CN108084324A - A kind of preparation method of high-intensity special-shaped poly- (methyl) acrylimide foam - Google Patents
A kind of preparation method of high-intensity special-shaped poly- (methyl) acrylimide foam Download PDFInfo
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- CN108084324A CN108084324A CN201711446287.0A CN201711446287A CN108084324A CN 108084324 A CN108084324 A CN 108084324A CN 201711446287 A CN201711446287 A CN 201711446287A CN 108084324 A CN108084324 A CN 108084324A
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- foam
- methyl
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- weight
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- 239000006260 foam Substances 0.000 title claims abstract description 131
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 238000005187 foaming Methods 0.000 claims abstract description 30
- 229920007790 polymethacrylimide foam Polymers 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 17
- 230000002159 abnormal effect Effects 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002347 injection Methods 0.000 claims abstract 2
- 239000007924 injection Substances 0.000 claims abstract 2
- 230000000379 polymerizing effect Effects 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 32
- 238000004945 emulsification Methods 0.000 claims description 14
- 239000004088 foaming agent Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 5
- 230000036772 blood pressure Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 210000003934 vacuole Anatomy 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical group CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000013022 venting Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 32
- 239000002245 particle Substances 0.000 description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 23
- 238000003756 stirring Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 239000003431 cross linking reagent Substances 0.000 description 13
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000000178 monomer Substances 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- 238000003754 machining Methods 0.000 description 8
- -1 poly- (methyl) acryloyl Chemical group 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000008258 liquid foam Substances 0.000 description 7
- 238000010926 purge Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 230000006641 stabilisation Effects 0.000 description 7
- 238000011105 stabilization Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229920006934 PMI Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical class CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 235000004443 Ricinus communis Nutrition 0.000 description 3
- 240000000528 Ricinus communis Species 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 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
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UJTPZISIAWDGFF-UHFFFAOYSA-N ethenylsulfonylbenzene Chemical compound C=CS(=O)(=O)C1=CC=CC=C1 UJTPZISIAWDGFF-UHFFFAOYSA-N 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical group CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-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
- RZYKUPXRYIOEME-UHFFFAOYSA-N CCCCCCCCCCCC[S] Chemical compound CCCCCCCCCCCC[S] RZYKUPXRYIOEME-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 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
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- PZBFGYYEXUXCOF-UHFFFAOYSA-N TCEP Chemical compound OC(=O)CCP(CCC(O)=O)CCC(O)=O PZBFGYYEXUXCOF-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 150000001344 alkene derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- FYIBPWZEZWVDQB-UHFFFAOYSA-N dicyclohexyl carbonate Chemical compound C1CCCCC1OC(=O)OC1CCCCC1 FYIBPWZEZWVDQB-UHFFFAOYSA-N 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical group CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229950010765 pivalate Drugs 0.000 description 1
- 238000012545 processing 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
- 238000005086 pumping Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/48—Isomerisation; Cyclisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of preparation methods of high-intensity special-shaped poly- (methyl) acrylimide foam; the raw material for preparing poly- (methyl) acrylimide foam is added in reaction kettle; nitrogen protection is lower to carry out prepolymerization; the viscosity of reaction solution reduces reaction temperature when reaching preset value, add in low temperature initiators；Gained reaction solution is foamed；It will be in the reaction solution injection mold after foaming under nitrogen protection；Foam curing temperature is controlled to carry out polymerizing curable, foam is taken out in form removal；The foam of taking-up is transferred in baking oven and carries out solidify afterwards；Special-shaped polymethacrylimide foam obtained by solidify afterwards is reentered into mold, again fretting map, cooling, form removal to obtain the final product.High-intensity special-shaped PMI foams can be efficiently prepared in the present inventive method, greatly reduce the cost of production abnormal shape PMI foams at present, efficiency is improved, improves performance, the field of special-shaped polymethacrylimide foam is needed available for new-energy automobile, cycle hub, propeller blade etc..
Description
Technical field
The present invention relates to the technical fields of high molecular material, and in particular to a kind of high-intensity special-shaped poly- (methyl) acryloyl is sub-
The preparation method of amine foamed material.
Background technology
PMI foamed plastics was one of current mechanical property and the highest foamed plastics of heat resistance, from Degussa in 1972
Since commercially producing PMI foamed materials, PMI is due to performances such as its high intensity, high rigidity and excellent heat-resisting and creep resistants,
It is widely used in the fields such as aerospace, communications and transportation, wind-powered electricity generation, ship.
But PMI foamed materials are obtained currently on the market, product form only has a kind of form of unique plate, this list
One product form limits its application range；If by PMI Foam machinings into profile shapes, in bicycle rim, lightweight
Automobile, propeller blade etc. need high specific strength, high heat-resisting special-shaped foam art to have great advantage, but prepare at present
Special-shaped PMI foams need just obtain required structural member by mechanical processing (such as cutting is polished) mode, and foam waste is big,
Machining cost is high, efficiency is low.
Therefore, it is imperative to study poly- (methyl) acrylimide abnormal shape foam.
At present, the starting stage is still in for the research of poly- (methyl) acrylimide abnormal shape foam both at home and abroad.Patent
In CN101341227A heat-expandable macrospheres and its manufacturing method and purposes gathering comprising foaming agent is prepared for using suspension polymerisation
(methyl) acrylimide heat-expandable macrosphere, special-shaped poly- (methyl) acrylimide foam can be obtained by being packed into mold；
Patent CN101857656A first will for producing in the expandable particles of poly- (methyl) acrylimide foamed material and its application
Methacrylic acid/methacrylonitrile and related auxiliaries are uniformly mixed, and are poured into mold, and it is poly- (methyl) that bulk polymerization obtains plate
Then acrylimide plate crushes and obtains expandable particles, expandable particles prefoam is obtained pre-expanded beads, then will be pre-
Expanded particle inserts foaming in mold and obtains special-shaped PMI foams；Patent CN103814068A include adhesion promotor based on poly-
First poly- (methyl) acrylimide plate is ground in the preparation method of the foaming copolymer of (methyl) acrylimide, is obtained
To the expandable polymer particle of certain particle size range, then prefoam at a certain temperature obtains pre-expanded beads, Ran Houzai
Adhesive is mixed into pre-expanded beads, finally particle is injected in mold and is foamed, special-shaped PMI foams is obtained, partly changes
It has been apt to the problem of boundary strength is low between foam inside particle in patent CN101857656A；Poly- (the first of patent CN103923337A
Base) method that abnormal shape PMI foams are prepared in patent CN101857656A has been used for reference in acrylimide composite foam absorbing material,
Surface treated wave absorbing agent is introduced simultaneously, has obtained poly- (methyl) the acrylimide bubble of abnormal shape with absorbing property
Foam；It is hard so as to prepare that patent CN106170508A carries out foaming in closed mould to poly- (methyl) acrylimide particle
First poly- (methyl) acrylimide plate is ground to have obtained expandability particle in matter foam core, then send out expandability particle in advance
Bubble finally inserts foaming in mold and obtains special-shaped PMI foams；Patent 105793338A is for the then foaming mould in Guan Bi mould
First poly- (methyl) acrylimide plate is ground to obtain particle in the prefoam of poly- (methyl) the acrylimide particle of modeling, so
Particle specific wavelength IR light is irradiated afterwards, then prefoam in a short time, finally insert foaming in mold and obtain special-shaped PMI
Foam；The molding that patent CN106459465A carries out poly- (methyl) acrylimide particle in closed mould pressure correlation is sent out
Obtained poly- (methyl) acrylimide particle is carried out prefoam, Ran Houchong by bubble under stress so as to prepare in rigid foam core
Enter in mold, decompression foaming, obtain the smaller special-shaped foam of density gradient.Poly- (methyl) propylene of foam-in-mould on the market at present
Acid imide foam is crushed by poly- (methyl) acrylimide plate, prefoam, foaming basic principle be prepared, phase
Product is closed from apparent, foam surface has subtle border, but more smooth, and foam inside can be embedded in metal
Component.
As it can be seen that it is to the preparation main thought of special-shaped poly- (methyl) acrylimide foam both at home and abroad at present：1st, poly- (first
Base) acrylimide expandability particle preparation, system can be crushed by suspension polymerisation or by poly- (methyl) acrylimide plate
It is standby to obtain；2nd, expandability particle is subjected to prefoam；3rd, pre-expanded beads are filled in mold and are foamed to obtain special-shaped bubble again
Foam；4th, by adding in adhesive, high pressure prefoam into system, the means such as low pressure foams again improve the performance of special-shaped foam.
But there are many defects for process above：1st, polymer plate is crushed to obtain satisfactory poly- (methyl) acrylimide
Rates of particles is extremely low, substantially increases the cost for preparing special-shaped foam, even more than machining mode prepare special-shaped foam into
This；2nd, since, there are border, and the bond strength between border is relatively low between the particle of foam-in-mould body, although adhesive can be passed through
Mode improved, but the special-shaped foaming properties finally obtained, compared with foam board, hydraulic performance decline is still very big.
The content of the invention
The defects of in order to which more than foam-in-mould method is overcome to prepare special-shaped poly- (methyl) and alkene acid imide foam, this patent propose
A kind of re-solidified new method for preparing high-intensity special-shaped poly- (methyl) acrylimide foam that first foams.
A kind of preparation method of poly- (methyl) the acrylimide foam of abnormal shape, includes the following steps：
(1) pre-polymerization：By (methyl) acrylic acid, (methyl) acrylonitrile, Third monomer, viscosity-adjusting agent resin, foaming agent, middle height
The raw materials such as warm initiator, foaming stabilizer, crosslinking agent, antishrinking agent, functional aid and other related auxiliaries are added to reaction
In kettle, nitrogen protection is lower to carry out prepolymerization, to certain viscosity after stop reaction；Reacting liquid temperature is reduced, adds in low temperature initiators；
(2) foam：Reaction solution is foamed to obtain the fine and smooth foam stablized of abscess；
(3) injection molding：Preprepared mold with reaction kettle is connected, is injected under nitrogen protection in mold, by mold
Mouth is closed；
(4) it is low-temperature fast-curing：Foam curing temperature is controlled, initiation reaction rapid polymerization cures, and foam is taken out in form removal；
(5) solidify afterwards：The foam of taking-up is transferred in baking oven and carries out solidify afterwards, residual monomer is made fully to participate in polymerizeing,
Obtain high-intensity special-shaped polymethacrylimide foam；
(6) foam afterwards：Obtained polymethacrylimide foam is reentered into mold, again fretting map, overcome few
The change in size that shrinkage band is come is measured, makes foam size and die size completely the same, is cooled down, form removal, obtains final special-shaped poly- first
Base acrylimide froth pulp.
The method of the present invention is suitable for all PMI and is formulated.Preferably, the proportioning of raw material is in step (1)：
It is further preferred that the proportioning of raw material is in step (1)：
Still more preferably (with reference to embodiment 6 in case substantive examination is useful when changing), the proportioning of raw material is in step (1)：
The Third monomer is (methyl) acrylic amide, (methyl) esters of acrylic acid, maleimide, maleic anhydride
Class it is at least one or several, i.e., any one or it is arbitrary two kinds and more than arbitrary proportion mixture.
The viscosity-adjusting agent resin is thickener class such as polyacrylamide, polyvinyl alcohol, polymethyl methacrylate and gathers
At least one of methacrylic acid etc., i.e., any one or it is arbitrary two kinds and more than arbitrary proportion mixture.
The low temperature initiators form for the redox system of redox system such as BPO and DMA composition, BPO and DMT
Redox system, the redox system of isopropyl benzene hydroperoxide and DMT compositions, the oxygen of persulfate and fatty amine composition
Change at least one of reduction system etc., i.e., any one or it is arbitrary two kinds and more than arbitrary proportion mixture.
The high temperature initiator is alkyl peroxide such as dibenzoyl peroxide, dilauroyl peroxide, peroxidating two
Dicyclohexyl carbonate, dicetyl peroxydicarbonate isopropyl ester and peroxide tert pivalate ester, azo such as azodiisobutyronitrile, idol
At least one of two different heptonitrile of nitrogen, i.e., any one or it is arbitrary two kinds and more than arbitrary proportion mixture.
The foaming stabilizer is to be surfactant-based such as the castor-oil plant sodium alkoxide of sulfonation, polyether silicone, dodecyl sulphur
At least one of sour sodium, sodium sulfate of polyethenoxy ether of fatty alcohol, α-sodium olefin sulfonate, alkylolamides and silicone amide etc.,
I.e. any one or it is arbitrary two kinds and more than arbitrary proportion mixture.
The crosslinking agent is (methyl) acrylamide, allyl methacrylate, zinc methacrylate, methacrylic acid fourth
At least one of ester and magnesinm methacrylate, i.e., any one or it is arbitrary two kinds and more than arbitrary proportion mixture.
The antishrinking agent be the alkene derivatives containing larger rigid side group for example styrene, 4- acetoxy-styrenes,
At least one of α-methylstyrene, maleimide and phenyl vinyl sulfone etc., i.e., any one or it is arbitrary two kinds and with
On arbitrary proportion mixture.
The functional aid is the phosphorus nitrogen systems such as fire retardant such as TCEP, TCPP, TDCPP, DMMP, triphenyl phosphate and MPP
Halogen-free flame retardants, wave absorbing agent is such as through surfactant-modified conductive black, carbon nanotubes, Nano carbon fibers peacekeeping metal dispersion
Deng at least one of conductive absorbing material, i.e., any one or it is arbitrary two kinds and more than arbitrary proportion mixture.
Preferably, mixed liquor dispersing technology is in step (1), and the mulser of 2000-3000r/min is passed through in Scattered Kettle
High speed shear 5-10min.
Preferably, reaction temperature is 40-85 DEG C, mixing speed 10-20r/min, reaction time 60- in step (1)
120min, viscosity is 30-100mpa.s after reaction；It is further preferred that mixing speed is 18-20r/min, the reaction time is
100-120min, viscosity is 60-80mpa.s after reaction.
Preferably, it is continually fed into step (1) with the flow velocity of 10~20mL/min in reaction kettle.
Preferably, temperature drops to 5-15 DEG C after reaction in step (1), it is further preferred that 5-10 DEG C is down to, it can be by cold
But water recirculating still chuck obtains, and stirring 30min makes its dissolving complete after adding in low temperature initiators at such a temperature.
Preferably, foaming method can emulsification makes the thick liquid in kettle become to steep at a high speed by mulser in step (2)
Foam, mulser rotating speed are 1600-2200r/min, and emulsification times 5-15min is then injected into mold；First feed liquid can also be turned
Enter in autoclave, be pressed into the nitrogen of 5-10MPa, pressurize 10-30min, then reduction of blood pressure in high-speed to certain volume, obtains reaction vacuole
Foam is then injected into mold；Sodium acid carbonate, zinc carbonate or magnesium carbonate that can also be by adding in 5-10 parts by weight in reaction solution etc.
Chemical foaming agent generates reaction solution foam, is then injected into mold；By the above-mentioned means, uniform foam cell, controllable bubble can be obtained
Foam；
Preferably, in step (3) die venting mode first by container vacuum-pumping to -0.1, then to lead to nitrogen to normal pressure,
And so on 5 times, to ensure fully to drain air, then logical nitrogen to normal pressure, injects mold by gravity by reaction solution,
Ensure cell stability.
Preferably, reaction temperature is 25-35 DEG C, reaction time 1-3h in step (4), and foam solidification has some strength,
To meet the production requirement of higher efficiency, enter baking oven after collapsible die in batches and carry out solidify afterwards；For convenience of form removal, die surface passes through
Teflon spray treatment.
Preferably, in step (5) solidify afterwards temperature be 40-90 DEG C/20-100h, 90-150 DEG C/10-60h；
Preferably, backfoaming process is 190-250 DEG C/10-60min in step (6).
It is further preferred that temperature drops to 8-10 DEG C after reaction in step (1)；Foaming method passes through breast in step (2)
Emulsification makes the thick liquid in kettle become foam to change machine at a high speed, and mulser rotating speed is 1800-2000r/min, emulsification times 8-
12min；Reaction temperature is 28-32 DEG C in step (4), reaction time 1.5-2.5h；Solidify afterwards temperature is 65- in step (5)
75 DEG C/35-45h, 130-150 DEG C/10-12h；Backfoaming process is 230-240 DEG C/25-35min in step (6).
Most preferably, temperature drops to 10 DEG C after reaction in step (1)；Foaming method passes through mulser high speed in step (2)
Emulsification makes the thick liquid in kettle become foam, and mulser rotating speed is 1900r/min, emulsification times 10min；In step (4)
Reaction temperature is 30 DEG C, reaction time 2h；In step (5) solidify afterwards temperature be 60 DEG C/40h, 140 DEG C/10h；In step (6)
Backfoaming process is 235 DEG C/30min.
It is summarized herein according to embodiment 6, in case modification right requirement is useful when reply is creative
Abnormal shape polymethacrylimide foam of the present invention can be used for new-energy automobile, cycle hub, propeller
Blade etc. needs the field of special-shaped polymethacrylimide foam.
Compared with prior art, the present invention has the following advantages：
(1) compared with by being machined out to obtain the method for special-shaped foam to polymethacrylimide foam plate, this
Method can save 40% or so raw material, foam prepares speed faster, more efficient, eliminates machining without waste of material
The time of engraving；And the present invention first foams and polymerize afterwards, more crosslinking agents can be added in, so as to adjust within the specific limits
Foamy body；
(2) with by the way that Polymethacrylimide plate is broken into particle prefoam, being then filled with the method phase of mold
Than present invention gained foam various aspects of performance is more preferable, and Compression and Expansion performance is its 2 times or so, and without wastage of material, can be saved
50% wastage of material is gone, it is more efficient, the time of foam-in-mould can be saved, there is huge advantage.
Specific embodiment
Example below is the further explanation to the present invention rather than limits the scope of the invention.
Foam density is tested according to ISO 845；
Foam compression intensity is tested according to ISO 844；
Foam tensile performance is tested according to ASTM D638；
Foam heat distortion temperature is tested according to DIN53424；
Initiator used, foaming agent and crosslinking agent are convenient source in following embodiment.
Embodiment 1
(1) pre-polymerization：By 50 parts by weight of (methyl) acrylic acid, 50 parts by weight of (methyl) acrylonitrile, 20 parts by weight of acrylamide,
8.5 parts by weight of polyether silicone, 1 parts by weight of foaming agent, 0.6 parts by weight of high temperature initiator, 7.5 weight of castor-oil plant sodium alkoxide of sulfonation
Amount part, 8 parts by weight of crosslinking agent, 8 parts by weight of styrene are added in Scattered Kettle, are vacuumized, inflated with nitrogen, exclude the air in kettle,
Then maintaining nitrogen purge, nitrogen flow 13mL/min, be uniformly dispersed to obtain mixed liquor, then heats while stirring, reaction temperature 85
DEG C, mixing speed 20r/min reacts 105min, and test pre-polymerization liquid viscosity is 63mpa.s；Reacting liquid temperature is reduced to 7 DEG C, is added
Enter 1 parts by weight low temperature initiators, stirring and dissolving；
(2) foam：Feed liquid is transferred in autoclave, is pressed into the nitrogen of 9MPa, pressurize 25min, then reduction of blood pressure in high-speed to thing
The volume first calculated obtains reaction solution foam, is then injected into mold；
(3) injection molding：Preprepared mold is vacuumized, then inflated with nitrogen to normal pressure is connected with autoclave, pass through weight
Power effect pours into foamed liquid foam in mold, and mold mouth is closed；
(4) it is low-temperature fast-curing：Foam reactant liquid temperature degree is controlled as 25 DEG C, the initiation reaction 1h in the case of cell stabilization
Cure, form removal, take out foam；
(5) solidify afterwards：The foam of taking-up is transferred to 40 DEG C/100h in baking oven, 90 DEG C/60h solidify afterwards make residual monomer
Polymerization is fully participated in, obtains high-intensity special-shaped polymethacrylimide foam；
(6) foam afterwards：Foam after solidify afterwards is reentered into mold and carries out fretting map again, foam process for 190 DEG C/
60min；
Performance：Foaming properties are shown in Table 1.
Embodiment 2
(1) pre-polymerization：By 40 parts by weight of (methyl) acrylic acid, 60 parts by weight of (methyl) acrylonitrile, 10 weight of methyl acrylate
Part, 10 parts by weight of polyacrylamide, 2.5 parts by weight of foaming agent, 0.7 parts by weight of high temperature initiator, 8 weight of lauryl sodium sulfate
Amount part, 4 parts by weight of crosslinking agent, 7.6 parts by weight of 4- acetoxy-styrenes are added in Scattered Kettle, are vacuumized, inflated with nitrogen, are excluded
Air in kettle, then maintaining nitrogen purge, nitrogen flow 12mL/min, be uniformly dispersed to obtain mixed liquor, then heats while stirring,
85 DEG C, mixing speed 18r/min of reaction temperature, reacts 100min, and test pre-polymerization liquid viscosity is 61mpa.s；Reduce reaction liquid temperature
It spends to 9 DEG C, adds in 0.73 parts by weight low temperature initiators, stirring and dissolving；
(2) foam：The sodium acid carbonate of 7.5 parts by weight is added in reaction solution, is stirred evenly, reacts 60min, obtains reaction vacuole
Foam is then injected into mold；
(3) injection molding：Preprepared mold is vacuumized, then inflated with nitrogen to normal pressure is connected with autoclave, pass through weight
Power effect pours into foamed liquid foam in mold, and mold mouth is closed；
(4) it is low-temperature fast-curing：Foam reactant liquid temperature degree is controlled as 27 DEG C, the initiation reaction in the case of cell stabilization
1.6h cures, form removal, takes out foam；
(5) solidify afterwards：The foam of taking-up is transferred to 50 DEG C/85h in baking oven, 100 DEG C/50h solidify afterwards make residual monomer
Polymerization is fully participated in, obtains high-intensity special-shaped polymethacrylimide foam；
(6) foam afterwards：Foam after solidify afterwards is reentered into mold and carries out fretting map again, foam process for 245 DEG C/
20min；
Performance：Foaming properties are shown in Table 1.
Embodiment 3
(1) pre-polymerization：By 65 parts by weight of (methyl) acrylic acid, 35 parts by weight of (methyl) acrylonitrile, 15 weight of maleimide
Part, 8 parts by weight of polyvinyl alcohol, 3 parts by weight of foaming agent, 0.9 parts by weight of high temperature initiator, sodium sulfate of polyethenoxy ether of fatty alcohol
7 parts by weight, 2 parts by weight of crosslinking agent, 5 parts by weight of α-methylstyrene are added in Scattered Kettle, are vacuumized, inflated with nitrogen, exclude kettle
Interior air, then maintaining nitrogen purge, nitrogen flow 14mL/min, be uniformly dispersed to obtain mixed liquor, then heats while stirring, instead
78 DEG C, mixing speed 20r/min of temperature is answered, reacts 120min, test pre-polymerization liquid viscosity is 70mpa.s；Reduce reacting liquid temperature
To 8 DEG C, 0.4 parts by weight low temperature initiators, stirring and dissolving are added in；
(2) foam：The magnesium carbonate of 5 parts by weight is added in reaction solution, is stirred evenly, 45min is reacted, obtains reaction solution foam,
It is then injected into mold；
(3) injection molding：Preprepared mold is vacuumized, then inflated with nitrogen to normal pressure is connected with autoclave, pass through weight
Power effect pours into foamed liquid foam in mold, and mold mouth is closed；
(4) it is low-temperature fast-curing：Foam reactant liquid temperature degree is controlled as 35 DEG C, the initiation reaction in the case of cell stabilization
1.5h cures, form removal, takes out foam；
(5) solidify afterwards：The foam of taking-up is transferred to 60 DEG C/65h in baking oven, 110 DEG C/40h solidify afterwards make residual monomer
Polymerization is fully participated in, obtains high-intensity special-shaped polymethacrylimide foam；
(6) foam afterwards：Foam after solidify afterwards is reentered into mold and carries out fretting map again, foam process for 250 DEG C/
10min；
Performance：Foaming properties are shown in Table 1.
Embodiment 4
(1) pre-polymerization：By 70 parts by weight of (methyl) acrylic acid, 30 parts by weight of (methyl) acrylonitrile, 10 parts by weight of maleic anhydride,
9 parts by weight of PMMA, 3 parts by weight of foaming agent, 0.7 parts by weight of high temperature initiator, 7.8 parts by weight of alkylolamides, crosslinking agent 3
Parts by weight, 7.3 parts by weight of phenyl vinyl sulfone are added in Scattered Kettle, are vacuumized, inflated with nitrogen, exclude the air in kettle, then
Maintaining nitrogen purge, nitrogen flow 11mL/min, be uniformly dispersed to obtain mixed liquor, then heats while stirring, and 75 DEG C of reaction temperature is stirred
Speed 19r/min is mixed, reacts 98min, test pre-polymerization liquid viscosity is 60mpa.s；Reacting liquid temperature is reduced to 9 DEG C, adds in 0.75
Parts by weight low temperature initiators, stirring and dissolving；
(2) foam：By mulser, emulsification makes the thick liquid in kettle become foam at a high speed, and mulser rotating speed is 2000r/
Min, emulsification times 8min, is then injected into mold；
(3) injection molding：Preprepared mold is vacuumized, then inflated with nitrogen to normal pressure is connected with autoclave, pass through weight
Power effect pours into foamed liquid foam in mold, and mold mouth is closed；
(4) it is low-temperature fast-curing：Foam reactant liquid temperature degree is controlled as 28 DEG C, the initiation reaction in the case of cell stabilization
1.6h cures, form removal, takes out foam；
(5) solidify afterwards：The foam of taking-up is transferred to 70 DEG C/40h in baking oven, 120 DEG C/30h solidify afterwards make residual monomer
Polymerization is fully participated in, obtains high-intensity special-shaped polymethacrylimide foam；
(6) foam afterwards：Foam after solidify afterwards is reentered into mold and carries out fretting map again, foam process for 225 DEG C/
40min；
Performance：Foaming properties are shown in Table 1.
Embodiment 5
(1) pre-polymerization：By 60 parts by weight of (methyl) acrylic acid, 40 parts by weight of (methyl) acrylonitrile, 15 weight of Methacrylamide
Measure part, 8 parts by weight of polyvinyl alcohol, 1.4 parts by weight of foaming agent, 0.9 parts by weight of high temperature initiator, 7 parts by weight of alkylolamides,
6 parts by weight of crosslinking agent, 8 parts by weight of 4- acetoxy-styrenes are added in Scattered Kettle, are vacuumized, inflated with nitrogen, are excluded in kettle
Air, then maintaining nitrogen purge, nitrogen flow 16mL/min, be uniformly dispersed to obtain mixed liquor, then heats while stirring, reaction temperature
45 DEG C, mixing speed 20r/min of degree, reacts 120min, and test pre-polymerization liquid viscosity is 60mpa.s；Reacting liquid temperature is reduced to 7
DEG C, add in 0.4 parts by weight low temperature initiators, stirring and dissolving；
(2) foam：Feed liquid is transferred in autoclave, is pressed into the nitrogen of 7.5MPa, pressurize 25min, then reduction of blood pressure in high-speed to thing
The volume first calculated obtains reaction solution foam, is then injected into mold；
(3) injection molding：Preprepared mold is vacuumized, then inflated with nitrogen to normal pressure is connected with autoclave, pass through weight
Power effect pours into foamed liquid foam in mold, and mold mouth is closed；
(4) it is low-temperature fast-curing：Foam reactant liquid temperature degree is controlled as 35 DEG C, the initiation reaction in the case of cell stabilization
1.5h cures, form removal, takes out foam；
(5) solidify afterwards：The foam of taking-up is transferred to 80 DEG C/20h in baking oven, 130 DEG C/20h solidify afterwards make residual monomer
Polymerization is fully participated in, obtains high-intensity special-shaped polymethacrylimide foam；
(6) foam afterwards：Foam after solidify afterwards is reentered into mold and carries out fretting map again, foam process for 205 DEG C/
50min；
Performance：Foaming properties are shown in Table 1.
Embodiment 6
(1) pre-polymerization：By 65 parts by weight of (methyl) acrylic acid, 35 parts by weight of (methyl) acrylonitrile, methyl methacrylate 25
Parts by weight, 6 parts by weight of polyacrylamide, 3 parts by weight of foaming agent, 0.8 parts by weight of high temperature initiator, lauryl sodium sulfate 5
Parts by weight, 2.5 parts by weight of crosslinking agent, 6.5 parts by weight of α-methylstyrene are added in Scattered Kettle, are vacuumized, inflated with nitrogen, are excluded
Air in kettle, then maintaining nitrogen purge, nitrogen flow 15mL/min, be uniformly dispersed to obtain mixed liquor, then heats while stirring,
60 DEG C, mixing speed 15r/min of reaction temperature, reacts 110min, and test pre-polymerization liquid viscosity is 61mpa.s；Reduce reaction liquid temperature
It spends to 10 DEG C, adds in 0.6 parts by weight low temperature initiators, stirring and dissolving；
(2) foam：By mulser, emulsification makes the thick liquid in kettle become foam at a high speed, and mulser rotating speed is 1900r/
Min, emulsification times 10min, is then injected into mold；
(3) injection molding：Preprepared mold is vacuumized, then inflated with nitrogen to normal pressure is connected with autoclave, pass through weight
Power effect pours into foamed liquid foam in mold, and mold mouth is closed；
(4) it is low-temperature fast-curing：Foam reactant liquid temperature degree is controlled as 30 DEG C, the initiation reaction 2h in the case of cell stabilization
Cure, form removal, take out foam；
(5) solidify afterwards：The foam of taking-up is transferred to 70 DEG C/40h in baking oven, 140 DEG C/10h solidify afterwards make residual monomer
Polymerization is fully participated in, obtains high-intensity special-shaped polymethacrylimide foam；
(6) foam afterwards：Foam after solidify afterwards is reentered into mold and carries out fretting map again, foam process for 235 DEG C/
30min；
Performance：Foaming properties are shown in Table 1.
Embodiment 7
(1) pre-polymerization：By 30 parts by weight of (methyl) acrylic acid, 70 parts by weight of (methyl) acrylonitrile, 20 parts by weight of acrylamide,
8.5 parts by weight of polyether silicone, 1 parts by weight of foaming agent, 0.6 parts by weight of high temperature initiator, 7.5 weight of castor-oil plant sodium alkoxide of sulfonation
Amount part, 8 parts by weight of crosslinking agent, 8 parts by weight of styrene are added in Scattered Kettle, are vacuumized, inflated with nitrogen, exclude the air in kettle,
Then maintaining nitrogen purge, nitrogen flow 13mL/min, be uniformly dispersed to obtain mixed liquor, then heats while stirring, reaction temperature 85
DEG C, mixing speed 20r/min reacts 105min, and test pre-polymerization liquid viscosity is 63mpa.s；Reacting liquid temperature is reduced to 7 DEG C, is added
Enter 1 parts by weight low temperature initiators, stirring and dissolving；
(2) foam：By mulser, emulsification makes the thick liquid in kettle become foam at a high speed, and mulser rotating speed is 1000r/
Min, emulsification times 8min, is then injected into mold；
(3) injection molding：Preprepared mold is vacuumized, then inflated with nitrogen to normal pressure is connected with autoclave, pass through weight
Power effect pours into foamed liquid foam in mold, and mold mouth is closed；
(4) it is low-temperature fast-curing：Foam reactant liquid temperature degree is controlled as 25 DEG C, the initiation reaction 1h in the case of cell stabilization
Cure, form removal, take out foam；
(5) solidify afterwards：The foam of taking-up is transferred to 40 DEG C/100h in baking oven, 90 DEG C/60h solidify afterwards make residual monomer
Polymerization is fully participated in, obtains high-intensity special-shaped polymethacrylimide foam；
(6) foam afterwards：Foam after solidify afterwards is reentered into mold and carries out fretting map again, foam process for 190 DEG C/
60min；
Performance：Foaming properties are shown in Table 1.
Comparative example 1- machining modes prepare abnormal shape PMI foams
(1) pre-polymerization：By 65 parts by weight of (methyl) acrylic acid, 35 parts by weight of (methyl) acrylonitrile, methyl methacrylate 25
Parts by weight, 0.8 parts by weight of initiator, 2.5 parts by weight of crosslinking agent, 5 parts by weight of foaming agent are added in container, and stirring 3h makes material
Then fully dissolving injects material in mold, mold then is put into 35 DEG C/120h in hot water, 70 DEG C/40h in baking oven,
140 DEG C/10h, Polymethacrylimide pre-polymerization plate is fully obtained by the reaction；
(2) foam：Polymethacrylimide pre-polymerization plate is put into baking oven, 140 DEG C/4h, 230 DEG C/5h, foaming obtains
Polymethacrylimide foam plate；
(3) machine：Special-shaped Polymethacrylimide bubble is obtained by the way that cystosepiment is removed the peel, then with engraving machining
Foam, remaining foam leftover pieces directly make waste disposal；
Performance：Foaming properties are shown in Table 1；Machining causes the leftover pieces for making waste disposal to account for 40% or so, and waste of material is big；
Engraving machining foam efficiency is low, single can only carve, and the method for the invention can enter in batches after low-temperature fast-curing
Oven post-cure prepares special-shaped foam, efficient.
Foaming prepares special-shaped polymethacrylimide foam in comparative example 2- particle molds
(1) pre-polymerization：By 65 parts by weight of (methyl) acrylic acid, 35 parts by weight of (methyl) acrylonitrile, methyl methacrylate 25
Parts by weight, 0.8 parts by weight of initiator, 2.5 parts by weight of crosslinking agent, 5 parts by weight of foaming agent are added in container, and stirring 3h makes material
Then fully dissolving injects material in mold, mold then is put into 35 DEG C/120h in hot water, 70 DEG C/40h in baking oven,
140 DEG C/10h, Polymethacrylimide pre-polymerization plate is fully obtained by the reaction；
(2) crush：By Polymethacrylimide pre-polymerization plate by broken sieving, 1-3mm pre-polymerization plate particles are obtained；
(3) foaming in particle mold：Pre-polymerization particle is first obtained into pre-expanded beads in 230 DEG C/30min, then will be sent out in advance
It steeps particle and adds in adhesive, full of mold, 230 DEG C/4.5h fully foams, and form removal obtains special-shaped Polymethacrylimide bubble
Foam；
Performance：Foaming properties are shown in Table 1, poor performance；It is only 50% or so that pre-polymerization plate, which crushes yield, and waste of material is big, production
Efficiency is low.
The different embodiments of table 1 obtain foaming properties
It can be obtained from upper table, the present invention can prepare 50-200kg/m by adjusting3In the range of each density foam；
Under equal densities, the foam compression performance and tensile property that are obtained by the present invention are that conventional foam-in-mould method obtains foam
2 times or so, than conventional slab foam, compression and tensile property can improve 10% or so；Under equal densities, heat distortion temperature
10-20 DEG C or so can be risen；
High-intensity special-shaped PMI foams can be efficiently prepared in the present inventive method, greatly reduce production abnormal shape PMI at present
The cost of foam, improves efficiency, improves performance, available for needs such as new-energy automobile, cycle hub, propeller blades
The field of special-shaped polymethacrylimide foam.
The foregoing is merely the specific implementation case of patent of the present invention, but the technical characteristic of patent of the present invention is not limited to
This, any those skilled in the relevant art in the field of the invention, all cover in the special of the present invention by the variation or modification made
Among sharp scope.
Claims (10)
1. a kind of preparation method of poly- (methyl) the acrylimide foam of abnormal shape, which is characterized in that include the following steps：
(1) raw material for preparing poly- (methyl) acrylimide foam is added in reaction kettle, nitrogen protection is lower to carry out prepolymerization, instead
Reaction temperature is reduced when the viscosity of liquid being answered to reach preset value, adds in low temperature initiators；
(2) reaction solution obtained by step (1) is foamed；
It (3) will be in the reaction solution injection mold after foaming under nitrogen protection；
(4) foam curing temperature is controlled to carry out polymerizing curable, form removal, taking-up foam after curing；
(5) foam of taking-up is transferred in baking oven and carries out solidify afterwards, obtain special-shaped polymethacrylimide foam；
(6) special-shaped polymethacrylimide foam obtained by step (5) is reentered into mold, fretting map, cools down, tears open again
Mould obtains special-shaped poly- (methyl) acrylimide froth pulp.
2. preparation method according to claim 1, which is characterized in that prepolymerization conditions are in step (1)：Reaction temperature is
40-85 DEG C, mixing speed 10-20r/min, reaction time 60-120min, viscosity is 30-100mpa.s after reaction.
3. preparation method according to claim 1, which is characterized in that reaction temperature is reduced in step (1) to 5-15 DEG C.
4. preparation method according to claim 1, which is characterized in that foaming method is one in following method in step (2)
Kind：
(1) by mulser, emulsification makes the thick liquid in kettle become foam at a high speed, and mulser rotating speed is 1600-2200r/min,
Emulsification times are 5-15min；
(2) first feed liquid is transferred in autoclave, is pressed into the nitrogen of 5-10MPa, pressurize 10-30min, then reduction of blood pressure in high-speed obtain instead
Answer vacuole foam；
(3) reaction solution foam is generated by adding in chemical foaming agent in reaction solution.
5. preparation method according to claim 1, which is characterized in that die venting mode is first to take out container in step (3)
Vacuum extremely -0.1, then logical nitrogen to normal pressure, and so on 5 times, air is fully drained with guarantee, then logical nitrogen to normal pressure,
Reaction solution is injected by mold by gravity.
6. preparation method according to claim 1, which is characterized in that condition of cure in step (4)：Reaction temperature is 25-35
DEG C, reaction time 1-3h.
7. preparation method according to claim 1, which is characterized in that post cure condition in step (5)：40-90 DEG C of curing 20-
Then 100h cures 10-60h for 90-150 DEG C.
8. preparation method according to claim 1, which is characterized in that fretting map condition in step (6)：190-250 DEG C of heat preservation
10-60min。
9. preparation method according to claim 1, which is characterized in that raw material proportioning is as follows in step (1)：
10. a kind of poly- (methyl) propylene of abnormal shape that preparation method as described in any one of claim 1~9 claim is prepared
Acid imide foam.
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