CN117069722A - 一种含氮杂环芳香聚醚多元醇及其制备方法和聚氨酯硬质泡沫 - Google Patents
一种含氮杂环芳香聚醚多元醇及其制备方法和聚氨酯硬质泡沫 Download PDFInfo
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- CN117069722A CN117069722A CN202310966998.XA CN202310966998A CN117069722A CN 117069722 A CN117069722 A CN 117069722A CN 202310966998 A CN202310966998 A CN 202310966998A CN 117069722 A CN117069722 A CN 117069722A
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- Prior art keywords
- polyether polyol
- nitrogen
- containing heterocyclic
- polyurethane foam
- heterocyclic aromatic
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 45
- 229920000570 polyether Polymers 0.000 title claims abstract description 45
- 229920005862 polyol Polymers 0.000 title claims abstract description 45
- 150000003077 polyols Chemical class 0.000 title claims abstract description 45
- 239000006260 foam Substances 0.000 title claims abstract description 20
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 16
- 239000004814 polyurethane Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 16
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 16
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 25
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 11
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 7
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- -1 propylene ester Chemical class 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
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- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 4
- 239000004604 Blowing Agent Substances 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical group FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
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- 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 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 14
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- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000004088 foaming agent Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
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- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920000582 polyisocyanurate Polymers 0.000 description 2
- 239000011495 polyisocyanurate Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- WZLFPVPRZGTCKP-UHFFFAOYSA-N 1,1,1,3,3-pentafluorobutane Chemical compound CC(F)(F)CC(F)(F)F WZLFPVPRZGTCKP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- 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
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- 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
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- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开一种含氮杂环芳香聚醚多元醇及其制备方法和聚氨酯硬质泡沫。含氮杂环芳香聚醚多元醇的结构式示意为:
Description
技术领域
本发明属于聚氨酯硬泡材料领域,具体涉及一种含氮杂环芳香聚醚多元醇及其在聚氨酯硬泡中的应用。
背景技术
硬质聚氨酯泡沫作为一种高分子绝热保温材料,由于具有高强度、隔热保温等优良特性,在保温隔热领域有广泛的应用。但是随着全球资源越来越紧缺,社会对资源节约型产品的要求越来越高,尤其是近年来碳达峰和碳中和的政策加持,建设零碳园区和零碳社区成为未来的一个发展方向。因此高强度和较好的导热聚氨酯泡沫是目前研究的重要方向之一。
CN106590379A公开以含溴二元醇/酚为起始剂,在催化剂作用下与环氧氯丙烷进行开环聚合反应,得到双官能度的聚环氧氯丙烷,再将上述产物与强碱溶液反应得到端环氧基化合物,最后该端环氧基化合物进行水解反应后再经后处理得到含卤阻燃聚醚多元醇。该工艺优点是原料价廉易得,反应简单;但是该方法制备的聚醚多元醇较苯胺聚醚活性低,所制得的泡沫强度和导热也未得到较好提升。
CN104877105 A公开了一种聚氨酯硬泡组合料及其制备方法,该方法使用HFC-365mfc/227ea作为发泡剂,成本较高,且不环保。
CN101257947 A公开了一种用于甲酸发泡的聚异氰脲酸酯硬质泡沫的催化剂体系以及生产该聚异氰脲酸酯硬质泡沫的方法和可由这种方法得到的聚异氰酸酯硬质泡沫。该方法制得的组合料无法应用于管道喷涂体系,且含有物理发泡剂戊烷,易燃易爆。
因而,鉴于以上问题,希望合成一种简单高效的反应型多元醇,可以解决上述组合料不环保、不安全的问题,并提高聚氨酯泡沫的强度和降低导热。
发明内容
本发明的目的是提供一种含氮杂环芳香聚醚多元醇及其制备方法和聚氨酯硬质泡沫。以含氮的杂环为起始剂,通过环氧化合成聚醚多元醇,该聚醚多元醇可以改善泡沫泡孔的物理结构,从而使得泡沫能有很好的物理强度,同时可得到较好尺寸稳定性和较低导热。
本发明采用的技术方案如下:
一个方面,本发明提供一种含氮杂环芳香聚醚多元醇,其结构式示意为:
其中,n为2-6,优选为2-5中的任意整数。
本发明所述的含氮杂环芳香聚醚多元醇,平均羟值优选为120~315mgKOH/g,更优选130~240mgKOH/g,官能度为1。
另一个方面,本发明提供上述含氮杂环芳香聚醚多元醇的制备方法:
一种含氮杂环芳香聚醚多元醇的制备方法,包括以下步骤:氮杂环芳香化合物和环氧烷烃进行醚化反应;所述氮杂环芳香化合物为嘌呤;
作为一个优选的方案,本发明所述的方法,环氧烷烃为环氧丙烷;
作为一个优选的方案,本发明所述的方法,在惰性气体的存在下进行;
作为一个优选的方案,本发明所述的方法,在一定压力下进行,所述压力为相对压力0.2~0.3MPa;
作为一个优选的方案,本发明所述的方法,反应温度为80~160℃,优选100~130℃;
作为一个优选的方案,本发明所述的方法,反应结束后,进行粗处理,包括以下步骤:向产物中加入吸附剂,在一定温度下进行过滤,收集滤液得到粗聚醚多元醇;
作为一个优选的方案,本发明所述的方法,进行粗处理后,再进行精制,包括以下步骤:将粗聚醚多元醇在一定温度下及高真空下脱除水分及其它副产物,得到产品。
再一个方面,本发明提供上述含氮杂环芳香聚醚多元醇在制备聚氨酯硬质泡沫中的应用:
一种聚氨酯硬质泡沫,包括以下组成:按照质量份,
本发明所述聚醚多元醇组合物,包括以下组成:按照质量份,
本发明所述山梨醇聚醚多元醇是以山梨醇为起始剂,以环氧丙烷开环聚合得到,羟值为450~500mgKOH/g;
本发明所述蔗糖聚醚多元醇是以蔗糖为起始剂,环氧丙烷开环聚合得到,羟值为360~500mgKOH/g;
本发明所述丙二醇聚醚多元醇是以丙二醇为起始剂,以环氧丙烷开环聚合得到,羟值为100~150mgKOH/g。
本发明所述的表面活性剂为硅氧烷类表面活性剂,优选自:B84806、AK8805、东峻H3636、DC193、M88108、B8423、B84806、Y16368、B8404、AK8812中的任意一种或多种的组合,优选B84806。
本发明所述的降粘剂选自丙烯酯、烷酮类有机物、磷酸三(2-氯丙基)酯、磷酸三乙酯、有机硅低聚物、邻苯二甲酸酯、脂肪族二元酸酯、异丁酸酯、苯多酸酯、环氧烃类、和烷基磺酸酯中的任意一种或多种的组合;优选为丙烯酯、烷酮类有机物、磷酸三(2-氯丙基)酯和磷酸三乙酯中的一种或多种;进一步优选为碳酸丙烯酯和/或磷酸三乙酯。
本发明所述的催化剂主要有胺类催化剂和/或有机金属盐类催化剂;所述胺类催化剂为双(二甲胺基乙基)醚、五甲基二亚乙基三胺、N,N-二甲基环己胺、三乙烯二胺、三乙胺、1,4-二甲基哌嗪、N,N-二甲基苄胺和双(2-二甲氨基乙基)醚中的任意一种或多种的组合,优选为双(二甲胺基乙基)醚、五甲基二亚乙基三胺和三乙烯二胺中的一种或多种;所述有机金属盐类催化剂为醋酸钾、辛酸亚锡、异辛酸钾和二月桂酸二丁基锡中的任意一种或多种的组合,优选为二月桂酸二丁基锡、异辛酸钾和醋酸钾中的一种或多种。
本发明所述的发泡剂优选为HFC-245fa发泡剂。
本发明所述的异氰酸酯是聚合MDI(多亚甲基多苯基多异氰酸酯),NCO含量为30~32%,优选万华化学的PM-200。
本发明的组合料在制备聚氨酯泡沫时,可按照常规方法制备。在一种实施方式中,将组合料中的组分按照比例加入料罐中,并经高压机或喷涂机喷在旋转并匀速前进的钢管上自动固化成型,制得聚氨酯泡沫;优选地,混合发泡条件为:料温45-50℃,表压700-850psi。
本发明具有以下优势:
本发明制备的硬质聚氨酯泡沫具有高强度,较好尺寸稳定性和较低的导热。
本发明所述的发泡剂为HFC-245fa,作为第三代的替代发泡剂,臭氧消耗潜值(ODP)为0,对臭氧层无破坏作用。
本发明制得的泡沫密度较低的情况下也能达到良好性能,成品密度可达60-78kg/m3,吸水率≤8%,闭孔率≥90%,50℃导热系数≤0.033W/(mK),径向压缩强度≥0.3Mpa。
具体实施方式
下面结合实施例进一步说明本发明的实施方案。但是本发明不限于所列出的实施例,还应包括在本发明所要求的权利范围内其它任何公知的改变。
实施例和对比例中所用原料如下:
聚醚多元醇B:山梨醇为起始剂,环氧丙烷为聚合单体,羟值为470mgKOH/g,官能度5.2,万华化学(烟台)容威聚氨酯有限公司;
聚醚多元醇C:蔗糖为起始剂,环氧丙烷为聚合单体,羟值为410mgKOH/g,官能度4.3,万华化学(烟台)容威聚氨酯有限公司;
聚醚多元醇D:丙二醇为起始剂,环氧丙烷为聚合单体,羟值为110mgKOH/g,官能度2.0,万华化学(烟台)容威聚氨酯有限公司;
降粘剂:碳酸丙烯酯,简称PC,购自上海泰坦科技股份有限公司;
表面活性剂:B84806,购自赢创特种化学(上海)有限公司;
胺类催化剂:双(二甲胺基乙基)醚、五甲基二亚乙基三胺、三乙烯二胺,购自赢创特种化学(上海)有限公司;
有机金属盐类催化剂:二月桂酸二丁基锡、异辛酸钾、醋酸钾,新典化学材料(上海)有限公司;
发泡剂:HFC-245fa,购自霍尼韦尔公司;
异氰酸酯:PM200,万华化学集团股份有限公司。
聚醚多元醇A制备:
1)将500g嘌呤(分子式C5H4N4)和5gKOH加入到反应釜中,充分进行氮气置换,搅拌;
2)将反应温度升至100℃,缓慢加入环氧丙烷500g,在100℃下反应至环氧丙烷加料完成,而后升温至110℃再熟化1小时;
3)升温至120℃,加入剩余500g环氧丙烷,保持反应釜压力0.2~0.3Mpa,直至剩余环氧丙烷添加完毕;再升温至120~125℃后继续熟化2~3小时;
4)反应产物加入7.5g磷酸去除溶液中的钾离子,加入分子筛进行吸附,真空抽滤后得到粗聚醚多元醇;
5)将粗聚醚多元醇加热到115℃真空脱除未反应的环氧丙烷及其他副产物,得到最终产品。羟值为237mgKOH/g。
聚醚多元醇a制备:
1)将500g嘌呤和5gKOH加入到反应釜中,充分进行氮气置换,搅拌;
2)将反应温度升至100℃,缓慢加入环氧丙烷3000g,在100℃下反应至环氧丙烷加料完成,而后升温至110℃再熟化1小时;
3)升温至120℃,加入剩余3050g环氧丙烷,保持反应釜压力0.2~0.3Mpa,直至剩余环氧丙烷添加完毕;再升温至120~125℃后继续熟化2~3小时;
4)反应产物加入7.5g磷酸去除溶液中的钾离子,加入分子筛进行吸附,真空抽滤后得到粗聚醚多元醇;
5)将粗聚醚多元醇加热到115℃真空脱除未反应的环氧丙烷及其他副产物,得到最终产品。羟值为136mgKOH/g。
聚醚多元醇A1制备:
1)将500g嘌呤和5gKOH加入到反应釜中,充分进行氮气置换,搅拌;
2)将反应温度升至100℃,缓慢加入环氧丙烷121g,在100℃下反应至环氧丙烷加料完成,而后升温至110℃再熟化1小时;
3)升温至120℃,加入剩余120g环氧丙烷,保持反应釜压力0.2~0.3Mpa,直至剩余环氧丙烷添加完毕;再升温至120~125℃后继续熟化2~3小时;
4)反应产物加入7.5g磷酸去除溶液中的钾离子,加入分子筛进行吸附,真空抽滤后得到粗聚醚多元醇;
5)将粗聚醚多元醇加热到115℃真空脱除未反应的环氧丙烷及其他副产物,得到最终产品。羟值为315mgKOH/g。
聚醚多元醇A的n约为2,聚醚多元醇a的n约为5,聚醚多元醇A1的n约为1。
聚氨酯硬质泡沫的制备:
按照表1中对比例和实施例的不同配比,将聚醚多元醇组合物、降粘剂、表面活性剂、催化剂和水混合均匀,然后加入发泡剂混合均匀得到对应的白料,制备的白料和黑料(异氰酸酯)按照比例加入料罐中并经喷涂机喷在旋转并匀速前进的钢管上自动固化成型,制得聚氨酯泡沫;其中,混合发泡条件为:料温45-50℃,表压700-850psi。
泡沫性能见表2。
表1实施例1~5、对比例1~2原料及重量份
表2实施例1~5、对比例1~2泡沫性能
根据表1、2可知,实施例1~5的组合料均能够制备得到符合技术指标的聚氨酯泡沫。对比例1~2的组合料制备得到的聚氨酯泡沫达不到技术指标的要求。
Claims (10)
1.一种含氮杂环芳香聚醚多元醇,其结构式为:
其中,n为2-6中的任意整数,优选为2-5中的任意整数。
2.一种聚氨酯硬质泡沫,包括以下组成:按照质量份,
所述聚醚多元醇组合物包含权利要求1所述的含氮杂环芳香聚醚多元醇。
3.根据权利要求2所述的聚氨酯硬质泡沫,其特征在于,所述聚醚多元醇组合物包括以下组成:按照质量份,
4.根据权利要求3所述的聚氨酯硬质泡沫,其特征在于,所述山梨醇聚醚多元醇是以山梨醇为起始剂,以环氧丙烷开环聚合得到,羟值为450~500mgKOH/g。
5.根据权利要求3所述的聚氨酯硬质泡沫,其特征在于,所述蔗糖聚醚多元醇是以蔗糖为起始剂,环氧丙烷开环聚合得到,羟值为360~500mgKOH/g。
6.根据权利要求3所述的聚氨酯硬质泡沫,其特征在于,所述丙二醇聚醚多元醇是以丙二醇为起始剂,以环氧丙烷开环聚合得到,羟值为100~150mgKOH/g。
7.根据权利要求2-6任一项所述的聚氨酯硬质泡沫,其特征在于,所述表面活性剂为硅氧烷类表面活性剂,优选自:B84806、AK8805、东峻H3636、DC193、M88108、B8423、B84806、Y16368、B8404、AK8812中的任意一种或多种的组合;和/或
所述降粘剂选自丙烯酯、烷酮类有机物、磷酸三(2-氯丙基)酯、磷酸三乙酯、有机硅低聚物、邻苯二甲酸酯、脂肪族二元酸酯、异丁酸酯、苯多酸酯、环氧烃类、烷基磺酸酯中的任意一种或多种的组合;优选为丙烯酯、烷酮类有机物、磷酸三(2-氯丙基)酯和磷酸三乙酯中的一种或多种;进一步优选为碳酸丙烯酯和/或磷酸三乙酯。
8.根据权利要求2-7任一项所述的聚氨酯硬质泡沫,其特征在于,所述的催化剂包括胺类催化剂和/或有机金属盐类催化剂;
优选的,所述胺类催化剂为双(二甲胺基乙基)醚、五甲基二亚乙基三胺、N,N-二甲基环己胺、三乙烯二胺、三乙胺、1,4-二甲基哌嗪、N,N-二甲基苄胺和双(2-二甲氨基乙基)醚中的任意一种或多种的组合;所述有机金属盐类催化剂为醋酸钾、辛酸亚锡、异辛酸钾和二月桂酸二丁基锡中的任意一种或多种的组合。
9.根据权利要求2-8任一项所述的聚氨酯硬质泡沫,其特征在于,所述的发泡剂为HFC-245fa发泡剂。
10.根据权利要求2-9任一项所述的聚氨酯硬质泡沫,其特征在于,所述的异氰酸酯是聚合MDI,NCO含量优选为30~32%。
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