CN106832275A - A kind of Foam preparation processes - Google Patents
A kind of Foam preparation processes Download PDFInfo
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- CN106832275A CN106832275A CN201510880790.1A CN201510880790A CN106832275A CN 106832275 A CN106832275 A CN 106832275A CN 201510880790 A CN201510880790 A CN 201510880790A CN 106832275 A CN106832275 A CN 106832275A
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- aromatic dianhydride
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- 239000006260 foam Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000013064 chemical raw material Substances 0.000 claims abstract description 7
- 239000004642 Polyimide Substances 0.000 claims description 27
- 229920001721 polyimide Polymers 0.000 claims description 27
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 239000005056 polyisocyanate Substances 0.000 claims description 19
- 229920001228 polyisocyanate Polymers 0.000 claims description 19
- 238000005187 foaming Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 150000005690 diesters Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 10
- 150000002191 fatty alcohols Chemical class 0.000 claims description 10
- 239000002798 polar solvent Substances 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 9
- 239000004088 foaming agent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 239000006193 liquid solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- -1 tertiary amine compound Chemical class 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229920006389 polyphenyl polymer Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000004872 foam stabilizing agent Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 101000598921 Homo sapiens Orexin Proteins 0.000 description 2
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 description 2
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000009261 D 400 Substances 0.000 description 1
- 101000777220 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 3 Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- QMMAAHFIIBFLRK-UHFFFAOYSA-N NC1=CC=CC=C1.C1(=CC=CC=C1)C#C Chemical compound NC1=CC=CC=C1.C1(=CC=CC=C1)C#C QMMAAHFIIBFLRK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 102100031287 Ubiquitin carboxyl-terminal hydrolase 3 Human genes 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- YLFBFPXKTIQSSY-UHFFFAOYSA-N dimethoxy(oxo)phosphanium Chemical compound CO[P+](=O)OC YLFBFPXKTIQSSY-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000008258 liquid foam Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of Foam preparation processes, methods described is prepared foams using Preparation equipment and chemical raw material, and the foam precursor solution storage stabilization of the foams of making, foam bubble hole is uniform, with pliability, reduce rigidity and fragility.Preparation process is simple, it is cheap for manufacturing cost, it is easy to industrialized production, it is easy to utilize.
Description
Technical field
The present invention relates to a kind of novel high polymer foamed material field, and in particular to a kind of Foam preparation processes.
Background technology
The research of Polyimide foams is started from 1966, DuPont applies for a patent USP3 earliest, 249,561, the patent is that dehydrating agent or tertiary amine compound are added in polyamic acid solution and the acid of gas can be produced, to produce carbon monoxide or carbon dioxide to prepare foam intermediate, cured prepared Polyimide foams as foaming agent.Foam bubble hole is uneven obtained in the method.The patents of USP 6,172,127 are that aromatic dianhydride is obtained into two acid diesters fatty alcohol solutions in low molecule fat alcohol, and the solution is obtained polyimide acid precursor solution with aromatic amine reaction, and polyimide acid precursor powder is formed after steaming solvent.Heating powder is obtained polyimide foam, and the method is to prepare polyimide foam with powder foam technique.USP 7,541,388 is the one-step method NCO polyimide foam patent of NASA companies of U.S. previous application.The patent is that aromatic dianhydride is dissolved in dimethylformamide polar solvent, adds methyl alcohol to carry out esterification and prepares two acid diesters solution, then reacts free foaming with polyisocyanates, is solidified through microwave and electrical heating, prepares polyimide foam.Foam density is low obtained in the method, bad mechanical strength.
CN 1,528,808A is using hydroxy polyethers modified polyimides foam, its preparation method is that aromatic dianhydride is esterified in fatty alcohol and hydroxy polyethers solution, dianhydride is changed into two acid diesters and is coupled with hydroxy polyethers, adding aromatic diamines carries out reacting prepared polyimides salting liquid, steams solvent and pulverizes, high temperature powder foaming.Powder foam complex process, prepares precursor powder technology condition and is difficult to control.
CN 101,402,795A uses polymethyl siloxane modified polyimides foam, its preparation method is that back flow reaction is obtained two acid diesters methanol solutions in methyl alcohol by aromatic dianhydride, reacted with aromatic diamines again and blocked with phenylacetylene aniline, after adding polymethyl siloxane, solvent, drying, crushing, grinding, sieving is evaporated off, polyimide precursor powder is obtained, polyimide foam is prepared through powder foam technique.The complex process, is more expensive to manufacture.
The content of the invention
The present invention overcomes the deficiencies in the prior art, there is provided a kind of Foam preparation processes.The foam precursor solution storage stabilization of the foams that methods described makes, foam bubble hole is uniform, with pliability, reduce rigidity and fragility.Preparation process is simple, it is cheap for manufacturing cost, it is easy to industrialized production, it is easy to utilize.
The technical scheme is that：A kind of Foam preparation processes, methods described prepares foams using Preparation equipment and chemical raw material, the Preparation equipment includes there-necked flask, industrial microwave oven, electric drying oven with forced convection and makes mould, the there-necked flask is provided with agitator, thermometer and reflux condenser, and the chemical raw material includes aromatic dianhydride, polar solvent, polyetheramine, fatty alcohol, foam stabiliser, catalyst, foaming agent, fire retardant, filler and polyisocyanate curing agent and isocyanates；The chemical composition of the chemical raw material is divided into by quality：Aromatic dianhydride is 100, and polar solvent is 100-200, and polyetheramine is 15-30, and fatty alcohol is 20-25, foam stabiliser is 10-35, and catalyst is 5-15, and foaming agent is 45-60, fire retardant is 0-250, and filler is 0-300, and polyisocyanate curing agent and isocyanates are 1.0-1.5.
The preparation process for being used for：
1）Aromatic dianhydride heating for dissolving and with fatty alcohol is carried out into esterification in polar solvent, solid aromatic dianhydride is converted into two acid diesters solution
Aromatic dianhydride and polar solvent are put into by quality proportioning scheme in there-necked flask, 90-130 DEG C is sufficiently stirred for and is to slowly warm up to,（Normal pressure）When solid aromatic dianhydride is all dissolved to clear solution, cooling addition fatty alcohol carries out refuxing esterification reaction, forms two as clear as crystal acid diesters solution；
2）Two acid diesters solution and polyetheramine reaction generation precursor solution
Two acid diesters solution are cooled to less than 60 DEG C, adds catalyst and polyetheramine that solution is stirred into constant temperature by quality proportioning scheme, precursor solution is obtained；
3）Precursor solution adds foam stabiliser, catalyst, foaming agent, fire retardant to prepare foam composition solution by quality proportioning scheme；
4）Foam composition solution quickly stirs with the polyisocyanates added by quality proportioning scheme, forms mixing liquid solution；Mixing liquid solution is poured into free foaming in mould foam intermediate is obtained；
5）Foam intermediate is obtained modified isocyanate base polyimide foam body through microwave or electrical heating solidification
The demoulding in 10-20 minutes is stopped after foam intermediate unsticking, is removed from the molds, foams are put into industrial microwave oven and is shaped 5-10 minutes, solidify in electric drying oven with forced convection, 200-220 DEG C solidifies 1 hour, polyimide foam body is obtained, and test foaming properties.
Aromatic dianhydride described above includes：3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride（ODPA）, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride（BTDA）, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride（BPDA）, equal benzene tertacarbonic acid's dianhydride (PMDA) of 1,2,4,5-
Polyetheramine described above is also known as amine terminated polyether, and main chain is generally included by the polyether polyamine of expoxy propane, oxirane or expoxy propane/ethylene oxide polymerization：PPOX ether diamine（D-400、D-2000、D-4000）, PPOX ether triamine（T-403、T-3000、T-5000）, PPOX-polyoxyethylene ether diamine（XTJ-502）, PolyTHF ether diamine (P-1000).
Fatty alcohol described above includes：Methyl alcohol, ethanol, low-molecular-weight polyethylene glycol.
Polar solvent described above includes：Dimethylformamide, dimethylacetylamide, 1-METHYLPYRROLIDONE.
Foam stabiliser described above includes：Non-hydrolytic type water soluble polyether siloxanes（DC-193、DC-195、AK-8805、AK-8808）, polyoxyethylene nonionic surfactant, cationic fluorosurfactants activating agent, polyoxyethylene ether fluorocarbon surfactant.
Foaming agent described above includes：Water, methyl alcohol, ethylene glycol ethyl ether, butyl glycol ether.
Catalyst described above includes：It is triethanolamine, triethylene diamine, double（2- dimethylaminoethyls）Ether, stannous octoate, dibutyl tin laurate.
Fire retardant described above includes：Three（2- chloroethyls）Phosphate, three（2- chloropropyls）Phosphate, first class dimethyl phosphonate, expansible graphite, APP, melamine phosphate；Filler includes：Hollow glass microbead, hollow ceramic microballon, expanded vermiculite, glass fibre, carbon fiber, to strengthen foam compression strength.
Polyisocyanates described above includes：Polyphenyl polymethylene polyisocyanates（PAPI）, methyl diphenylene diisocyanate（MDI）, toluene di-isocyanate(TDI)（TDI-80/20）.
Cardinal principle of the invention is to utilize two acid diesters, aminate and water and the polyisocyanates fast reaction of aromatic dianhydride, and its reclaimed water is received to thermally decompose and produce carbon dioxide and aminate with polyisocyanates reaction generation intermediate product, intermediate product.Carbon dioxide reacts to form polyimide structures as foaming agent, aminate with two acid diesters of aromatic dianhydride.Add foam stabiliser to be used to stable foam in formula, add catalyst to accelerate foamable reaction.Polyetheramine directly can be reacted with two acid diesters and polyisocyanates of dianhydride, and the soft segment of polyethers is incorporated on polyimide molecule chain, improve the pliability of strand, so as to the hard and soft polyimide foam body for getting both is obtained.
Beneficial effect of the present invention
The present invention makes preparation process of the present invention easy due to using polyethex amine modification polyimide foam preparation process method.Foam precursor solution storage stabilization, is conducive to craft, mechanical foaming.Because activity poly ether amines directly can react with two acid diesters and polyisocyanates, flexible polyether segments are incorporated on polyimide molecule chain, improve foam pliability, reduce rigidity.Compared with two step method powder foam technique, low cost of manufacture is easy to industrialized production and popularization and application to one-step method liquid foam process of the present invention, has reached the purpose of the present invention.
Specific embodiment
Further illustrate with reference to embodiments, not limit scope involved in the present invention.
In the 500ml there-necked flasks for having agitator, thermometer and reflux condenser, 80 gram 1,2,4,5 equal benzene tertacarbonic acid's dianhydrides are put into（PMDA）And 140 grams of dimethylformamides, it is sufficiently stirred for slowly being warmed up to 90-100 DEG C, treat 1,2,4,5 equal benzene tertacarbonic acid's dianhydride solid particles all dissolve, and when solution becomes clarification, cool to 65 DEG C of inputs, 10 grams of absolute methanols, esterification is carried out, treats that solution is as clear as crystal, cool to less than 60 DEG C.Add 1.5 grams of isoquinolin, 15 grams of polyoxypropylene diamines (D-2000).Above-mentioned solution is stirred to constant temperature, brownish red clear viscous precursor solution is obtained.
Weigh 20 grams of above-mentioned precursor solutions and add 1.5 grams of organic foam stabilizers, 3 grams of deionized waters, 0.5 gram of triethylene diamine, 0.2 gram of dibutyl tin laurate, 0.1 gram pair（Dimethylaminoethyl）Ether catalyst, is configured to foam composition solution.Foam composition solution quickly stirs with 25 grams of polyphenyl polymethylene polyisocyanates, when liquid to be mixed starts foaming and raising, pour into free foaming in mould, the demoulding in 10-20 minutes is stopped after foams unsticking, foams are shaped 5-10 minutes in being put into industrial microwave oven, it is transferred in electric drying oven with forced convection again, 220 DEG C solidify 1 hour, and polyimide foam body is obtained.
The performance for testing foam is as follows：
Thermal conductivity factor
0.036w/(m.k)
Compressive strength
80kpa
Water absorption rate（v/v）
2.6%
Embodiment
2
In the 500ml there-necked flasks for having agitator, thermometer and reflux condenser, 80 gram 1,2,4,5 equal benzene tertacarbonic acid's dianhydrides are put into（PMDA）And 140 grams of dimethylformamides, it is sufficiently stirred for slowly being warmed up to 90-100 DEG C, treat 1,2,4,5 equal benzene tertacarbonic acid's dianhydride solid particles all dissolve, when solution becomes clarification, cool to 65 DEG C of inputs, 10 grams of absolute methanols, esterification is carried out, treats that solution is as clear as crystal, cool to less than 60 DEG C, add 1.5 grams of isoquinolin, 15 grams of PolyTHF ether diamines (P-1000).Above-mentioned solution is stirred to constant temperature, brownish red clear viscous precursor solution is obtained.
Weigh 20 grams of above-mentioned precursor solutions and add 1.5 grams of organic foam stabilizers, 2.5 grams of deionized waters, 0.5 gram of triethylene diamine, 0.2 gram of dibutyl tin laurate, 0.1 gram pair（Dimethylaminoethyl）Ether catalyst, is configured to foam composition solution.Foam composition solution quickly stirs with 25 grams of polyphenyl polymethylene polyisocyanates, when liquid to be mixed starts foaming and raising, pour into free foaming in mould, the demoulding in 10-20 minutes is stopped after foams unsticking, foams are shaped 5-10 minutes in being put into industrial microwave oven, it is transferred in electric drying oven with forced convection again, 220 DEG C solidify 1 hour, and polyimide foam body is obtained.
The performance for testing foam is as follows：
Thermal conductivity factor
0.037w/(m.k)
Compressive strength
76kpa
Water absorption rate（v/v）
1.6%
Embodiment
3
In the 500ml there-necked flasks for having agitator, thermometer and reflux condenser, 70 gram 3,3 is put into’,4,4’Benzophenone tetracarboxylic dianhydride（BTDA）And 110 grams of dimethylformamides, it is sufficiently stirred for slowly being warmed up to 100-110 DEG C, treat 3,3’,4,4’Benzophenone tetracarboxylic dianhydride（BTDA）Solid particle all dissolves, and when solution becomes clarification, cools to 65 DEG C of inputs, 18 grams of absolute methanols, carries out esterification, treats that solution is as clear as crystal, cools to less than 60 DEG C.Add 1.5 grams of isoquinolin, 15 grams of polypropylene oxide triamines (T-403).Above-mentioned solution is stirred to constant temperature, the sticky precursor solution of pale yellow transparent is obtained.
Weigh 20 grams of above-mentioned precursor solutions and add 1.5 grams of organic foam stabilizers, 3 grams of deionized waters, 0.5 gram of triethylene diamine, 0.2 gram of dibutyl tin laurate, 0.1 gram pair（Dimethylaminoethyl）Ether catalyst, is configured to foam composition solution.Foam composition solution quickly stirs with 25 grams of polyphenyl polymethylene polyisocyanates, when liquid to be mixed starts foaming and raising, pour into free foaming in mould, the demoulding in 10-20 minutes is stopped after foams unsticking, foams are shaped 5-10 minutes in being put into industrial microwave oven, it is transferred in electric drying oven with forced convection again, 220 DEG C solidify 1 hour, and polyimide foam body is obtained.
The performance for testing foam is as follows：
Thermal conductivity factor
0.036w/(m.k)
Compressive strength
96kpa
Water absorption rate（v/v）
1.6%
Embodiment
4
In the 500ml there-necked flasks for having agitator, thermometer and reflux condenser, 80 gram 3,3 ', 4,4 ' biphenyl tetracarboxylic dianhydrides are put into（BPDA）And 210 grams of dimethylformamides, it is sufficiently stirred for slowly being warmed up to 100--110 DEG C, add 12 gram 4.4,Diaminodiphenyl ether（4,4,-ODA）, continue to be warmed up to 130 DEG C, make 3,3 ', 4,4 ' biphenyl tetracarboxylic dianhydrides and 4,4,Diaminodiphenyl ether solid particle all dissolves, and when solution becomes clarification, cools to 65 DEG C of inputs, 24 grams of absolute methanols, carries out esterification, treats that solution is as clear as crystal, cools to less than 60 DEG C.Add 1.5 grams of isoquinolin, 15 grams of polypropylene oxide triamines (T-5000).Above-mentioned solution is stirred to constant temperature, purplish red clear viscous precursor solution is obtained.
Weigh 20 grams of above-mentioned precursor solutions and add 1.5 grams of organic foam stabilizers, 3 grams of deionized waters, 0.5 gram of triethylene diamine, 0.2 gram of dibutyl tin laurate, 0.1 gram pair（Dimethylaminoethyl）Ether catalyst, 4 grams of dimethyl methyl phosphonates (DMMP), is configured to foam composition solution.Foam composition solution quickly stirs with 25 grams of polyphenyl polymethylene polyisocyanates, when liquid to be mixed starts foaming and raising, pour into free foaming in mould, the demoulding in 10-20 minutes is stopped after foams unsticking, foams are put into electric drying oven with forced convection, 220 DEG C solidify 1 hour, and polyimide foam body is obtained.
The performance for testing foam is as follows：
Thermal conductivity factor
0.037w/(m.k)
Compressive strength
96kpa
Water absorption rate（v/v）
1.6%
Embodiment
5
Weigh 20 grams of precursor solutions of embodiment 1 and add 1.5 grams of organic foam stabilizers, 3 grams of deionized waters, 0.5 gram of triethylene diamine, 0.2 gram of dibutyl tin laurate, 0.1 gram pair（Dimethylaminoethyl）Ether catalyst, 4 gram three（2- chloroethyls）Phosphate（TCEP）, 8 grams of hollow glass microballoons are well mixed to be configured to foam composition solution.Foam composition solution quickly stirs with 25 grams of polyphenyl polymethylene polyisocyanates, when liquid to be mixed starts foaming and raising, pour into free foaming in mould, the demoulding in 10-20 minutes is stopped after foams unsticking, foams are put into electric drying oven with forced convection, 220 DEG C solidify 1 hour, and polyimide foam body is obtained.
The performance for testing foam is as follows：
Thermal conductivity factor
0.035w/(m.k)
Compressive strength
115kpa
Water absorption rate（v/v）
1.6%
Embodiment
6
Weigh 20 grams of precursor solutions of embodiment 1 and add 1.5 grams of organic foam stabilizers, 0.5 gram of organofluoro surfactants, 3 grams of deionized waters, 0.5 gram of triethylene diamine, 0.2 gram of dibutyl tin laurate, 0.1 gram pair（Dimethylaminoethyl）Ether catalyst, 5 gram three（2- chloropropyls）Phosphate（TCPP）, 10 grams of expansible graphites are well mixed, and are configured to foam composition solution.Foam composition solution quickly stirs with 25 grams of polyphenyl polymethylene polyisocyanates, when liquid to be mixed starts foaming and raising, pour into free foaming in mould, the demoulding in 10-20 minutes is stopped after foams unsticking, foams are put into electric drying oven with forced convection, 220 DEG C solidify 1 hour, and polyimide foam body is obtained.
The performance for testing foam is as follows：
Density
0.026g/㎝3
Thermal conductivity factor
0.037w/(m.k)
Compressive strength
86kpa
Water absorption rate（v/v）
3.8%.
Claims (1)
1. a kind of Foam preparation processes, it is characterized in that：Methods described prepares foams using Preparation equipment and chemical raw material, the Preparation equipment includes there-necked flask, industrial microwave oven, electric drying oven with forced convection and makes mould, the there-necked flask is provided with agitator, thermometer and reflux condenser, the chemical raw material includes aromatic dianhydride, polar solvent, polyetheramine, fatty alcohol, foam stabiliser, catalyst, foaming agent, fire retardant, filler and polyisocyanate curing agent and isocyanates, and the chemical composition of the chemical raw material is divided into by quality：Aromatic dianhydride is 100, polar solvent is 100-200, polyetheramine is 15-30, and fatty alcohol is 20-25, and foam stabiliser is 10-35, catalyst is 5-15, foaming agent is 45-60, and fire retardant is 0-250, and filler is 0-300, polyisocyanate curing agent and isocyanates are 1.0-1.5, the preparation process for being used for：
1）Aromatic dianhydride heating for dissolving and with fatty alcohol is carried out into esterification in polar solvent, solid aromatic dianhydride is converted into two acid diesters solution；
Aromatic dianhydride and polar solvent are put into by quality proportioning scheme in there-necked flask, 90-130 DEG C is sufficiently stirred for and is to slowly warm up to,（Normal pressure）When solid aromatic dianhydride is all dissolved to clear solution, cooling addition fatty alcohol carries out refuxing esterification reaction, forms two as clear as crystal acid diesters solution；
2）Two acid diesters solution and polyetheramine reaction generation precursor solution；
Two acid diesters solution are cooled to less than 60 DEG C, adds catalyst and polyetheramine that solution is stirred into constant temperature by quality proportioning scheme, precursor solution is obtained；
3）Precursor solution adds foam stabiliser, catalyst, foaming agent, fire retardant to prepare foam composition solution by quality proportioning scheme；
4）Foam composition solution quickly stirs with the polyisocyanates added by quality proportioning scheme, forms mixing liquid solution；Mixing liquid solution is poured into free foaming in mould foam intermediate is obtained；
5）Foam intermediate is obtained modified isocyanate base polyimide foam body through microwave or electrical heating solidification.
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| CN114335526A (en) * | 2020-09-29 | 2022-04-12 | 拓米(成都)应用技术研究院有限公司 | Silicon-based negative electrode, lithium ion battery comprising silicon-based negative electrode and preparation method of silicon-based negative electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114335526A (en) * | 2020-09-29 | 2022-04-12 | 拓米(成都)应用技术研究院有限公司 | Silicon-based negative electrode, lithium ion battery comprising silicon-based negative electrode and preparation method of silicon-based negative electrode |
| CN114335526B (en) * | 2020-09-29 | 2024-07-05 | 拓米(成都)应用技术研究院有限公司 | Silicon-based negative electrode, lithium ion battery comprising silicon-based negative electrode and preparation method of lithium ion battery |
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