CN108084324B - Preparation method of high-strength special-shaped poly (methyl) acrylimide foam - Google Patents
Preparation method of high-strength special-shaped poly (methyl) acrylimide foam Download PDFInfo
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- CN108084324B CN108084324B CN201711446287.0A CN201711446287A CN108084324B CN 108084324 B CN108084324 B CN 108084324B CN 201711446287 A CN201711446287 A CN 201711446287A CN 108084324 B CN108084324 B CN 108084324B
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- Prior art keywords
- foam
- reaction
- curing
- methyl
- foaming
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- 239000006260 foam Substances 0.000 title claims abstract description 130
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000005187 foaming Methods 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 238000011417 postcuring Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 28
- 230000001804 emulsifying effect Effects 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 14
- 239000004088 foaming agent Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 11
- 230000005484 gravity Effects 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 2
- 229920007790 polymethacrylimide foam Polymers 0.000 abstract description 37
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
- 239000003431 cross linking reagent Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000011049 filling Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 239000006185 dispersion Substances 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
- 238000007789 sealing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000008258 liquid foam Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000006261 foam material Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- -1 alkyl peroxide Chemical class 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound 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
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 239000004005 microsphere Substances 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
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920006934 PMI Polymers 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
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 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
- 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal 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
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 230000001105 regulatory effect Effects 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
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 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
- 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
- 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
- 239000004604 Blowing Agent Substances 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
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 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
- 241000276425 Xiphophorus maculatus Species 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
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 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
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- DZBOAIYHPIPCBP-UHFFFAOYSA-L magnesium;2-methylprop-2-enoate Chemical compound [Mg+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O DZBOAIYHPIPCBP-UHFFFAOYSA-L 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 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
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 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
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 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
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 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
Abstract
The invention discloses a preparation method of high-strength heterotype poly (methyl) acrylimide foam, which comprises the steps of adding raw materials for preparing the poly (methyl) acrylimide foam into a reaction kettle, carrying out prepolymerization under the protection of nitrogen, reducing the reaction temperature when the viscosity of reaction liquid reaches a preset value, and adding a low-temperature initiator; foaming the obtained reaction liquid; injecting the foamed reaction liquid into a mould under the protection of nitrogen; controlling the foam curing temperature to carry out polymerization curing, removing the mold and taking out the foam body; transferring the taken foam body into an oven for post-curing; and putting the special-shaped polymethacrylimide foam obtained by post-curing into a mold again, carrying out micro-foaming again, cooling and demolding to obtain the composite material. The method can efficiently prepare the high-strength special-shaped PMI foam, greatly reduces the cost of producing the special-shaped PMI foam at present, improves the efficiency and the performance, and can be used in the fields of new energy automobiles, bicycle hubs, propeller blades and the like which need the special-shaped polymethacrylimide foam.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of a high-strength special-shaped poly (methyl) acrylimide foam material.
Background
PMI foam is one of foam plastics with highest mechanical property and heat resistance at present, and since the commercial production of PMI foam materials in Degussa in 1972, PMI has been widely applied to the fields of aerospace, transportation, wind power, ships and the like due to the high strength, high rigidity, excellent heat resistance, creep resistance and the like.
However, PMI foam materials are currently available on the market, and the product form of the PMI foam materials is only one form of a single plate, so that the application range of the PMI foam materials is limited by the single product form; if the PMI foam is processed into a profiled bar, the PMI foam has great advantages in the field of profiled foam which needs high specific strength and high heat resistance, such as bicycle rims, light automobiles, propeller blades and the like, but the required structural member can be obtained only by machining (such as cutting, grinding and the like) in the prior art, so that the foam waste is large, the machining cost is high, and the efficiency is low.
Therefore, it is imperative to investigate poly (meth) acrylimide profile foams.
At present, the research on the poly (methyl) acrylimide profiled foam at home and abroad is still in the initial stage. In patent CN101341227A, the thermal foaming microspheres and the preparation method and application thereof, suspension polymerization is utilized to prepare poly (methyl) acrylimide thermal foaming microspheres containing foaming agent, and the poly (methyl) acrylimide thermal foaming microspheres are filled into a mould to obtain heterotype poly (methyl) acrylimide foam; the patent CN101857656A discloses expandable particles for producing poly (meth) acrylimide foam materials and application thereof, wherein methacrylic acid/methacrylonitrile and related auxiliary agents are uniformly mixed and poured into a mold, a body is polymerized to obtain a plate-shaped poly (meth) acrylimide plate, then the plate-shaped poly (meth) acrylimide plate is crushed to obtain expandable particles, the expandable particles are pre-expanded to obtain pre-expanded particles, and the pre-expanded particles are filled into the mold to be expanded to obtain special-shaped PMI foam; in the preparation method of the poly (meth) acrylimide-based foamed copolymer containing the adhesion promoter disclosed in patent CN103814068A, a poly (meth) acrylimide plate is ground to obtain expandable polymer particles with a certain particle size range, then pre-expanded at a certain temperature to obtain pre-expanded particles, then an adhesive is mixed into the pre-expanded particles, and finally the particles are injected into a mold to be foamed to obtain the profiled PMI foam, so that the problem of low interfacial strength between particles in the foam in patent CN101857656A is partially solved; in the CN103923337A poly (methyl) acrylimide composite foam wave-absorbing material, a method for preparing heterotype PMI foam in the CN101857656A is used for reference, and a wave-absorbing agent subjected to surface treatment is introduced to obtain heterotype poly (methyl) acrylimide foam with wave-absorbing performance; in the patent CN106170508A, poly (meth) acrylimide particles are foamed and molded in a closed mold so as to prepare a hard foam core, a poly (meth) acrylimide plate is firstly ground to obtain expandable particles, then the expandable particles are pre-foamed, and finally the expandable particles are filled in the mold to be foamed so as to obtain the special-shaped PMI foam; patent 105793338A discloses prefoaming of poly (meth) acrylimide particles by foam molding in a closed mold, wherein a poly (meth) acrylimide sheet is first ground to obtain particles, the particles are then irradiated with IR light of a specific wavelength, prefoaming is carried out in a short time, and finally the particles are filled into a mold and foamed to obtain profiled PMI foams; patent CN106459465A discloses a method for preparing a rigid foam core by pressure-dependent molding foaming of poly (meth) acrylimide particles in a closed mold, wherein the obtained poly (meth) acrylimide particles are pre-foamed under pressure, and then filled into the mold and foamed under reduced pressure to obtain a profiled foam with smaller density gradient. At present, the in-mold foaming poly (methyl) acrylimide foam on the market is prepared according to the basic principle of crushing, pre-foaming and foaming of a poly (methyl) acrylimide plate, and related products are apparent that the foam surface has fine boundaries but is relatively flat, and metal parts can be embedded in the foam.
Therefore, the main preparation ideas for the heterotypic poly (methyl) acrylimide foam at home and abroad are as follows: 1. the preparation of the poly (methyl) acrylimide expandable particles can be prepared by suspension polymerization or crushing a poly (methyl) acrylimide plate; 2. pre-foaming the expandable particles; 3. filling the pre-foamed particles into a mold for re-foaming to obtain special-shaped foam; 4. the performance of the special-shaped foam is improved by adding an adhesive into the system, pre-foaming at high pressure, re-foaming at low pressure and the like. However, the above process has a number of drawbacks: 1. the yield of the poly (methyl) acrylimide particles meeting the requirements obtained by crushing the polymer plate is extremely low, the cost for preparing the special-shaped foam is greatly increased and even exceeds the cost for preparing the special-shaped foam by a machining mode; 2. because boundaries exist among particles of the in-mold foam, and the bonding strength among the boundaries is low, although the boundaries can be improved by means of an adhesive, the performance of the finally obtained special-shaped foam is still greatly reduced compared with that of a foam board.
Disclosure of Invention
In order to overcome the defect of preparing the special-shaped poly (methyl) imide foam by the in-mold foaming method, the patent provides a novel method for preparing the high-strength special-shaped poly (methyl) acrylimide foam by firstly foaming and then curing.
A preparation method of heterotype poly (methyl) acrylimide foam comprises the following steps:
(1) pre-polymerization: adding raw materials such as (methyl) acrylic acid, (methyl) acrylonitrile, a third monomer, viscosity regulating resin, a foaming agent, a medium-high temperature initiator, a cell stabilizer, a cross-linking agent, an anti-shrinking agent, a functional auxiliary agent and other related auxiliary agents into a reaction kettle, carrying out prepolymerization under the protection of nitrogen, and stopping reaction after a certain viscosity is reached; reducing the temperature of the reaction liquid, and adding a low-temperature initiator;
(2) foaming: foaming the reaction solution to obtain foam with fine and stable foam pores;
(3) injection molding: connecting a prepared mould with a reaction kettle, injecting the mould into the mould under the protection of nitrogen, and sealing the mould opening;
(4) and (3) low-temperature rapid curing: controlling the curing temperature of the foam, initiating a reaction to rapidly polymerize and cure, removing the mold, and taking out the foam body;
(5) post-curing: transferring the taken foam body into a drying oven for post-curing, so that residual monomers fully participate in polymerization to obtain high-strength special-shaped polymethacrylimide foam;
(6) post-foaming: and putting the obtained polymethacrylimide foam into a mold again, carrying out micro-foaming again to overcome the size change caused by a small amount of shrinkage, so that the size of the foam is completely consistent with that of the mold, cooling, and removing the mold to obtain the final special-shaped polymethacrylimide foam product.
The method of the invention is applicable to all PMI formulations. Preferably, the mixture ratio of the raw materials in the step (1) is as follows:
further preferably, the mixture ratio of the raw materials in the step (1) is as follows:
more preferably, the ratio of the raw materials in the step (1) is as follows:
the third monomer is at least one or more of (meth) acrylamides, (meth) acrylates, maleimides and maleic anhydrides, namely, any one or mixture of any two or more in any proportion.
The viscosity regulating resin is at least one of thickening agents such as polyacrylamide, polyvinyl alcohol, polymethyl methacrylate, polymethacrylic acid and the like, namely any one or a mixture of any two or more of the thickening agents in any proportion.
The low-temperature initiator is at least one of a redox system such as a redox system consisting of BPO and DMA, a redox system consisting of BPO and DMT, a redox system consisting of cumene hydroperoxide and DMT, a redox system consisting of persulfate and fatty amine, and the like, namely any one or a mixture of any two or more of the above in any proportion.
The medium-high temperature initiator is alkyl peroxide such as dibenzoyl peroxide, lauroyl peroxide, dicyclohexyl peroxydicarbonate, isopropyl peroxydicarbonate and tert-butyl peroxypivalate, and azo such as at least one of azobisisobutyronitrile and azobisisoheptonitrile, namely any one or a mixture of any two or more of the azo-compounds in any proportion.
The cell stabilizer is at least one of surfactants such as sulfonated ricinol sodium salt, polyether siloxane, lauryl sodium sulfate, fatty alcohol-polyoxyethylene ether sodium sulfate, alpha-alkenyl sodium sulfonate, alkylolamide, silicone amide and the like, namely any one or a mixture of any two or more of the surfactants in any proportion.
The cross-linking agent is at least one of (methyl) acrylamide, allyl methacrylate, zinc methacrylate, butyl methacrylate and magnesium methacrylate, namely any one or a mixture of any two or more in any proportion.
The antishrinking agent is at least one of olefin derivatives containing larger rigid side groups, such as styrene, 4-acetoxystyrene, alpha-methylstyrene, maleimide, phenyl vinyl sulfone and the like, namely any one or a mixture of any two or more of the above in any proportion.
The functional additive is a flame retardant such as TCEP, TCPP, TDCPP, DMMP, triphenyl phosphate, MPP and other phosphorus-nitrogen halogen-free flame retardants, and the wave absorbing agent is at least one of conductive carbon black, carbon nano tubes, nano carbon fibers, metal dispersion and other conductive wave absorbing materials modified by a surfactant, namely any one or a mixture of any two or more in any proportion.
Preferably, the mixed liquid dispersing process in the step (1) is to perform high-speed shearing for 5-10min in a dispersing kettle by an emulsifying machine with the speed of 2000-3000 r/min.
Preferably, in the step (1), the reaction temperature is 40-85 ℃, the stirring speed is 10-20r/min, the reaction time is 60-120min, and the viscosity after reaction is 30-100 mpa.s; further preferably, the stirring speed is 18-20r/min, the reaction time is 100-120min, and the viscosity after the reaction is 60-80 mpa.s.
Preferably, the mixture is continuously introduced into the reaction kettle in the step (1) at a flow rate of 10-20 mL/min.
Preferably, the temperature after the reaction in step (1) is reduced to 5-15 ℃, more preferably to 5-10 ℃, which is obtained by cooling a water circulation kettle jacket, and the low-temperature initiator is added at the temperature and stirred for 30min to be completely dissolved.
Preferably, in the foaming method in the step (2), the viscous liquid in the kettle can be changed into foam through high-speed emulsification by an emulsifying machine, the rotating speed of the emulsifying machine is 1600-; or transferring the feed liquid into a high-pressure kettle, pressing in 5-10MPa nitrogen, maintaining the pressure for 10-30min, rapidly reducing the pressure to a certain volume to obtain reaction liquid foam, and injecting into a mold; or adding 5-10 weight parts of chemical foaming agent such as sodium bicarbonate, zinc carbonate or magnesium carbonate into the reaction solution to generate reaction solution foam, and injecting into a mold; by the mode, foam with uniform and controllable foam holes can be obtained;
preferably, in the step (3), the exhaust mode of the die is that the container is vacuumized to-0.1, then nitrogen is introduced to the normal pressure, the reciprocating is carried out for 5 times so as to ensure that air is fully exhausted, then nitrogen is introduced to the normal pressure, and the reaction liquid is injected into the die through the action of gravity so as to ensure the stability of the foam holes.
Preferably, in the step (4), the reaction temperature is 25-35 ℃, the reaction time is 1-3h, the foam body is solidified, has certain strength, and can be placed into an oven in batches after being demoulded for post-curing in order to meet the production requirement of higher efficiency; in order to facilitate the removal of the mold, the surface of the mold is subjected to Teflon spraying treatment.
Preferably, the post-curing temperature in the step (5) is 40-90 ℃/20-100h, 90-150 ℃/10-60 h;
preferably, the post-foaming process in step (6) is 190-.
Still more preferably, the temperature after the reaction in step (1) is reduced to 8-10 ℃; in the foaming method in the step (2), the viscous liquid in the kettle is changed into foam through the high-speed emulsification of an emulsifying machine, the rotating speed of the emulsifying machine is 1800 plus 2000r/min, and the emulsifying time is 8-12 min; in the step (4), the reaction temperature is 28-32 ℃, and the reaction time is 1.5-2.5 h; the post-curing temperature in the step (5) is 65-75 ℃/35-45h, and 130-; the post-foaming process in the step (6) is 230-.
Most preferably, the temperature is reduced to 10 ℃ after the reaction in step (1); in the foaming method in the step (2), the viscous liquid in the kettle is changed into foam through high-speed emulsification by an emulsifying machine, the rotating speed of the emulsifying machine is 1900r/min, and the emulsifying time is 10 min; in the step (4), the reaction temperature is 30 ℃, and the reaction time is 2 hours; in the step (5), the post-curing temperature is 60 ℃/40h and 140 ℃/10 h; the post-foaming process in step (6) is 235 ℃/30 min.
The special-shaped polymethacrylimide foam can be used in the fields of new energy automobiles, bicycle hubs, propeller blades and the like which need the special-shaped polymethacrylimide foam.
Compared with the prior art, the invention has the following advantages:
(1) compared with the method for obtaining the special-shaped foam by machining the polymethacrylimide foam plate, the method has the advantages that no material is wasted, about 40% of raw materials can be saved, the foam preparation speed is higher, the efficiency is higher, and the time for machining and carving is saved; in addition, the foaming is carried out firstly and then the polymerization is carried out, and more cross-linking agents can be added, so that the foam strength can be adjusted within a certain range;
(2) compared with the method of crushing the polymethacrylimide plate into particles for prefoaming and filling the particles into a die, the foam obtained by the method has better performances in all aspects, the tensile and compression performances are about 2 times of those of the polymethacrylimide plate, no raw material waste is generated, 50% of raw material waste can be saved, the efficiency is higher, the time for in-die foaming can be saved, and the method has great advantages.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Foam density was tested according to ISO 845;
the foam compression strength was tested according to ISO 844;
foam tensile properties were tested according to ASTM D638;
foam heat distortion temperature test DIN 53424;
the initiator, blowing agent and crosslinking agent used in the following examples are all conventional raw materials.
Example 1
(1) Pre-polymerization: adding 50 parts by weight of (meth) acrylic acid, 50 parts by weight of (meth) acrylonitrile, 20 parts by weight of acrylamide, 8.5 parts by weight of polyether siloxane, 1 part by weight of a foaming agent, 0.6 part by weight of a medium-high temperature initiator, 7.5 parts by weight of sulfonated ricinol sodium salt, 8 parts by weight of a cross-linking agent and 8 parts by weight of styrene into a dispersion kettle, vacuumizing, charging nitrogen, removing air in the kettle, continuously introducing nitrogen, wherein the nitrogen flow is 13mL/min, uniformly dispersing to obtain a mixed solution, heating while stirring, the reaction temperature is 85 ℃, the stirring speed is 20r/min, reacting for 105min, and testing the viscosity of a prepolymerization solution to be 63 mpa.s; reducing the temperature of the reaction solution to 7 ℃, adding 1 part by weight of low-temperature initiator, and stirring for dissolving;
(2) foaming: transferring the feed liquid into a high-pressure kettle, pressing 9MPa of nitrogen, maintaining the pressure for 25min, then quickly reducing the pressure to a pre-calculated volume to obtain reaction liquid foam, and then injecting the reaction liquid foam into a mold;
(3) injection molding: vacuumizing a prepared mould, filling nitrogen to normal pressure, connecting the mould with a high-pressure kettle, pouring foamed liquid foam into the mould under the action of gravity, and sealing the opening of the mould;
(4) and (3) low-temperature rapid curing: controlling the temperature of the foam reaction liquid to be 25 ℃, initiating the reaction for 1h to solidify under the condition that the foam holes are stable, removing the mold, and taking out the foam body;
(5) post-curing: transferring the taken foam body into an oven at 40 ℃/100h, and curing at 90 ℃/60h to ensure that residual monomers fully participate in polymerization to obtain high-strength special-shaped polymethacrylimide foam;
(6) post-foaming: putting the cured foam into a mold again and carrying out micro-foaming, wherein the foaming process is 190 ℃/60 min;
performance: the foam properties are shown in Table 1.
Example 2
(1) Pre-polymerization: adding 40 parts by weight of (methyl) acrylic acid, 60 parts by weight of (methyl) acrylonitrile, 10 parts by weight of methyl acrylate, 10 parts by weight of polyacrylamide, 2.5 parts by weight of foaming agent, 0.7 part by weight of medium-high temperature initiator, 8 parts by weight of sodium dodecyl sulfate, 4 parts by weight of cross-linking agent and 7.6 parts by weight of 4-acetoxystyrene into a dispersion kettle, vacuumizing, filling nitrogen, removing air in the kettle, continuously introducing nitrogen, ensuring the nitrogen flow to be 12mL/min, uniformly dispersing to obtain a mixed solution, heating while stirring, wherein the reaction temperature is 85 ℃, the stirring speed is 18r/min, the reaction time is 100min, and the viscosity of the pre-polymerization solution is tested to be 61 mpa.s; reducing the temperature of the reaction solution to 9 ℃, adding 0.73 weight part of low-temperature initiator, and stirring for dissolving;
(2) foaming: adding 7.5 parts by weight of sodium bicarbonate into the reaction solution, stirring uniformly, reacting for 60min to obtain reaction solution foam, and injecting into a mold;
(3) injection molding: vacuumizing a prepared mould, filling nitrogen to normal pressure, connecting the mould with a high-pressure kettle, pouring foamed liquid foam into the mould under the action of gravity, and sealing the opening of the mould;
(4) and (3) low-temperature rapid curing: controlling the temperature of the foam reaction liquid to be 27 ℃, initiating the reaction for 1.6h to solidify under the condition that the foam holes are stable, removing the mold, and taking out the foam body;
(5) post-curing: transferring the taken foam body into an oven at 50 ℃/85h, and curing at 100 ℃/50h to ensure that residual monomers fully participate in polymerization to obtain high-strength special-shaped polymethacrylimide foam;
(6) post-foaming: putting the cured foam into a mold again for micro-foaming, wherein the foaming process is 245 ℃/20 min;
performance: the foam properties are shown in Table 1.
Example 3
(1) Pre-polymerization: adding 65 parts by weight of (methyl) acrylic acid, (35 parts by weight of (methyl) acrylonitrile, 15 parts by weight of maleimide, 8 parts by weight of polyvinyl alcohol, 3 parts by weight of foaming agent, 0.9 part by weight of medium-high temperature initiator, 7 parts by weight of fatty alcohol-polyoxyethylene ether sodium sulfate, 2 parts by weight of cross-linking agent and 5 parts by weight of alpha-methyl styrene into a dispersion kettle, vacuumizing, charging nitrogen, removing air in the kettle, continuously introducing nitrogen, ensuring that the nitrogen flow is 14mL/min, uniformly dispersing to obtain a mixed solution, heating while stirring, wherein the reaction temperature is 78 ℃, the stirring speed is 20r/min, reacting for 120min, and testing the viscosity of the pre-polymerization solution to be 70 mpa.s; reducing the temperature of the reaction liquid to 8 ℃, adding 0.4 part by weight of low-temperature initiator, and stirring for dissolving;
(2) foaming: adding 5 parts by weight of magnesium carbonate into the reaction solution, stirring uniformly, reacting for 45min to obtain reaction solution foam, and injecting into a mold;
(3) injection molding: vacuumizing a prepared mould, filling nitrogen to normal pressure, connecting the mould with a high-pressure kettle, pouring foamed liquid foam into the mould under the action of gravity, and sealing the opening of the mould;
(4) and (3) low-temperature rapid curing: controlling the temperature of the foam reaction liquid to be 35 ℃, initiating the reaction for 1.5h to solidify under the condition that the foam holes are stable, removing the mold, and taking out the foam body;
(5) post-curing: transferring the taken foam body into a drying oven for 60 ℃/65h and 110 ℃/40h, and then curing to ensure that residual monomers fully participate in polymerization to obtain high-strength special-shaped polymethacrylimide foam;
(6) post-foaming: putting the cured foam into a mold again and carrying out micro-foaming, wherein the foaming process is 250 ℃/10 min;
performance: the foam properties are shown in Table 1.
Example 4
(1) Pre-polymerization: adding 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 part by weight of medium-high temperature initiator, 7.8 parts by weight of alkylolamide, 3 parts by weight of cross-linking agent and 7.3 parts by weight of phenyl vinyl sulfone into a dispersion kettle, vacuumizing, filling nitrogen, removing air in the kettle, continuously introducing nitrogen, ensuring the nitrogen flow to be 11mL/min, uniformly dispersing to obtain a mixed solution, heating while stirring, wherein the reaction temperature is 75 ℃, the stirring speed is 19r/min, reacting for 98min, and testing the viscosity of the pre-polymerization solution to be 60 mpa.s; reducing the temperature of the reaction solution to 9 ℃, adding 0.75 weight part of low-temperature initiator, and stirring for dissolving;
(2) foaming: emulsifying at high speed by an emulsifying machine to convert viscous liquid in the kettle into foam, wherein the rotating speed of the emulsifying machine is 2000r/min, the emulsifying time is 8min, and then injecting into a mold;
(3) injection molding: vacuumizing a prepared mould, filling nitrogen to normal pressure, connecting the mould with a high-pressure kettle, pouring foamed liquid foam into the mould under the action of gravity, and sealing the opening of the mould;
(4) and (3) low-temperature rapid curing: controlling the temperature of the foam reaction liquid to be 28 ℃, initiating the reaction for 1.6h to solidify under the condition that the foam holes are stable, removing the mould, and taking out the foam body;
(5) post-curing: transferring the taken foam body into an oven at 70 ℃/40h and after curing at 120 ℃/30h, and enabling residual monomers to fully participate in polymerization to obtain high-strength special-shaped polymethacrylimide foam;
(6) post-foaming: putting the cured foam into a mold again and carrying out micro-foaming, wherein the foaming process is 225 ℃/40 min;
performance: the foam properties are shown in Table 1.
Example 5
(1) Pre-polymerization: adding 60 parts by weight of (meth) acrylic acid, 40 parts by weight of (meth) acrylonitrile, 15 parts by weight of methacrylamide, 8 parts by weight of polyvinyl alcohol, 1.4 parts by weight of a foaming agent, 0.9 part by weight of a medium-high temperature initiator, 7 parts by weight of alkylolamide, 6 parts by weight of a crosslinking agent and 8 parts by weight of 4-acetoxystyrene into a dispersion kettle, vacuumizing, charging nitrogen, removing air in the kettle, continuously introducing nitrogen, wherein the nitrogen flow is 16mL/min, uniformly dispersing to obtain a mixed solution, heating while stirring, reacting at the temperature of 45 ℃, at the stirring speed of 20r/min, reacting for 120min, and testing the viscosity of a pre-polymerization solution to be 60 mpa.s; reducing the temperature of the reaction liquid to 7 ℃, adding 0.4 part by weight of low-temperature initiator, and stirring for dissolving;
(2) foaming: transferring the feed liquid into a high-pressure kettle, pressing 7.5MPa of nitrogen, maintaining the pressure for 25min, then quickly reducing the pressure to a pre-calculated volume to obtain reaction liquid foam, and then injecting the reaction liquid foam into a mold;
(3) injection molding: vacuumizing a prepared mould, filling nitrogen to normal pressure, connecting the mould with a high-pressure kettle, pouring foamed liquid foam into the mould under the action of gravity, and sealing the opening of the mould;
(4) and (3) low-temperature rapid curing: controlling the temperature of the foam reaction liquid to be 35 ℃, initiating the reaction for 1.5h to solidify under the condition that the foam holes are stable, removing the mold, and taking out the foam body;
(5) post-curing: transferring the taken foam body into a drying oven for curing at 80 ℃/20h and 130 ℃/20h, and fully participating in polymerization of residual monomers to obtain high-strength special-shaped polymethacrylimide foam;
(6) post-foaming: putting the cured foam into a mold again for micro-foaming, wherein the foaming process is 205 ℃/50 min;
performance: the foam properties are shown in Table 1.
Example 6
(1) Pre-polymerization: adding 65 parts by weight of (meth) acrylic acid, (35 parts by weight of (meth) acrylonitrile, 25 parts by weight of methyl methacrylate, 6 parts by weight of polyacrylamide, 3 parts by weight of a foaming agent, 0.8 part by weight of a medium-high temperature initiator, 5 parts by weight of sodium dodecyl sulfate, 2.5 parts by weight of a crosslinking agent and 6.5 parts by weight of alpha-methylstyrene into a dispersion kettle, vacuumizing, charging nitrogen, removing air in the kettle, continuously introducing nitrogen, wherein the nitrogen flow is 15mL/min, uniformly dispersing to obtain a mixed solution, heating while stirring, reacting at the temperature of 60 ℃, at the stirring speed of 15r/min, reacting for 110min, and testing the viscosity of the pre-polymerization solution to be 61 mpa.s; reducing the temperature of the reaction liquid to 10 ℃, adding 0.6 part by weight of low-temperature initiator, and stirring for dissolving;
(2) foaming: emulsifying at high speed by an emulsifying machine to convert viscous liquid in the kettle into foam, wherein the rotating speed of the emulsifying machine is 1900r/min, the emulsifying time is 10min, and then injecting into a mold;
(3) injection molding: vacuumizing a prepared mould, filling nitrogen to normal pressure, connecting the mould with a high-pressure kettle, pouring foamed liquid foam into the mould under the action of gravity, and sealing the opening of the mould;
(4) and (3) low-temperature rapid curing: controlling the temperature of the foam reaction liquid to be 30 ℃, initiating the reaction for 2h to solidify under the condition that the foam holes are stable, removing the mold, and taking out the foam body;
(5) post-curing: transferring the taken foam body into an oven for 70 ℃/40h and 140 ℃/10h, and then curing to ensure that residual monomers fully participate in polymerization to obtain high-strength special-shaped polymethacrylimide foam;
(6) post-foaming: putting the cured foam into a mold again for micro-foaming, wherein the foaming process is 235 ℃/30 min;
performance: the foam properties are shown in Table 1.
Example 7
(1) Pre-polymerization: adding 30 parts by weight of (meth) acrylic acid, 70 parts by weight of (meth) acrylonitrile, 20 parts by weight of acrylamide, 8.5 parts by weight of polyether siloxane, 1 part by weight of a foaming agent, 0.6 part by weight of a medium-high temperature initiator, 7.5 parts by weight of sulfonated ricinol sodium salt, 8 parts by weight of a cross-linking agent and 8 parts by weight of styrene into a dispersion kettle, vacuumizing, charging nitrogen, removing air in the kettle, continuously introducing nitrogen, wherein the nitrogen flow is 13mL/min, uniformly dispersing to obtain a mixed solution, heating while stirring, the reaction temperature is 85 ℃, the stirring speed is 20r/min, reacting for 105min, and testing the viscosity of a prepolymerization solution to be 63 mpa.s; reducing the temperature of the reaction solution to 7 ℃, adding 1 part by weight of low-temperature initiator, and stirring for dissolving;
(2) foaming: emulsifying at high speed by an emulsifying machine to convert viscous liquid in the kettle into foam, wherein the rotating speed of the emulsifying machine is 1000r/min, the emulsifying time is 8min, and then injecting into a mold;
(3) injection molding: vacuumizing a prepared mould, filling nitrogen to normal pressure, connecting the mould with a high-pressure kettle, pouring foamed liquid foam into the mould under the action of gravity, and sealing the opening of the mould;
(4) and (3) low-temperature rapid curing: controlling the temperature of the foam reaction liquid to be 25 ℃, initiating the reaction for 1h to solidify under the condition that the foam holes are stable, removing the mold, and taking out the foam body;
(5) post-curing: transferring the taken foam body into an oven at 40 ℃/100h, and curing at 90 ℃/60h to ensure that residual monomers fully participate in polymerization to obtain high-strength special-shaped polymethacrylimide foam;
(6) post-foaming: putting the cured foam into a mold again and carrying out micro-foaming, wherein the foaming process is 190 ℃/60 min;
performance: the foam properties are shown in Table 1.
Comparative example 1 preparation of profiled PMI foams by means of machining
(1) Pre-polymerization: adding 65 parts by weight of (meth) acrylic acid, 35 parts by weight of (meth) acrylonitrile, 25 parts by weight of methyl methacrylate, 0.8 part by weight of an initiator, 2.5 parts by weight of a crosslinking agent and 5 parts by weight of a foaming agent into a container, stirring for 3 hours to fully dissolve the materials, then injecting the materials into a mold, then putting the mold into hot water for 35 ℃/120 hours, and fully reacting in an oven for 70 ℃/40 hours and 140 ℃/10 hours to obtain a polymethacrylimide pre-polymerization plate;
(2) foaming: placing the polymethacrylimide prepolymerization plate into a drying oven, and foaming at 140 ℃/4h and 230 ℃/5h to obtain a polymethacrylimide foam plate;
(3) machining: the foam plate is peeled, and then is processed by a carving machine to obtain the special-shaped polymethacrylimide foam, and the residual foam leftover materials are directly used as waste materials for treatment;
performance: the foam properties are shown in Table 1; leftover materials treated by machining account for about 40 percent, and material waste is large; the engraving machine has low foam processing efficiency and can only engrave singly, and the method of the invention can be used for preparing the special-shaped foam by batch curing in the oven after low-temperature rapid curing, and has high efficiency.
Comparative example 2 preparation of Special-shaped Polymethacrylimide foam by particle in-mold foaming method
(1) Pre-polymerization: adding 65 parts by weight of (meth) acrylic acid, 35 parts by weight of (meth) acrylonitrile, 25 parts by weight of methyl methacrylate, 0.8 part by weight of an initiator, 2.5 parts by weight of a crosslinking agent and 5 parts by weight of a foaming agent into a container, stirring for 3 hours to fully dissolve the materials, then injecting the materials into a mold, then putting the mold into hot water for 35 ℃/120 hours, and fully reacting in an oven for 70 ℃/40 hours and 140 ℃/10 hours to obtain a polymethacrylimide pre-polymerization plate;
(2) crushing: crushing and sieving a polymethacrylimide pre-polymerization plate to obtain pre-polymerization plate particles with the particle size of 1-3 mm;
(3) foaming in the particle mold: pre-polymerized particles are firstly subjected to 230 ℃/30min to obtain pre-foamed particles, then the pre-foamed particles are added with an adhesive to fill a mold, the pre-foamed particles are fully foamed at 230 ℃/4.5h, and the mold is removed to obtain the special-shaped polymethacrylimide foam;
performance: the foam properties are shown in table 1, and the properties are poor; the yield of the pre-polymerization plate is only about 50%, the material waste is large, and the production efficiency is low.
TABLE 1 foam properties obtained in the different examples
From the above table, the present invention can be adjusted to prepare 50-200kg/m3Foams of various densities within the range; under the same density, the compression performance and the tensile performance of the foam obtained by the method are about 2 times of those of the foam obtained by the conventional in-mold foaming method, and the compression performance and the tensile performance can be improved by about 10 percent compared with the conventional platy foam; under the same density, the thermal deformation temperature can be increased by about 10-20 ℃;
the method can efficiently prepare the high-strength special-shaped PMI foam, greatly reduces the cost of producing the special-shaped PMI foam at present, improves the efficiency and the performance, and can be used in the fields of new energy automobiles, bicycle hubs, propeller blades and the like which need the special-shaped polymethacrylimide foam.
The above description is only an embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any person skilled in the relevant art can change or modify the present invention within the scope of the present invention.
Claims (9)
1. The preparation method of the special-shaped poly (methyl) acrylimide foam is characterized by comprising the following steps:
(1) adding raw materials for preparing poly (methyl) acrylimide foam into a reaction kettle, carrying out prepolymerization under the protection of nitrogen, reducing the reaction temperature when the viscosity of reaction liquid reaches a preset value, and adding a low-temperature initiator; the raw materials are as follows:
(2) foaming the reaction liquid obtained in the step (1);
(3) injecting the foamed reaction liquid into a mould under the protection of nitrogen;
(4) controlling the foam curing temperature to carry out polymerization curing, and removing the mold and taking out the foam body after curing;
(5) transferring the taken foam body into an oven for post-curing to obtain the special-shaped poly (methyl) acrylimide foam;
(6) putting the special-shaped poly (methyl) acrylimide foam obtained in the step (5) into a mould again, carrying out micro foaming again, cooling and demoulding to obtain a special-shaped poly (methyl) acrylimide foam product;
the third monomer is at least one of (methyl) acrylamide, (methyl) acrylate, maleimide and maleic anhydride;
the functional auxiliary agent is at least one of a flame retardant and a wave absorbing agent.
2. The process according to claim 1, wherein the prepolymerization conditions in the step (1) are as follows: the reaction temperature is 40-85 ℃, the stirring speed is 10-20r/min, the reaction time is 60-120min, and the viscosity after reaction is 30-100 mpa.s.
3. The method according to claim 1, wherein the reaction temperature is lowered to 5 to 15 ℃ in the step (1).
4. The method according to claim 1, wherein the foaming method in the step (2) is one of the following methods:
(1) emulsifying at high speed by an emulsifying machine to convert the viscous reaction liquid in the kettle into foam, wherein the rotating speed of the emulsifying machine is 1600-2200r/min, and the emulsifying time is 5-15 min;
(2) firstly, transferring the reaction liquid into a high-pressure kettle, pressing 5-10MPa of nitrogen, maintaining the pressure for 10-30min, and then quickly reducing the pressure to obtain reaction liquid foam;
(3) the reaction liquid foam is generated by adding a chemical foaming agent into the reaction liquid.
5. The process according to claim 1, wherein the step (3) of evacuating the mold is carried out by evacuating the vessel to-0.1, introducing nitrogen gas to atmospheric pressure, repeating the evacuation 5 times to ensure sufficient exhaustion of air, introducing nitrogen gas to atmospheric pressure, and injecting the reaction solution into the mold by gravity.
6. The production method according to claim 1, wherein the curing conditions in the step (4): the reaction temperature is 25-35 ℃, and the reaction time is 1-3 h.
7. The production method according to claim 1, wherein the post-curing conditions in the step (5): curing at 40-90 deg.C for 20-100h, and then curing at 90-150 deg.C for 10-60 h.
8. The method of claim 1, wherein the microfoaming conditions in step (6): 190 ℃ and 250 ℃ for 10-60 min.
9. The profiled poly (meth) acrylimide foam prepared by the method according to any one of claims 1 to 8.
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| CN110317290B (en) * | 2019-07-08 | 2022-03-22 | 湖南兆恒材料科技有限公司 | Large-aperture polymethacrylimide foam and preparation method thereof |
| CN115322292B (en) * | 2022-10-11 | 2023-02-28 | 河南博源新材料有限公司 | Antioxidant polyacrylamide, preparation method and application |
| CN115651339A (en) * | 2022-11-05 | 2023-01-31 | 浙江中科恒泰新材料科技有限公司 | PMI foaming method by using dihydric alcohol |
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