical class [K+].[K+].[O-][Cr]([O-])(=O)=O XMXNVYPJWBTAHN-UHFFFAOYSA-N 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 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
- 238000003825 pressing Methods 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
- 239000000565 sealant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical class [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
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- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
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- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 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
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920002397 thermoplastic olefin 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
- 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
- 229940113165 trimethylolpropane Drugs 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
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Abstract
The present invention relates to a kind of heat-swellable thermoplastic microspheres, it mainly can be gathered monomer by olefinic and expandable substance obtains through suspension polymerisation, obtained heat-swellable thermoplastic microspheres be with thermoplastic polymer for shell and be core with expandable substance the microsphere with nucleocapsid structure, it is characterized in that, wherein said olefinic can gather monomer by acrylonitrile, acrylic ester monomer, acrylamide monomers, acrylate containing fluorine monomer and acrylic monomer composition, the gross weight of monomer can be gathered for 100wt% for calculating benchmark with described olefinic, can gather in monomer at described olefinic, acrylonitrile accounts for 30wt%��90wt%, methacrylate-based monomer accounts for 5wt%��50wt%, acrylamide monomers accounts for 1wt%��20wt%, acrylate containing fluorine monomer accounts for 0.01wt%��1.0wt%, acrylic monomer accounts for 0wt%��40wt%. the T of heat-swellable thermoplastic microspheres provided by the invention starts to be 160 DEG C-200 DEG C.
Description
Technical field
The present invention relates to the thermoplastic microspheres of a kind of heat-swellable.
Background technology
The thermoplastic microspheres of heat-swellable is a kind of main by with thermoplastic polymer for shell and the microsphere with nucleocapsid structure that constituted for core with expandable substance. In this type of microsphere, expandable substance is usually the boiling point liquid not higher than the softening temperature of thermoplastic polymer (shell). Heat, described liquid evaporates and increases intrinsic pressure, and meanwhile, described thermoplastic polymer (shell) softens, thus causing that (temperature that microsphere starts when expanding is abbreviated as T to described microsphere expansionStart, and temperature when realizing maximum swelling is abbreviated as TMaximum)��
In some applications, user wishes that the thermoplastic microspheres of the heat-swellable that supplier provides has higher TStart(being typically in 160 DEG C-200 DEG C). But, existing, there is higher TStartHeat-swellable thermoplastic microspheres in, methacrylonitrile becomes the necessary component (methacrylonitrile complex manufacturing and expensive) constituting thermoplastic polymer (shell), when there is no methacrylonitrile, performance (the mainly T of the thermoplastic microspheres of the heat-swellable preparedStartAnd swelliong power) user still can not be made satisfied.
Therefore it provides a kind of without methacrylonitrile and there is higher TStartThe heat-swellable thermoplastic microspheres of (being typically in 160 DEG C-200 DEG C) and relatively highly expanded ability becomes the technical issues that need to address of the present invention.
Summary of the invention
It is an object of the invention to, it is provided that a kind of without methacrylonitrile and there is higher TStartThe heat-swellable thermoplastic microspheres of (being typically in 160 DEG C-200 DEG C) and relatively highly expanded ability.
Heat-swellable thermoplastic microspheres provided by the present invention, it mainly can be gathered monomer by olefinic and expandable substance obtains through suspension polymerisation, obtained heat-swellable thermoplastic microspheres be with thermoplastic polymer for shell and be core with expandable substance the microsphere with nucleocapsid structure, it is characterized in that, wherein said olefinic can gather monomer by acrylonitrile, acrylic ester monomer, acrylamide monomers, acrylate containing fluorine monomer and acrylic monomer composition, the gross weight of monomer can be gathered for 100wt% for calculating benchmark with described olefinic, can gather in monomer at described olefinic, acrylonitrile accounts for 30wt%��90wt%, methacrylate-based monomer accounts for 5wt%��50wt%, acrylamide monomers accounts for 1wt%��20wt%, acrylate containing fluorine monomer accounts for 0.01wt%��1.0wt%, acrylic monomer accounts for 0wt%��40wt% (preferred 1wt%��30wt%),
Wherein, described acrylic ester monomer is selected from: the mixture of one or two or more kinds (containing two kinds) in compound race described in Formulas I, described acrylamide monomers is selected from: the mixture of one or two or more kinds (containing two kinds) in compound race described in Formula II, described acrylate containing fluorine monomer is selected from: the mixture of one or two or more kinds (containing two kinds) in compound race described in formula III, and described acrylic monomer is acrylic acid or/and methacrylic acid;
In formula, R1For C1��C10Straight chain, side chain or cyclic alkyl, R2And R3It is respectively and independently selected from: H, C1��C6The C that straight or branched alkyl or hydroxyl replace1��C6One, R in straight or branched alkyl4For C1��C6Straight or branched containing fluoroalkyl, R5For H or methyl.
The present invention mainly substitutes methacrylonitrile (monomer) in prior art with acrylamide monomers and acrylate containing fluorine monomer, it is thus achieved that have higher TStartThe heat-swellable thermoplastic microspheres of (being typically in 160 DEG C-200 DEG C) and relatively highly expanded ability, reaches the present invention and expects purpose.
Detailed description of the invention
Prepare the thermoplastic microspheres of heat-swellable of the present invention, existing suspension polymerization can be adopted. In described suspension polymerization, expandable substance and the polymerizable compound including polymerisable monomer by continuous stirring or add dispersion stabilizer (such as magnesium hydroxide or silica sol etc.) and keep suspended state. Through suspension polymerisation, polymer can be formed spherical.
In the present invention, to initiator used in expandable substance used and suspension polymerisation and cross-linking agent and have no special requirements.
For the selection of expandable substance, as long as meeting the boiling point of the selected expandable substance softening temperature not higher than thermoplastic polymer (shell) prepared by the present invention. The present invention recommends C5��C12Aliphatic hydrocarbon compounds, preferred expandable substance is C5��C12Straight or branched saturated hydrocarbons compound, it is preferred that expandable substance be C5��C8Straight or branched saturated hydrocarbons compound.
For the selection of cross-linking agent, the cross-linking agent being suitable for the present invention is the compound containing one or two or more kinds (containing two kinds) bridging property official group, and concrete cross-linking agent is one or two or more kinds (containing two kinds) mixture in following compounds:
Divinylbenzene, ethylene glycol bisthioglycolate (methyl) acrylate, two (ethylene glycol) two (methyl) acrylate, triethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, glycerol two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, decamethylene-glycol two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, triallylformal t pi three (methyl) acrylate, allyl methacrylate, trimethylolpropane tris (methyl) acrylate, three butanediol two (methyl) acrylate, PEG#200 bis-(methyl) acrylate, PEG#400 bis-(methyl) acrylate, PEG#600 bis-(methyl) acrylate, 3 acrylic acid oxygen base diol mono-acrylate, three acyl group formals, triallyl isocyanate, Triallyl isocyanurate, divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethyleneglycol divinylether, or TEG divinyl ether etc.
The consumption of cross-linking agent is the 0.1wt%��10wt% being used for preparing the total monomer weight of thermoplastic polymer (shell), and its preferred consumption is the 0.1wt%��3wt% being used for preparing the total monomer weight of thermoplastic polymer (shell).
Selection for initiator, the initiator (such as organic peroxide or azo compound etc.) being currently used for radical polymerization is suitable for the present invention, and concrete initiator is one or two or more kinds (containing two kinds) mixture in following compounds:
Two (cetyl) peroxy dicarbonate, two (4-tert-butylcyclohexyl) peroxy dicarbonate, peroxidating two is sad, diphenyl peroxide formic acid, peroxidating tin dilaurate, peroxidating two capric acid, t-butyl peracetate ester, the tert-butyl group crosses laurate, tert butyl peroxy benzoate, t-butyl hydroperoxide, cumene hydroperoxide, ethyl cumene peroxide, diisopropyl hydroxydicarboxylic acid's ester, 2, 2 '-azo double, two ((2, 4-methyl pentane nitrile), 2, 2 '-azo double, two (isopropyl cyanide), 1, 1 '-azo double, two (hexamethylene-1-nitrile), dimethyl 2, 2,-azo double, two (2 Methylpropionic acid ester), or 2, 2 '-azo double, two [2-methyl-N-(2-ethoxy)-propionic acid amide .] etc.
Can determining according to the kind of initiator used as described suspension polymerization temperatures, the suspension polymerization temperatures that the present invention recommends is 40 DEG C��100 DEG C, it is preferred that suspension polymerization temperatures is 45 DEG C��90 DEG C, and preferred suspension polymerization temperatures is 50 DEG C��85 DEG C.
For polymerization initial stage pressure, it is preferable that gauge pressure is 0-5.0MPa, and then preferred 0.1-3.0MPa, it is particularly preferred to 0.2-2.0MPa.
Additionally, preferably make it carry out suspension polymerisation in the aqueous dispersion medium containing dispersion stabilizer and/or stably dispersing auxiliary agent in the present invention. For the consumption that makes of described aqueous dispersion medium, there is no particular limitation, relative to the polymerizable components (can gather monomer total amount) of 100 weight portions, it is preferred to use 100 weight portions are to the aqueous dispersion medium of 1000 weight portions.
Wherein said dispersion stabilizer, it is possible to be that silica sol, gel calcium carbonate, magnesium hydroxide, calcium phosphate, aluminium hydroxide, hydrated ferric oxide., calcium sulfate, sodium sulfate, calcium oxalate, calcium carbonate, brium carbonate, magnesium carbonate are or/and alumina sol etc. The consumption of dispersion stabilizer is preferably the 0.1wt%��20wt% of polymerizable components (can gather monomer total amount) gross weight.
Further, above-mentioned stably dispersing auxiliary agent is selected from: the stably dispersing auxiliary agent of the polymer electrolytes such as diethanolamine and the condensation product of aliphatic dicarboxylic acid, gelatin, polyvinylpyrrolidone, methylcellulose, poly(ethylene oxide), polyvinyl alcohol, the cationic surfactants such as alkyl trimethylammonium chloride or chlorination dialkyl dimethyl ammonium, the anion surfactants such as alkyl sodium sulfate, the various emulsifying agents such as zwitterionic surfactant such as alkyl dimethyl aminoacetic acid glycine betaine, alkyl dihydroxyethyl aminoacetic acid glycine betaine. The consumption of stably dispersing auxiliary agent is preferably the 0.001wt%��2.0wt% of polymerizable components (can gather monomer total amount) gross weight.
The pH of aqueous dispersion medium during polymerization suitably determines according to the kind of the dispersion stabilizer used. Such as, if dispersion stabilizer is selected from: metal Ca, Mg, Ba, Zn, the salt of Ni and Mn, oxide or hydroxide are (concrete such as calcium phosphate, calcium carbonate, magnesium hydroxide, magnesium oxide, barium sulfate, calcium oxalate, with one or two or more kinds (containing two kinds) mixture in the hydroxide of zinc, nickel or manganese), the then preferred 5-12 of pH value, more preferably 6-10; If dispersion stabilizer is selected from: the oxide of starch, methylcellulose, hydroxypropyl methyl cellulose, carboxyl methylcellulose, glue agar, silica sol, colloidal clays or aluminum or ferrum or hydroxide, the then preferred 1-6 of pH value, more preferably 3-5.
It addition, water solublity free radical inhibitor also can be contained in aqueous dispersion medium, to suppress the generation of the cohesion microsphere in polymerization. As water solublity free radical inhibitor, can be alkali metal nitrites (sodium nitrite and/or potassium nitrite etc.), bichromate (Ammonium bichromate. (two ammonium chromates), sodium dichromate (two sodium chromates) and/or potassium dichromate (two Neutral potassium chromates) etc.), stannous chloride, stannic chloride, ferrous chloride, iron chloride, ferrous sulfate, the free radical inhibitor such as water soluble ascorbic acid class and derivant thereof. In the stability water, it is preferable that alkali metal nitrites. Every 100 parts by weight polymerizable components (can gather monomer total amount), the consumption of water solublity free radical inhibitor is 0.0001-1 parts by weight, it is preferable that 0.0003-0.1 parts by weight.
In aqueous dispersion medium used by the present invention, also can contain electrolyte. For electrolyte, there is no particular limitation, as being selected from: lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bicarbonate, lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, sulphuric acid are by one or two or more kinds (containing two kinds) such as, sodium carbonate or benzoic acids. Relative to the aqueous dispersion medium of 100 parts by weight, electrolytical consumption is advisable with 0.1-50 parts by weight.
The average diameter of thermo-expandable microspheres provided by the present invention is 5 ��m��100 ��m, it is preferred that average diameter is 10 ��m��100 ��m, it is preferred that average diameter 10 ��m��60 ��m.
Additionally, with the thermo-expandable microspheres gross weight that provides for 100wt% for calculating benchmark, expandable substance accounts for 5wt%��50wt%, it is preferred that content is 10wt%��50wt%, it is preferred that content be 10wt%��40wt%, the optimum content of expandable substance is 10wt%��35wt%.
In presently preferred technical scheme, R1For C1��C6Straight or branched alkyl, preferred R1For C1��C3Straight or branched alkyl, best R1For methyl.
In a further preferred technical solution of the present invention, R2And R3It is respectively and independently selected from: H, C1��C3The C that straight or branched alkyl or hydroxyl replace1��C3One, preferred R in straight or branched alkyl2And R3It is respectively and independently selected from: a kind of in H, methyl or methylol, compound shown in best Formula II is acrylamide, N hydroxymethyl acrylamide or N,N-DMAA.
In a further preferred technical solution of the present invention, R4For C2��C4Straight or branched containing fluoroalkyl, best R4For trifluoroethyl or hexafluoro butyl.
When the polymerisation is essentially complete, can obtaining the microsphere of water paste or dispersion, they can be used as is or obtain so-called wet cake by any conventional method (such as bed filter, filter pressing, leaf filter, turn filter, band are filtered or are centrifuged and carry out dehydration). But, it is possible to by any conventional method (such as spray drying, support dry, tunnel drying, Rotary drying, drum dried, aeration-drying, turbo shelf dry, disk dries or fluid bed drying etc.), this microsphere is dried.
Outer surface at heat-swellable microsphere provided by the present invention also can attaching surface modifying agent, it is achieved dispersibility improve further or mobility is improved further.
Accompanying surface modifier can be one or two or more kinds (containing two kinds) mixture in organic system or inorganic system modifying agent,
Described organic system modifying agent, such as (but not limited to): metal soaps such as magnesium stearate, calcium stearate, zinc stearate, barium stearate, lithium stearates; Tissuemat E, lauric acid acid amide, nutmeg acid amide, palm fibre put the synthetic wax classes such as acid amide, stearmide, hardened castor oil; Polyacrylamide, polyimides, nylon, poly-methyl methacrylate vinegar, polyethylene or politef etc.
Described inorganic system modifying agent, such as (but not limited to): Talcum, Muscovitum, bentonite, sericite, white carbon black, curing aluminum, tungsten disulfide, fluorographite, calcium fluoride, boron nitride, silicon dioxide, aluminium oxide, Muscovitum, calcium carbonate, calcium hydroxide, calcium phosphate, magnesium hydroxide, magnesium phosphate, barium sulfate, titanium dioxide are admired, zinc oxide, ceramic bead, bead or crystal pearl etc.
The adhesion amount (being attached to heat-swellable microsphere surface) of described surface modifier is not particularly limited. But if it is considered that the function etc. of surface modifier can be played fully, count with unattached heat-swellable microsphere gross weight for 100 parts by weight, the adhesion amount of described surface modifier is 0.1-95 parts by weight, it is preferably 0.5-60 parts by weight, more preferably 5-50 parts by weight, it is most preferred that for 8-30 parts by weight.
The attachment of surface modifier can be undertaken by the unattached heat-swellable microsphere of mixing and surface modifier. For mixing, it does not have be particularly limited to, can carry out in the container have agitating device. Alternatively, it is also possible to use the powder mixer that can carry out common shake or stirring. As powder mixer, for instance zonate frond type mixer, vertical spin type mixer etc. can be enumerated and can carry out the powder mixer of shake stirring or stirring. Alternatively, it is also possible to use in recent years by the multi-functional powder mixer in hgher efficiency of combination agitating device and super mixer and high-speed mixer, SV mixer etc.
Thermo-expandable microspheres provided by the present invention can be used for papermaking, printing-ink (such as water-based inks, solvent-based ink, plastisol, uv curing ink etc.), putty, sealant, ultralight clay, base coat, binding agent, the degumming of binding agent, artificial leather, corium, paint, nonwoven fabric material, paper and plate, for various materials such as paper, plate, plastics, the coating (such as nonskid coating etc.) of metal and fabric, explosive, cable insulation, thermoplastic (such as polyethylene, polrvinyl chloride and ethane-acetic acid ethyenyl ester) or thermoplastic elastomer (TPE) (such as styrene-ethylene-butylene-styrene copolymer, styrene-butadiene-styrene, thermoplastic polyurethane and TPO), butadiene-styrene rubber, natural rubber, vulcanite, silicone rubber, thermosetting polymer (such as epoxy resin, polyurethane and polyester) etc. field.
The present invention is further elaborated by the examples below. In listed embodiment, except as otherwise noted, in embodiment, all numbers and percentage rate refer to number by weight and percentage rate, and the analysis of heat-swellable microsphere adopts following method and instrument:
(1) particle size distribution profiles analysis:
The particle size distribution of microsphere is that the particle size distribution sub laser diffraction analyzer LS13320 produced by Bekmancoulter company is measured. Average diameter is measured as volume average particle size, and particle size distribution is calculated as C.V. value (standard deviation/average diameter) X100.
(2) foam characteristics analysis:
The thermomechanical analyzer TMAQ-400 that the characteristic of heat-expandable microsphere is produced by TAInstrument company measures.
Sample is prepared by the 1.0mg heat-expandable microsphere held in the aluminum dish of diameter 6.7mm and degree of depth 4.5mm. Then, the aluminum dish of described aluminum dish diameter 6.5mm and degree of depth 4.0mm seals. According to TMA expanding probe type, sample temperature is increased to 230 DEG C with the programming rate of 50 DEG C/min from ambient temperature, and is applied the power of 0.5N by probe. Analyze and undertaken by measuring probe vertical displacement.
-expanding initial temperature (Tstart): probe displacement starts the temperature (DEG C) when increasing.
-foaming maximum temperature (Tmax): the temperature (DEG C) when probe displacement reaches maximum.
-maximum foaming displacement ((Dmax): the displacement (��m) when probe displacement reaches maximum.
Embodiment 1
By mixing 140 grams of acrylonitrile, 20 grams of N, N-DMAA, 40 grams of methyl methacrylates, 0.1 gram of methacrylic acid-2,2,2-trifluoro ethyl esters, 0.4 gram of trimethylol-propane trimethacrylate, 4 grams of benzoyl peroxides and 50 grams of isobutyltrimethylmethane .s obtain the oil phase of suspension polymerisation.
Adding 280 grams of deionized waters, 30 grams of sodium hydroxide in No. 1 beaker, 40 grams of sodium chloride and 0.2 gram of sodium lauryl sulphate fully dissolve; Adding 280 grams of deionized waters, 85 grams of Magnesium dichloride hexahydrates, 30 grams of sodium chloride in No. 2 beakers, the sodium nitrite of 0.01 gram is fully dissolved; First the solution in No. 1 beaker is poured in 2.5 liters of there-necked flasks with stirring paddle, then under 1200rpm rotating speed stirs, then be slowly added to the solution in No. 2 beakers in this there-necked flask. It is sufficiently stirred for again after adding 15 minutes, obtains the aqueous phase of suspension polymerisation.
Oil phase and aqueous phase is disperseed, thus preparing aaerosol solution by stirring 2 minutes under 7000rpm with homogeneous mixer. Injecting in 1 liter of autoclave by aaerosol solution at once, logical nitrogen replaces air, and to reactor supercharging to reach the initial pressure of 0.3MPa. Then, at 69-71 DEG C, polyreaction is carried out 20 hours. After being polymerized, obtain object (heat-swellable microsphere of the present invention) by filtering, wash, drying. The performance of object is in Table 2.
Embodiment 2
By mixing 40 grams of acrylonitrile, 2 grams of N, N-DMAA, 3 grams of methyl methacrylates, 4 grams of acrylic acid methyl ester .s, 0.1 gram of methacrylic acid-2,2,2-trifluoro ethyl esters, 0.5 gram of methacrylic acid, 0.1 gram of acrylic acid, 0.4 gram of trimethylol-propane trimethacrylate, 1 gram of azodiisobutyronitrile, 12 grams of isobutyltrimethylmethane .s and 3 grams of isopentane obtain the oil phase of suspension polymerisation.
In 200 weight portion ion exchange waters, add 23 parts by wt NaCl, 10 weight portions (effective ingredient amount: 20 weight %) silica sol, 0.1 weight account polyethylene ketopyrrolidine and 0.01 weight portion sodium nitrite, then by pH regulator to 2.4, mix equably, it can be used as aqueous dispersion medium.
Oil phase and aqueous phase is disperseed, thus preparing aaerosol solution by stirring 3 minutes under 6000rpm with homogeneous mixer. Injecting in 1 liter of autoclave by aaerosol solution at once, logical nitrogen replaces air, and to reactor supercharging to reach the initial pressure of 0.3MPa. Then, at 60-61 DEG C, polyreaction is carried out 20 hours. After being polymerized, obtain object (heat-swellable microsphere of the present invention) by filtering, wash, drying. The performance of object is in Table 2.
Embodiment 3-6
Except the kind changing monomer used, cross-linking agent, initiator and expandable substance and consumption and polymer temperature (referring specifically to table 1), other condition is identical with embodiment 1, prepares different heat-swellable microspheres, and its performance is in Table 2.
Table 1
In table 1, AN: acrylonitrile, MMA: methyl methacrylate, DMAA:N, N-DMAA, AM: acrylamide, HMAA:N-n-methylolacrylamide, TFEMA: trifluoroethyl methacrylate, HFBA: hexafluorobutyl acrylate, TMPDMA: trimethylol-propane trimethacrylate, EGDMA: Ethylene glycol dimethacrylate, DEGDE: diethylene glycol divinyl ether, BPO: benzoyl peroxide, AIBN: azodiisobutyronitrile, LPO: lauroyl peroxide, DCPD: peroxidating dicyclohexyl carbonate, IO: isobutyltrimethylmethane., NH: normal hexane, IP: isopentane.
Table 2
Comparative example 1��3
Except the kind changing monomer used, cross-linking agent, initiator and expandable substance and consumption and polymer temperature (referring specifically to table 1), other condition is identical with embodiment 1, prepares different heat-swellable microspheres, and its performance is in Table 2.
By table 1 with table 2 it can be seen that compare with comparative example 1-3, the embodiment 1-6 including N,N-DMAA (DMAA) and the monomer mixture of trifluoroethyl methacrylate shows the foam characteristics significantly improved, and has narrow particle size distribution.
Comparative examples 1 and 2, when replacing part AN as monomer with DMAA, and when being not added with trifluoroethyl methacrylate, TStartAnd TMaximumSignificantly improve, but particle size distribution is substantially wider.
Additionally, for only using trifluoroethyl methacrylate to be not added with the comparative example 3 of DMAA, although narrow particle size distribution, but TStartAnd TMaximumDo not significantly improve.
Method given according to the above description, those skilled in the art are it is conceivable that the multiple amendment of the present invention and other embodiments. It will thus be appreciated that protection scope of the present invention is not limited to the embodiment disclosed, protection scope of the present invention is set forth in the claims.
Claims (15)
1. a heat-swellable thermoplastic microspheres, it mainly can be gathered monomer by olefinic and expandable substance obtains through suspension polymerisation, obtained heat-swellable thermoplastic microspheres be with thermoplastic polymer for shell and be core with expandable substance the microsphere with nucleocapsid structure, it is characterized in that, wherein said olefinic can gather monomer by acrylonitrile, acrylic ester monomer, acrylamide monomers, acrylate containing fluorine monomer and acrylic monomer composition, the gross weight of monomer can be gathered for 100wt% for calculating benchmark with described olefinic, can gather in monomer at described olefinic, acrylonitrile accounts for 30wt%��90wt%, methacrylate-based monomer accounts for 5wt%��50wt%, acrylamide monomers accounts for 1wt%��20wt%, acrylate containing fluorine monomer accounts for 0.01wt%��1.0wt%, acrylic monomer accounts for 0wt%��40wt%,
Wherein, described methacrylate-based monomer is selected from: the mixture of one or two or more kinds in compound race described in Formulas I, described acrylamide monomers is selected from: the mixture of one or two or more kinds in compound race described in Formula II, described acrylate containing fluorine monomer is selected from: the mixture of one or two or more kinds in compound race described in formula III, described acrylic monomer is acrylic acid or/and methacrylic acid
The boiling point of described expandable substance not higher than the softening temperature of prepared thermoplastic polymer,
The polymerization temperature of described suspension polymerisation is 40 DEG C��100 DEG C, and the polymerization gauge pressure of described suspension polymerisation is 0.1MPa��3.0MPa,
In formula, R1For C1��C10Straight chain, side chain or cyclic alkyl, R2And R3It is respectively and independently selected from: H, C1��C6The C that straight or branched alkyl or hydroxyl replace1��C6One, R in straight or branched alkyl4For C1��C6Straight or branched containing fluoroalkyl, R5For H or methyl.
2. heat-swellable thermoplastic microspheres as claimed in claim 1, it is characterised in that wherein said acrylic monomer accounts for 1wt%��30wt%.
3. heat-swellable thermoplastic microspheres as claimed in claim 1 or 2, it is characterised in that with described thermo-expandable microspheres gross weight for 100wt% for calculating benchmark, expandable substance accounts for 5wt%��50wt%.
4. heat-swellable thermoplastic microspheres as claimed in claim 3, it is characterised in that wherein expandable substance accounts for 10wt%��35wt%.
5. heat-swellable thermoplastic microspheres as claimed in claim 4, it is characterised in that wherein said expandable substance C5��C12Aliphatic hydrocarbon compounds.
6. heat-swellable thermoplastic microspheres as claimed in claim 5, it is characterised in that wherein said expandable substance is C5��C8Straight or branched saturated hydrocarbons compound.
7. the heat-swellable thermoplastic microspheres as described in claim 1,2 or 6, it is characterised in that wherein R1For C1��C6Straight or branched alkyl.
8. heat-swellable thermoplastic microspheres as claimed in claim 7, it is characterised in that wherein R1For C1��C3Straight or branched alkyl.
9. heat-swellable thermoplastic microspheres as claimed in claim 8, it is characterised in that wherein R1For methyl.
10. the heat-swellable thermoplastic microspheres as described in claim 1,2 or 6, it is characterised in that wherein R2And R3It is respectively and independently selected from: H, C1��C3The C that straight or branched alkyl or hydroxyl replace1��C3One in straight or branched alkyl.
11. heat-swellable thermoplastic microspheres as claimed in claim 10, it is characterised in that wherein R2And R3It is respectively and independently selected from: a kind of in H, methyl or methylol.
12. heat-swellable thermoplastic microspheres as claimed in claim 11, it is characterised in that acrylamide monomers wherein used is that acrylamide, N hydroxymethyl acrylamide are or/and N,N-DMAA.
13. the heat-swellable thermoplastic microspheres as described in claim 1,2 or 6, it is characterised in that wherein R4For C2��C4Straight or branched containing fluoroalkyl.
14. heat-swellable thermoplastic microspheres as claimed in claim 13, it is characterised in that wherein R4For trifluoroethyl or hexafluoro butyl.
15. heat-swellable thermoplastic microspheres as claimed in claim 1, it is characterised in that wherein the polymerization temperature of suspension polymerisation is 50 DEG C��85 DEG C, and the polymerization gauge pressure of suspension polymerisation is 0.2MPa��2.0MPa.
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| CN104379647B (en) * | 2012-09-04 | 2018-06-05 | 西能化工科技(上海)有限公司 | Heat-expandable microsphere and its preparation and application |
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| JP6218998B1 (en) | 2016-02-19 | 2017-10-25 | 松本油脂製薬株式会社 | Thermally expandable microspheres and their applications |
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| CN108912384B (en) * | 2018-07-20 | 2021-03-30 | 西能化工科技(上海)有限公司 | Ultrahigh-temperature expandable thermoplastic microspheres and preparation method and application thereof |
| CN109749534A (en) * | 2019-01-10 | 2019-05-14 | 西能化工科技(上海)有限公司 | Automobile PVC stone-impact-proof paint and preparation method thereof |
| CN111647235B (en) * | 2019-03-04 | 2022-04-01 | 合肥华凌股份有限公司 | Novel migration-resistant PVC sealing material and application thereof |
| CN109970466A (en) * | 2019-03-29 | 2019-07-05 | 东莞市泰赛特汽车用品科技有限公司 | A kind of environmental protection brick face antilubricant and preparation method thereof |
| CN110698721B (en) * | 2019-10-15 | 2022-02-08 | 江苏科技大学 | Polymethacrylimide thermal expansion microsphere and preparation method thereof |
| CN111116969B (en) * | 2020-01-03 | 2022-04-01 | 潘自地 | Method for preparing thermal expansion microspheres based on interfacial polymerization |
| CN113549241A (en) * | 2020-04-23 | 2021-10-26 | 南京工业大学 | Polymer foaming microsphere and preparation method thereof |
| US11505687B2 (en) | 2020-08-05 | 2022-11-22 | Nano And Advanced Materials Institute Limited | Environmentally degradable foamed master batch composition and using thereof |
| EP4206245A1 (en) | 2020-08-25 | 2023-07-05 | Zhejiang Quzhou Jusu Chemical Industry Co., Ltd. | Thermally expandable polyvinylidene chloride microsphere and preparation method therefor |
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