CN114555669A - 硬质聚氨酯泡沫的生产 - Google Patents
硬质聚氨酯泡沫的生产 Download PDFInfo
- Publication number
- CN114555669A CN114555669A CN202080070458.8A CN202080070458A CN114555669A CN 114555669 A CN114555669 A CN 114555669A CN 202080070458 A CN202080070458 A CN 202080070458A CN 114555669 A CN114555669 A CN 114555669A
- Authority
- CN
- China
- Prior art keywords
- amino acid
- rigid polyurethane
- polyurethane foams
- ammonium
- foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 48
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 58
- 150000003077 polyols Chemical class 0.000 claims abstract description 54
- 239000006260 foam Substances 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 40
- 150000003862 amino acid derivatives Chemical class 0.000 claims abstract description 24
- 239000012948 isocyanate Substances 0.000 claims abstract description 23
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 23
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims abstract description 4
- -1 aromatic acid halide Chemical class 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 10
- 238000007906 compression Methods 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001413 amino acids Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- WIEZPMIEWPJAOF-UHFFFAOYSA-N 2-hydroxypropyl(tripropyl)azanium Chemical compound CCC[N+](CCC)(CCC)CC(C)O WIEZPMIEWPJAOF-UHFFFAOYSA-N 0.000 claims description 2
- JPKKMFOXWKNEEN-UHFFFAOYSA-N 2-methylcholine Chemical compound CC(O)C[N+](C)(C)C JPKKMFOXWKNEEN-UHFFFAOYSA-N 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 2
- NEUNOKQNYOCZNP-UHFFFAOYSA-N benzyl-(2-hydroxyethyl)-dimethylazanium Chemical compound OCC[N+](C)(C)CC1=CC=CC=C1 NEUNOKQNYOCZNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000005207 tetraalkylammonium group Chemical class 0.000 claims description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 2
- PPOMHYHIAFOMRU-UHFFFAOYSA-N tributyl(2-hydroxypropyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC(C)O PPOMHYHIAFOMRU-UHFFFAOYSA-N 0.000 claims description 2
- ZSPDDMXDEWGOCE-UHFFFAOYSA-N triethyl(2-hydroxypropyl)azanium Chemical compound CC[N+](CC)(CC)CC(C)O ZSPDDMXDEWGOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 description 19
- 229920002635 polyurethane Polymers 0.000 description 17
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- QIAFMBKCNZACKA-UHFFFAOYSA-N N-benzoylglycine Chemical compound OC(=O)CNC(=O)C1=CC=CC=C1 QIAFMBKCNZACKA-UHFFFAOYSA-N 0.000 description 11
- 125000002947 alkylene group Chemical group 0.000 description 11
- 229920000582 polyisocyanurate Polymers 0.000 description 11
- 239000004721 Polyphenylene oxide Substances 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 10
- 238000007373 indentation Methods 0.000 description 10
- 229920000570 polyether Polymers 0.000 description 10
- 229920001228 polyisocyanate Polymers 0.000 description 10
- 239000005056 polyisocyanate Substances 0.000 description 10
- 238000005829 trimerization reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000009472 formulation Methods 0.000 description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000005187 foaming Methods 0.000 description 8
- 239000011495 polyisocyanurate Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000016709 nutrition Nutrition 0.000 description 4
- 230000035764 nutrition Effects 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- 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 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001718 carbodiimides Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical class COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241001425800 Pipa Species 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
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- 239000002666 chemical blowing agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- 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 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- ZBCAZEFVTIBZJS-UHFFFAOYSA-M sodium;2-benzamidoacetate Chemical compound [Na+].[O-]C(=O)CNC(=O)C1=CC=CC=C1 ZBCAZEFVTIBZJS-UHFFFAOYSA-M 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
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- 239000004970 Chain extender Substances 0.000 description 1
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- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种用于生产硬质聚氨酯泡沫的组合物,其包含至少一种异氰酸酯组分、多元醇组分、任选存在的泡沫稳定剂和任选存在的发泡剂,所述组合物包含至少一种催化氨基甲酸酯或异氰脲酸酯键形成的催化剂,并且所述催化剂包括氨基酸衍生物的盐。
Description
本发明涉及聚氨酯领域,尤其是硬质聚氨酯泡沫领域。更具体地,本发明涉及使用特定盐生产硬质聚氨酯泡沫,并且还涉及用其生产的泡沫的用途。本发明涉及硬质聚氨酯泡沫。
在本发明的上下文中,聚氨酯(PU)尤其被理解为是指可通过多异氰酸酯与多元醇或具有异氰酸酯反应性基团的化合物的反应得到的产物。除了聚氨酯之外,还可以在反应中形成另外的官能团,例如脲二酮(uretdiones)、碳二亚胺、异氰脲酸酯、脲基甲酸酯、缩二脲、脲和/或脲酮亚胺(uretonimines)。因此,在本发明的上下文中PU被理解为是指聚氨酯和聚异氰脲酸酯、聚脲和含有脲二酮、碳二亚胺、脲基甲酸酯、缩二脲和脲酮亚胺基团的多异氰酸酯反应产物。在本发明的上下文中,聚氨酯泡沫(PU泡沫)尤其被理解为是指作为基于多异氰酸酯与多元醇或具有异氰酸酯反应性基团的化合物的反应产物得到的泡沫。除了同名的聚氨酯之外,还可以形成其他官能团,例如脲基甲酸酯、缩二脲、脲、碳二亚胺、脲二酮、异氰脲酸酯或脲酮亚胺。
本发明更具体地涉及聚异氰脲酸酯的形成。该反应被称为三聚化,因为在形式意义上三个异氰酸酯基团反应得到异氰脲酸酯环。
在硬质聚氨酯和聚异氰脲酸酯泡沫的生产中,使用了各种催化剂以在显著程度上积极影响发泡的反应曲线和泡沫的使用性能。聚异氰脲酸酯的形成在此是有利的,因为这些导致良好的机械性能(高压缩硬度)和改进的阻燃性能。
有各种已知的出版物涉及在硬质PU泡沫的生产中使用催化剂来提高压缩硬度或辅助三聚反应。
EP 1 745 847 A1描述了基于草酸钾和对与异氰酸酯的反应呈惰性的溶剂的三聚催化剂。
WO 2016/201675描述了由基于空间位阻羧酸盐的组合物和带有异氰酸酯反应性基团的叔胺组成的三聚催化剂。
WO 2013/074907 A1描述了芳族羧酸的四烷基胍盐作为聚氨酯泡沫的催化剂的用途。
本发明解决的问题为确保提供具有特别有利的使用性能的硬质聚氨酯或聚异氰脲酸酯泡沫,所述使用性能特别是诸如即使在短反应时间之后也具有良好的压缩硬度和/或压痕硬度。然而,与此同时,优选将对于上升曲线的影响降至最低。
现已令人意外地发现,在硬质PU泡沫生产中使用本发明的氨基酸衍生物的盐会导致硬质PU泡沫具有改进的使用性能。更具体地,改进了三聚化,结果泡沫更快地固化,这意味着泡沫在早期关键时刻具有高压缩硬度和高压痕硬度。本发明还有一个特别的优点为使用根据本发明的氨基酸衍生物能够将对于上升曲线的影响最小化。这是非常有利的,因为否则的话反应混合物的流动性可能会出现问题,这会导致相当大的加工问题。
因此可以通过根据本发明的解决方案生产基于硬质PU泡沫的产品,例如具有非常特别高质量的隔绝板或冷却单元,并且使生产硬质PU泡沫的方法更有效。
本发明的另外的优点为所用化学品、尤其是氨基酸衍生物的盐的良好环境毒理学分类。
本发明的其他的优点为可以帮助生产具有低水平泡沫缺陷的硬质PU泡沫。
本发明提供一种用于生产硬质聚氨酯泡沫的组合物,其包含至少一种异氰酸酯组分、多元醇组分、任选存在的泡沫稳定剂、任选存在的发泡剂,
其中所述组合物包含至少一种催化氨基甲酸酯或异氰脲酸酯键形成的催化剂,
其中所述催化剂包含氨基酸衍生物的盐。
本发明的氨基酸衍生物盐在形式意义上可衍生自芳族羧酸与氨基酸的反应;它们尤其还可以通过氨基酸与芳族羧酸、芳族羧酸酯、芳族碳酰卤和/或芳族羧酸酐的反应得到,这是本发明的一个优选的实施方案。在此可以通过常规方法进行向盐的转化,例如通过与常规碱例如KOH、NaOH或相应的氢氧化铵反应。
特别优选的本发明的氨基酸衍生物的盐满足下式(I):
其中
R3为芳族基团,任选地为可以具有取代基的多环芳族基团,任选地其还具有可以连接其他氨基酸的其他羧基官能团,
其中R3优选为
R1、R2、R4独立地为H、C1至C18烷基、烯基、芳基或烷芳基,其也可以被取代,
M+为阳离子,诸如优选碱金属阳离子或铵阳离子或取代的铵阳离子,优选Li+、Na+、K+、Rb+、Cs+或取代的铵阳离子,诸如有利地为四烷基铵、三烷基羟烷基铵、苄基三烷基铵、四甲基铵、四乙基铵、四丁基铵、四丙基铵、二甲基二烯丙基铵、三甲基(2-羟丙基)铵、三乙基(2-羟丙基)铵、三丙基(2-羟丙基)铵、三丁基(2-羟丙基)铵、二甲基苄基(2-羟丙基)铵、二甲基苄基(2-羟乙基)铵及它们的组合。
在此尤其优选R3为苯基、烷基苯基,或者为衍生自邻苯二甲酸、间苯二甲酸、对苯二甲酸或均苯四甲酸(pyromellitic acid)的基团。
在一个特别优选的实施方案中,所述盐衍生自下式(II)的氨基酸衍生物:
其中R1、R2、M+如上定义,
其中R2在每种情况下优选为H,
其中R1和R2进一步优选各自为H,
其中R1和R2尤其是各自为H且M+为Na+、K+或NR1 4 +,R1如上定义。
因此,特别优选的结构为:
其中M+和R1如上定义。
特别优选马尿酸盐
其中M+如上定义,优选钠、钾或铵作为阳离子,
尤其优选钠盐:
本发明的盐可以通过已知方法制备。
马尿酸及其盐是可商购的。其制备是本领域技术人员已知的。例如,马尿酸可以通过苯甲酰氯与甘氨酸反应来制备(Schotten-Baumann法)。基于苯甲酸酯(甲酯)与甘氨酸的酰胺化同样是可能的。在这种情况下,这些盐的制备例如用合适的碱(例如KOH、NaOH或相应的氢氧化铵)来进行。
工业级质量通常足以用于PU泡沫,因为来自制备过程中的任何次要成分都不会影响PU泡沫生产。这是本发明的另一个显著的优点。
在本发明的一个优选的实施方案中,根据本发明的盐可以添加到载体介质中的反应混合物中。使用的载体介质可以是所有适合作为溶剂的物质。有用的实例包括合成和/或天然来源的二醇、烷氧基化物或油。针对本发明的氨基酸衍生物的盐使用载体介质是本发明的一个优选的实施方案。根据本发明的盐也可以用作具有不同载体介质的组合物的一部分。
在本发明的一个优选的实施方案中,根据本发明的盐在成品聚氨酯泡沫中的总质量比例为0.01重量%至10重量%、优选0.1重量%至5重量%。
在本发明的一个优选的实施方案中,根据本发明的组合物包含水和/或发泡剂、任选的至少一种阻燃剂和/或可有利地用于生产硬质聚氨酯泡沫的其他添加剂。除了根据本发明的盐之外,还可以存在其他催化剂。
一种特别优选的根据本发明的组合物包含以下组分:
a)至少一种异氰酸酯反应性组分、尤其是多元醇
b)至少一种多异氰酸酯和/或多异氰酸酯预聚物
c)如上所述的根据本发明的催化剂(本发明的氨基酸衍生物的盐),
d)(任选的)其他催化剂,
e)(任选的)基于硅氧烷或其他表面活性剂的泡沫稳定组分,
f)一种或多种发泡剂,
g)其他添加剂、填充剂、阻燃剂等。
将在下文中对单独的可用组分(此处记作a)至g))进行更详细的描述。已对组分c)进行了描述。
在根据本发明的组合物中,基于100质量份的多元醇组分a),本发明的盐c)的质量比例优选为0.1至10pphp、更优选0.2至5pphp且尤其优选0.5至3pphp。
本发明还提供一种通过使一种或多种多元醇组分与一种或多种异氰酸酯组分反应来生产硬质聚氨酯泡沫的方法,其中所述反应在催化氨基甲酸酯或异氰脲酸酯键的形成的催化剂的存在下进行,
其中所述催化剂包含上文已描述的氨基酸衍生物的盐,尤其是使用如上所述的组合物。在此除了根据本发明的盐之外也可以使用其他催化剂。
在此优选将氨基酸衍生物的盐提供给反应混合物以在载体介质中生产硬质PU泡沫,所述载体介质优选包含合成和/或天然来源的二醇、烷氧基化物或油。
本发明还提供了上文已描述的氨基酸衍生物的盐作为催化剂在生产硬质聚氨酯泡沫塑料中的用途,与在无氨基酸衍生物的盐的情况下生产的硬质聚氨酯泡沫相比,优选用于改进硬质聚氨酯泡沫的使用性能,尤其是用于提高硬质聚氨酯泡沫在早期关键时刻的压缩硬度,所述压缩硬度可根据DIN EN ISO 844:2014-11确定。
本发明还提供了一种可通过如上所述的根据本发明的方法得到的硬质聚氨酯泡沫。
本发明额外地提供了根据本发明的硬质聚氨酯或聚异氰脲酸酯泡沫用于绝热目的的用途,优选作为隔绝板和隔绝体,和用于包括根据本发明的硬质聚氨酯或聚异氰脲酸酯泡沫作为隔绝材料的冷却装置的用途。
下文更详细地描述了各个可用组分(此处记作a)至g))。已经对组分c)进行了描述。
出于本发明的目的,适合作为多元醇组分a)的多元醇为具有一个或多个异氰酸酯反应性基团、优选OH基团的所有有机物质及其配制剂。优选的多元醇为常规用于生产聚氨酯体系、尤其是聚氨酯涂料、聚氨酯弹性体或泡沫的所有聚醚多元醇和/或聚酯多元醇和/或含羟基的脂族聚碳酸酯,尤其是聚醚聚碳酸酯多元醇,和/或被称作“基于天然油的多元醇(natural oil-based polyols,NOPs)”的天然来源的多元醇。多元醇通常具有1.8至8的官能度和在500至15000范围内的数均分子量。通常使用具有在10至1200mg KOH/g范围内的OH值的多元醇。
可以使用聚醚多元醇。这些聚醚多元醇可以通过已知方法制备,例如通过在作为催化剂的碱金属氢氧化物、碱金属醇盐或胺的存在下使环氧烷阴离子聚合并通过添加至少一种优选含有2或3个键合形式的反应性氢原子的起始剂分子,或通过在路易斯酸(例如五氯化锑或三氟化硼醚合物)的存在下使环氧烷阳离子聚合,或通过双金属氰化物催化。合适的环氧烷在亚烷基中含有2至4个碳原子。实例为四氢呋喃、1,3-环氧丙烷、1,2-环氧丁烷和2,3-环氧丁烷;优选使用环氧乙烷和1,2-环氧丙烷。环氧烷可以单独地、累加地以嵌段、交替的形式或作为混合物使用。使用的起始剂分子尤其可以为分子中具有至少2个、优选2至8个羟基,或具有至少两个伯氨基的化合物。使用的起始剂分子例如可以为水;二元醇、三元醇或四元醇,诸如乙二醇、1,2-丙二醇和1,3-丙二醇、二乙二醇、二丙二醇、甘油、三羟甲基丙烷、季戊四醇;蓖麻油等;高级多官能多元醇,尤其是糖类化合物,例如葡萄糖、山梨糖醇、甘露醇和蔗糖;多元酚;酚醛树脂,例如苯酚与甲醛的低聚缩合产物以及酚、甲醛和二链烷醇胺的曼尼希缩合物(Mannich condensates);以及三聚氰胺;或胺诸如苯胺、EDA、TDA、MDA和PMDA,更优选TDA和PMDA。合适的起始剂分子的选择取决于在聚氨酯生产中所得聚醚多元醇各自的应用领域。
可以使用聚酯多元醇。这些聚酯多元醇基于多元脂族或芳族羧酸的酯,优选具有2至12个碳原子。脂族羧酸的实例是琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二甲酸、马来酸和富马酸。芳族羧酸的实例是邻苯二甲酸、间苯二甲酸、对苯二甲酸和作为异构体的萘二甲酸。聚酯多元醇通过这些多元羧酸与多元醇的缩合得到,所述多元醇优选具有2至12个、更优选具有2至6个碳原子的二醇或三醇,优选三羟甲基丙烷和甘油。
可以使用聚醚碳酸酯多元醇。这些聚醚碳酸酯多元醇是含有以碳酸酯键合形式的二氧化碳的多元醇。由于二氧化碳在化学工业的许多工艺中作为副产物大量形成,因此从商业角度来看,在环氧烷聚合中使用二氧化碳作为共聚单体是特别令人感兴趣的。用二氧化碳部分替代多元醇中的环氧烷具有显著降低多元醇生产成本的潜力。此外,使用CO2作为共聚单体在环境方面非常有利,因为该反应构成了温室气体向聚合物的转化。通过使用催化剂将环氧烷和二氧化碳加成到H-官能起始剂物质上来制备聚醚聚碳酸酯多元醇早已为人所知。在此可以使用各种催化剂体系:第一代是非均相锌或铝盐,如US-A 3900424或US-A3953383中所述。此外,单核和双核金属络合物已成功地用于CO2与环氧烷的共聚(WO 2010/028362、WO 2009/130470、WO 2013/022932或WO 2011/163133)。用于二氧化碳与环氧烷的共聚的最重要的一类催化剂体系是双金属氰化物催化剂,也称为DMC催化剂(US-A4500704、WO 2008/058913)。合适的环氧烷和H-官能起始剂物质是也用于制备如上所述的不含碳酸酯的聚醚多元醇的那些。
可以使用基于可再生原料的多元醇,即“基于天然油的多元醇”(NOP)。鉴于化石资源(即石油、煤炭和天然气)的长期可得性有限并且针对原油价格上涨的背景,用于生产聚氨酯泡沫的NOP越来越受到关注,并且已在此类申请(WO 2005/033167、US 2006/0293400、WO 2006/094227、WO 2004/096882、US 2002/0103091、WO 2006/116456和EP 1678232)中多次描述。这些多元醇中的许多现在可从不同的制造商处购得(WO 2004/020497、US 2006/0229375、WO 2009/058367)。根据基础原料(例如豆油、棕榈油或蓖麻油)和随后的后处理,会产生具有不同性能特性的多元醇。在此可以基本上区分两组:a)基于可再生原料的多元醇,其经过改性使得它们可以100%的程度用于生产聚氨酯(WO 2004/020497、US 2006/0229375);b)基于可再生原料的多元醇,由于其加工和性能,其仅能以一定比例替代基于石油化学品的多元醇(WO 2009/058367)。
另一类可用的多元醇为所谓的填充多元醇(聚合物多元醇)。这些产品的一个特点为它们含有分散的固体有机填充剂,固体含量高达40%或更多。SAN、PUD和PIPA多元醇属于有用的多元醇。SAN多元醇为高反应性多元醇,其含有基于苯乙烯-丙烯腈(SAN)的分散的共聚物。PUD多元醇为同样呈分散形式的含有聚脲的高反应性多元醇。PIPA多元醇为含有分散的聚氨酯的高反应性多元醇,例如通过异氰酸酯与常规多元醇中的链烷醇胺原位反应形成。
另一类有用的多元醇为通过多元醇与异氰酸酯以优选100:1至5:1、更优选50:1至10:1的摩尔比反应作为预聚物得到的那些。优选这种预聚物以溶液的形式补充至聚合物中,并且所述多元醇优选对应于用于制备预聚物的多元醇。
异氰酸酯与多元醇的优选比率,表示为制剂的指数,即异氰酸酯基团与异氰酸酯反应性基团(例如OH基团、NH基团)的化学计量比乘以100,在10至1000、优选40至350的范围内。指数100表示反应基团的摩尔比为1:1。
使用的异氰酸酯组分b)优选为一种或多种具有两个或更多个异氰酸酯官能团的有机多异氰酸酯。使用的多元醇组分优选为一种或多种具有两个或更多个异氰酸酯反应性基团的多元醇。
适合作为用于本发明目的的异氰酸酯组分的异氰酸酯为所有含有至少两个异氰酸酯基团的异氰酸酯。通常,可以使用本身已知的所有脂族、脂环族、芳基脂族且优选芳族多官能异氰酸酯。相对于消耗异氰酸酯的组分的总和,异氰酸酯更优选在60至200摩尔%的范围内使用。
具体实例在此为在亚烷基中具有4至12个碳原子的亚烷基二异氰酸酯,例如十二烷1,12-二异氰酸酯、2-乙基四亚甲基1,4-二异氰酸酯、2-甲基五亚甲基1,5-二异氰酸酯、四亚甲基1,4-二异氰酸酯,且优选六亚甲基1,6-二异氰酸酯(HMDI),脂环族二异氰酸酯诸如环己烷1,3-和1,4-二异氰酸酯以及这些异构体的任何混合物、1-异氰酸酯基-3,3,5-三甲基-5-异氰酸酯基甲基环己烷(异佛尔酮二异氰酸酯或简称IPDI)、六氢甲苯2,4-和2,6-二异氰酸酯以及相应的异构体混合物,且优选芳族二异氰酸酯和多异氰酸酯,例如甲苯2,4-和2,6-二异氰酸酯(TDI)和相应的异构体混合物、萘二异氰酸酯、二乙基甲苯二异氰酸酯、二苯基甲烷2,4'-和2,2'-二异氰酸酯(MDI)和多苯基多亚甲基多异氰酸酯的混合物(粗MDI)以及粗MDI和甲苯二异氰酸酯(TDI)的混合物。有机二异氰酸酯和多异氰酸酯可以单独使用或以其混合物的形式使用。同样可以使用二异氰酸酯的相应“低聚物”(基于异氰脲酸酯、缩二脲、脲二酮的IPDI三聚体)。此外,可以使用基于上述异氰酸酯的预聚物。
也可以使用通过引入氨基甲酸酯、脲二酮、异氰脲酸酯、脲基甲酸酯和其他基团而改性的异氰酸酯,称为改性异氰酸酯。
因此特别优选使用的特别合适的有机多异氰酸酯为甲苯二异氰酸酯的各种异构体(甲苯2,4-和2,6-二异氰酸酯(TDI),以纯形式或作为具有各种组成的异构体混合物)、二苯基甲烷4,4'-二异氰酸酯(MDI)、“粗MDI”或“聚合型MDI”(含有MDI的4,4'异构体以及还有2,4'和2,2'异构体以及具有多于两个环的产品)以及被称作“纯MDI”且主要由2,4'和4,4'异构体混合物构成的二环产品,以及由此衍生的预聚物。特别合适的异氰酸酯的实例例如详述于EP 1712578、EP 1161474、WO 00/58383、US 2007/0072951、EP 1678232和WO 2005/085310中,这些文献在此通过引用全部并入。
除了根据本发明的催化剂即如上所述的氨基酸衍生物的盐之外,还可以使用任选的催化剂d)。在本发明的上下文中合适的任选的催化剂d)是能够加速异氰酸酯与OH官能团、NH官能团或其他异氰酸酯反应性基团以及与异氰酸酯本身的反应的所有化合物。在此可以使用现有技术已知的常规催化剂,包括例如胺(环状、无环;单胺、二胺、具有一个或多个氨基的低聚物)、铵化合物、有机金属化合物和金属盐,优选钾、锡、铁、铋和锌盐。特别地,可以使用多种组分的混合物作为催化剂。
作为组分e),可以使用不含Si的表面活性剂或有机改性的硅氧烷。这种物质在硬质泡沫中的使用是已知的。在本发明的上下文中,此处可以使用所有有助于产生泡沫(稳定化、泡孔调节、泡孔打开等)的化合物。这些化合物在现有技术中是众所周知的。
例如,在以下专利说明书中描述了可用于本发明上下文的相应硅氧烷:CN103665385、CN 103657518、CN 103055759、CN 103044687、US 2008/0125503、US 2015/0057384、EP 1520870 A1、EP 1211279、EP 0867464、EP 0867465、EP 0275563。上述文献在此通过引入并入并认为形成本发明公开内容的一部分。特别优选使用聚醚改性的硅氧烷。
发泡剂f)的使用是任选的,根据其使用发泡工艺。可以使用化学发泡剂和物理发泡剂。在此发泡剂的选择很大程度上取决于系统的类型。
根据使用的发泡剂的量,产生具有高密度或低密度的泡沫。例如,可以生产密度为5kg/m3至900kg/m3的泡沫。优选的密度为8至800、更优选10至600kg/m3,尤其是30至150kg/m3。
使用的物理发泡剂可以为具有适当沸点的相应化合物。同样可以使用与NCO基团反应以释放气体的化学发泡剂,例如水或甲酸。发泡剂的实例包括液化的CO2、氮气、空气、挥发性液体,例如具有3、4或5个碳原子的烃,优选环戊烷、异戊烷和正戊烷,氢氟烃,优选HFC 245fa、HFC 134a和HFC 365mfc、氯氟烃,优选HCFC 141b、氢氟烯烃(HFO)或氢卤烯烃,例如1234ze、1234yf、1233zd(E)或1336mzz,含氧化合物例如甲酸甲酯、丙酮和二甲氧基甲烷,或氯化烃,优选二氯甲烷和1,2-二氯乙烷。
用于本发明目的的合适的水含量取决于除水之外是否使用一种或多种发泡剂。在纯水发泡泡沫的情况下,该值优选为1至20pphp;当额外使用其他发泡剂时,水的用量优选减少到0.1至5pphp。
使用的添加剂g)可以为现有技术已知的并且用于生产聚氨酯、尤其是聚氨酯泡沫的任何物质,例如交联剂和扩链剂、抗氧化降解的稳定剂(称为抗氧化剂)、阻燃剂、表面活性剂、杀菌剂、泡孔细化添加剂、泡孔开放剂、固体填充剂、抗静电添加剂、成核剂、增稠剂、染料、颜料、色浆、香料、乳化剂等。
根据本发明的用于生产硬质PU泡沫的方法可以通过已知方法进行,例如通过手动混合或优选通过发泡机。如果所述方法使用发泡机进行,则可以使用高压或低压机器。根据本发明的方法可以间歇或连续地进行。
在本发明的上下文中,优选的硬质聚氨酯或聚异氰脲酸酯泡沫制剂产生的泡沫密度为5至900kg/m3,并且优选具有表1中所示的组成。
表1:优选的硬质聚氨酯或聚异氰脲酸酯制剂的组成
对于本发明方法的进一步优选的实施方案和配置,同样参考上文已经给出的与本发明的组合物有关的细节。
如已经提到的,本发明还提供了可通过所提到方法得到的硬质PU泡沫。
在本发明的一个优选的实施方案中,聚氨酯泡沫的密度为5至900kg/m3,优选8至800kg/m3、尤其优选10至600kg/m3,更特别是30至150kg/m3。
尤其可以生产主要为闭孔的泡沫。闭孔含量有利地>80%,优选>90%。
根据本发明的硬质PU泡沫可用作或用于生产隔绝材料,优选隔绝板、冰箱、隔绝泡沫、屋顶衬里、包装泡沫或喷涂泡沫。
本发明的PU泡沫可以有利地用在特别是冷藏仓库、制冷器具和家用电器工业中,例如用于生产用于屋顶和墙壁的隔绝板、作为冷冻货物的容器和仓库中的隔绝材料以及用于冷藏和冷冻设备。
其他优选的使用领域为在车辆构造中,尤其是用于生产车辆内顶衬里、车身部件、内部装饰、冷却车辆、大型容器、运输托盘、包装层压材料;在家具行业中,例如用于家具部件、门、衬里;在电子应用中。
本发明的冷却装置具有本发明的PU泡沫(聚氨酯或聚异氰脲酸酯泡沫)作为隔绝材料。
本发明还提供了硬质PU泡沫在制冷技术中、在制冷设备中、在建筑行业、汽车行业、造船行业和/或电子行业中作为隔绝材料;作为隔绝板;作为喷涂泡沫;作为单组分泡沫的用途。
本发明的主题将在下面通过实施例的方式进行描述,无意将本发明限制在这些示例性实施方案。在下文规定了化合物的范围、通式或群组的情况下,这些旨在不仅包括明确提及的化合物的相应范围或群组,而且还包括可以通过去除单个值(范围)或化合物而获得的化合物的所有子范围和子群组。在本说明书的上下文中引用文献的情况下,其全部内容、特别是关于形成该文献所引用的上下文的主题,旨在形成本发明公开内容的一部分。除非另有说明,否则百分比是按重量百分比表示的数字。当在下文中记录平均值时,除非另有说明,否则所讨论的值是重量平均值。在下文中记录了通过测定来确定参数的情况下,除非另有说明,否则这些测定在25℃的温度和101 325Pa的压力下进行。
以下实施例通过示例的方式描述本发明,但无意限制本发明,本发明的应用范围从说明书和权利要求书的全部内容到实施例中引用的实施方案显而易见。
实施例
使用以下原材料来生产泡沫:
Stepanpol PS2352:来自Stepan的聚酯多元醇
Daltolac R 471:来自Huntsman的聚醚多元醇
TCPP:来自Fyrol的磷酸三(2-氯异丙酯)
KOSMOS 75:来自Evonik Nutrition&Care GmbH的基于辛酸钾的催化剂
POLYCAT 5:来自Evonik Nutrition&Care GmbH的胺催化剂
POLYCAT 8:来自Evonik Nutrition&Care GmbH的胺催化剂
MDI(44V20):来自Covestro的Desmodur 44V20L,具有异构且更高官能度的同系物的二苯基甲烷4,4'-二异氰酸酯(MDI)
Tegostab B 8460,来自Evonik Nutrition&Care GmbH的泡沫稳定表面活性剂
用于制备根据本发明的三聚催化剂(盐)的合成实施例
实验A:
将马尿酸钠(可从Sigma-Aldrich得到)溶解在单乙二醇中,以得到含有25%马尿酸钠的溶液
实验B:
将马尿酸(可从Sigma-Aldrich得到)溶解在二乙二醇中,用NaOH水溶液中和盐,然后减压蒸馏掉水。将马尿酸钠含量调整为30%。
实验C:
将马尿酸(可从Sigma-Aldrich得到)溶解在二乙二醇中,用KOH水溶液中和盐,然后减压蒸馏掉水。将马尿酸钾含量调整为30%。
实验D:
使苯甲酸甲酯与甘氨酸在作为溶剂的DEG中反应,使用甲醇钠加速酰胺化并与形成的马尿酸形成盐。减压蒸馏去除过量的甲醇。将马尿酸钠含量调整为30%。
实施例:PU泡沫的生产
通过手动混合进行发泡。为此目的,将根据本发明的化合物、多元醇、阻燃剂、根据本发明的或非根据本发明的催化剂、水、硅氧烷表面活性剂和发泡剂称量到烧杯中并通过盘式搅拌器(直径6cm)在1000rpm下搅拌历时30秒。通过重新称量,确定在混合操作中蒸发的发泡剂的量并再次添加该量的发泡剂。随后,添加异氰酸酯(MDI),并用搅拌器在3000rpm下将反应混合物搅拌5秒。
将反应混合物引入上边缘处的直径为20cm的合适烧杯中以得到自由上升的泡沫。
选择反应混合物的量,使得结束时泡沫圆顶的尖端在烧杯的上边缘上方10至15cm。
在发泡期间,确定胶凝时间,以评价催化剂对发泡速度的影响。
3分钟后,将烧杯上边缘处的泡沫圆顶切掉,使得得到圆形泡沫表面。在该表面处确定泡沫的压痕硬度。
确定压痕硬度的方法
为此目的,测量了将直径为4cm的模具压入泡沫中的力。在压痕深度为5mm处测量压痕力。在切割表面上4个不同点处以圆形排列的方式压入模具,在4、6、8和10分钟后进行测量。
确定压缩硬度的方法
根据DIN EN ISO 844:2014-11用边长为5cm的立方体试样在高至10%的压缩下测定泡沫的压缩硬度(记录的数值为在该测量范围内发生的最大压缩应力)。
表2总结了使用的泡沫制剂(制剂1和制剂2)。
表2
制剂实施例 | 制剂1(PUR) | 制剂(PIR) |
Daltolac R 471 | 100 | |
PS 2352 | 100 | |
三聚催化剂(本发明的盐) | 变化 | 变化 |
POLYCAT 8 | 2.8 | |
POLYCAT 5 | 0.7 | 0.5 |
KOSMOS 75 | 0.7 | |
TEGOSTAB B 8460 | 2 | 2 |
TCPP | 15 | |
水 | 2.5 | 0.5 |
正戊烷 | 14 | |
环戊烷 | 13 | |
MDI(44V20) | 约200 | 约190 |
指数 | 130 | 255 |
使用根据本发明的三聚催化剂的形成结果。
表3
使用根据本发明的各种催化剂和泡沫制剂的发泡实验的总结。记录的数值为在(与MDI混合后)所记录的时间(以分钟为单位)后的压痕硬度(以牛顿为单位)
根据本发明的泡沫各自表现出明显高于比较例1和2的压痕硬度。
在比较例3中,在使用更高剂量的辛酸钾的情况下,压痕硬度同样得到改进。然而,在此,与根据本发明的候选物相比,胶凝时间缩短了15秒,因此更显著地干扰了泡沫的上升曲线,这是不期望的。
由此清楚的是,根据本发明的三聚催化剂能够改进泡沫的固化,同时胶凝时间的减少明显更小。
这是一个巨大的优势,因为由于对凝胶时间的影响很小,反应混合物的可加工性得以保持,例如在发泡混合物的流动性方面,并且同时加速了泡沫的固化。
从实验中清楚地看出,根据本发明的三聚催化剂导致改进的泡沫固化。根据本发明的泡沫的压痕硬度的上述非常好的结果对应于压缩硬度的结果。
Claims (11)
1.一种用于生产硬质聚氨酯泡沫的组合物,其包含至少一种异氰酸酯组分、多元醇组分、任选存在的泡沫稳定剂、任选存在的发泡剂,
其特征在于所述组合物包含至少一种催化氨基甲酸酯或异氰脲酸酯键形成的催化剂,
其中所述催化剂包括氨基酸衍生物的盐。
2.根据权利要求1所述的组合物,其特征在于所述氨基酸衍生物可通过使氨基酸与芳族羧酸、芳族羧酸酯、芳族酰卤和/或芳族羧酸酐反应得到。
3.根据权利要求1或2所述的组合物,其特征在于所述氨基酸衍生物的盐满足下式(I):
其中
R3为芳族基团,任选为多环的芳族基团,其可以具有取代基,任选地还具有可以连接其他氨基酸的其他羧基官能团,
其中R3优选为
R1、R2、R4独立地为H、C1至C18烷基、烯基、芳基或烷芳基,其也可以被取代,
M+为阳离子,诸如优选碱金属阳离子或铵阳离子或取代的铵阳离子,优选Li+、Na+、K+、Rb+、Cs+或取代的铵阳离子,诸如有利地为四烷基铵、三烷基羟烷基铵、苄基三烷基铵、四甲基铵、四乙基铵、四丁基铵、四丙基铵、二甲基二烯丙基铵、三甲基(2-羟丙基)铵、三乙基(2-羟丙基)铵、三丙基(2-羟丙基)铵、三丁基(2-羟丙基)铵、二甲基苄基(2-羟丙基)铵、二甲基苄基(2-羟乙基)铵及它们的组合。
4.根据权利要求3所述的组合物,其特征在于R3为苯基或烷基苯基,或者为衍生自邻苯二甲酸、间苯二甲酸、对苯二甲酸或均苯四甲酸的基团。
6.根据权利要求1至5中任一项所述的组合物,其特征在于,基于所得聚氨酯泡沫,存在的氨基酸衍生物的盐的总质量比例为0.01重量%至10重量%、优选0.1重量%至5重量%。
7.通过使一种或多种多元醇组分与一种或多种异氰酸酯组分反应来生产硬质聚氨酯泡沫的方法,其特征在于所述反应在催化氨基甲酸酯或异氰脲酸酯键的形成的催化剂的存在下进行,
其中所述催化剂包含优选符合权利要求1至6中至少一项的规定的氨基酸衍生物的盐,
尤其是使用根据权利要求1至6中任一项所述的组合物。
8.根据权利要求7所述的方法,其特征在于将所述氨基酸衍生物的盐供应至反应混合物中以在载体介质中生产硬质PU泡沫,所述载体介质优选包括合成和/或天然来源的二醇、烷氧基化物或油。
9.优选符合权利要求1至6中至少一项的规定的氨基酸衍生物的盐作为催化剂在生产硬质聚氨酯泡沫中的用途,与在无氨基酸衍生物的盐的情况下生产的硬质聚氨酯泡沫相比,优选用于改进硬质聚氨酯泡沫的使用性能,尤其是用于提高硬质聚氨酯泡沫在早期关键时刻的压缩硬度,所述压缩硬度可根据DIN EN ISO 844:2014-11确定。
10.可通过根据权利要求7或8所述的方法得到的硬质聚氨酯泡沫。
11.根据权利要求10所述的硬质聚氨酯泡沫用于绝热目的的用途,优选作为隔绝板和/或隔绝体,尤其是用于冷却装置。
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Also Published As
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EP3805285A1 (de) | 2021-04-14 |
US20220403089A1 (en) | 2022-12-22 |
WO2021069164A1 (de) | 2021-04-15 |
KR20220080129A (ko) | 2022-06-14 |
CA3153571A1 (en) | 2021-04-15 |
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