CN110621714A - 用于夹心板的具有低加工温度和增强粘附性的聚异氰脲酸酯泡沫 - Google Patents
用于夹心板的具有低加工温度和增强粘附性的聚异氰脲酸酯泡沫 Download PDFInfo
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- CN110621714A CN110621714A CN201880030591.3A CN201880030591A CN110621714A CN 110621714 A CN110621714 A CN 110621714A CN 201880030591 A CN201880030591 A CN 201880030591A CN 110621714 A CN110621714 A CN 110621714A
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- Prior art keywords
- foam according
- foam
- polyol
- amount
- phosphate
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- 239000006260 foam Substances 0.000 title claims abstract description 69
- 229920000582 polyisocyanurate Polymers 0.000 title claims abstract description 43
- 239000011495 polyisocyanurate Substances 0.000 title claims abstract description 43
- 239000003063 flame retardant Substances 0.000 claims abstract description 16
- 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 abstract description 10
- 229920005862 polyol Polymers 0.000 claims description 46
- 150000003077 polyols Chemical class 0.000 claims description 45
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 29
- 229920000570 polyether Polymers 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 20
- 229920005906 polyester polyol Polymers 0.000 claims description 19
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 14
- -1 DBU methylamine salt Chemical class 0.000 claims description 12
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 claims description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 7
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 claims description 6
- YWDFOLFVOVCBIU-UHFFFAOYSA-N 1-dimethoxyphosphorylpropane Chemical compound CCCP(=O)(OC)OC YWDFOLFVOVCBIU-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 230000003111 delayed effect Effects 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 60
- 239000000203 mixture Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 239000004604 Blowing Agent Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 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 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 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 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000000022 bacteriostatic agent Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
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- 238000005227 gel permeation chromatography Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
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- KOAWAWHSMVKCON-UHFFFAOYSA-N 6-[difluoro-(6-pyridin-4-yl-[1,2,4]triazolo[4,3-b]pyridazin-3-yl)methyl]quinoline Chemical compound C=1C=C2N=CC=CC2=CC=1C(F)(F)C(N1N=2)=NN=C1C=CC=2C1=CC=NC=C1 KOAWAWHSMVKCON-UHFFFAOYSA-N 0.000 description 1
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- 150000001409 amidines Chemical class 0.000 description 1
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- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
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- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
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- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种聚异氰脲酸酯泡沫、其在夹心板中的用途、包含该泡沫的夹心板和制备该夹心板的方法。本发明聚异氰脲酸酯泡沫显示甚至在无增粘剂下的良好粘附性能、在较低温度(≤50℃)下PIR体系的改进加工性和改进阻燃性能。
Description
发明的技术领域
本发明涉及一种聚异氰脲酸酯泡沫、其在夹心板中的用途、包含该泡沫的夹心板和制备夹心板的方法。
发明背景
具有多孔芯的夹心板由于其轻质和高强度而引人注目。该类面板通常通过在两个面层之间包夹具有低强度的多孔芯来构建,面层各自比多孔芯薄得多但具有优异机械性能。
由于夹心板市场中越来越高的阻燃性(FR)需求,聚异氰脲酸酯(PIR)泡沫由于其良好的FR性能而变得越来越受欢迎。然而,PIR夹心板生产存在两个主要问题:a)在PIR泡沫与金属面层之间的差粘附性,b)高加工需求,例如>60℃。许多客户使用增粘剂来解决粘附性问题。此外,高加工温度的成本高,尤其是在冬季时。这两个问题增加了夹心板生产的成本。
具有改进粘附性能的聚氨酯/聚异氰脲酸酯泡沫已公开于许多出版物中。
例如,CN 102666630 A公开了聚氨酯/聚异氰脲酸酯泡沫,其可通过使A)多元醇组分与B)聚异氰酸酯组分反应来获得,该多元醇组分包含A1)芳族聚酯多元醇、A2)以碳水化合物多元醇开始的聚醚多元醇和A3)以乙二醇开始的聚醚多元醇,其中多元醇组分A)的总羟基数为≥150mg KOH/g至≤300mg KOH/g,其中NCO基团与相对于NCO基团呈反应性的氢原子的总和的当量比为≥110:100至≤200:100。据说泡沫具有与面层的改进粘结性能且适用于在不需使用额外粘结剂下产生复合组件。然而,NCO指数减小至110-200,且这使得泡沫变为聚氨酯/聚异氰脲酸酯共混物(PUIR)泡沫。聚氨酯部分将改进粘附性能。然而,PUIR泡沫的阻燃性能比PIR泡沫的阻燃性能更差。
发明概述
本发明的一个目的为提供显示甚至在无增粘剂下的良好粘附性能、在较低温(≤60℃)下的改进加工性和改进阻燃性能的聚异氰脲酸酯泡沫。
该目的可通过聚异氰脲酸酯泡沫来实现,该聚异氰脲酸酯泡沫可通过使A)多元醇组分与B)具有约210至约500的NCO指数的聚异氰酸酯组分反应来获得,该多元醇组分包含:A1)聚酯多元醇、A2)短链聚醚多元醇和A3)长链聚醚多元醇。
在本发明的第一方面中,提供可通过使A)多元醇组分与B)具有约210至约500的NCO指数的聚异氰酸酯组分反应来获得的聚异氰脲酸酯泡沫,该多元醇组分包含:A1)聚酯多元醇、A2)短链聚醚多元醇和A3)长链聚醚多元醇。
在本发明的第二方面中,提供本发明聚异氰脲酸酯泡沫在夹心板中的用途。
在本发明的第三方面中,提供包含本发明聚异氰脲酸酯泡沫的夹心板。
在本发明的第四方面中,提供制备本发明夹心板的方法,该方法包括将产生本发明聚异氰脲酸酯泡沫的反应混合物施加至面层的步骤。
发明详述
在一个方面中,本发明涉及可通过使A)多元醇组分与B)具有约210至约500的NCO指数的聚异氰酸酯组分反应来获得的聚异氰脲酸酯泡沫,该多元醇组分包含:A1)聚酯多元醇、A2)短链聚醚多元醇和A3)长链聚醚多元醇。
聚酯多元醇A1)可为例如芳族聚酯多元醇。芳族聚酯多元醇可为例如二官能以及任选地三官能或更多官能的醇与芳族二官能以及任选地三官能和更多官能的羧酸或羟基羧酸或内酯的缩聚产物。代替游离聚羧酸,低级醇的相应聚羧酸酐或相应聚羧酸酯也可用于制备聚酯。
适用于制备聚酯多元醇的二醇的实例为乙二醇、丁二醇、二甘醇、三甘醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇及其异构体、1,6-己二醇及其异构体或新戊二醇,还有聚亚烷基二醇如聚乙二醇,其中优选乙二醇、丁二醇、1,6-己二醇及其异构体以及新戊二醇。此外,还可使用多元醇如三羟甲基丙烷、甘油、赤藓醇、季戊四醇或三羟甲基苯。
可使用例如邻苯二甲酸、间苯二甲酸、对苯二甲酸、萘二甲酸和/或四氯邻苯二甲酸作为芳族二羧酸。相应酸酐也可用作酸源。
聚酯多元醇A1)优选地具有约50mg KOH/g至约750mg KOH/g,更优选约100mg KOH/g至约500mg KOH/g,甚至更优选约150mg KOH/g至约400mg KOH/g,最优选约150mg KOH/g至约300mg KOH/g的羟基数。聚酯多元醇A1)的数均分子量可为约100至约3000,优选约200至约2000,更优选约300至约1000,最优选约400至约800,如通过使用聚苯乙烯标准的凝胶渗透色谱法(GPC)所测量。
聚酯多元醇A1)的量基于组分A)和B)的总重量可为约1%至约35%,优选约5%至约30%,更优选约15%至约25%。
短链聚醚多元醇A2)和长链聚醚多元醇A3)中的聚醚多元醇通过已知方法获得,例如在催化剂存在下通过加入至少一种包含2-8个,优选2-6个,尤其优选2-4个反应性氢原子的起始剂分子经由氧化烯的阴离子或阳离子聚合获得。所用催化剂可包含碱金属氢氧化物如氢氧化钠或氢氧化钾;或碱金属醇化物如甲醇钠、乙醇钠、乙醇钾或异丙醇钾;或在阳离子聚合的情况下路易斯酸如五氯化锑、醚合三氟化硼或漂白土。可使用的其他催化剂为双金属氰化物化合物,称为DMC催化剂。用于制备A2)和A3)的氧化烯包含一种或多种在亚烷基结构部分中具有2-8个碳原子的化合物,例如四氢呋喃、氧化乙烯、氧化丙烯、1,2-氧化丁烯、2,3-氧化丁烯或氧化苯乙烯,在每种情况下单独或呈混合物形式,且优选为氧化丙烯和/或氧化乙烯。
可使用的起始剂分子的实例为乙二醇、二甘醇、甘油、三羟甲基丙烷、季戊四醇、糖衍生物如蔗糖、己糖醇衍生物如山梨糖醇、甲胺、乙胺、异丙胺、丁胺、苯甲胺、苯胺、甲苯胺、甲苯二胺、萘胺、乙二胺、二亚乙基三胺、4,4'-亚甲基二苯胺、1,3-丙二胺、1,6-己二胺、乙醇胺、二乙醇胺、三乙醇胺以及其他二元醇或多元醇或二元胺或多元胺。
在一个优选实施方案中,短链聚醚多元醇A2)由在二羟甲基丙烷、三羟甲基丙烷或甘油或乙二醇上,优选地在乙二醇上引发的氧化乙烯和/或氧化丙烯,尤其是氧化丙烯的反应产物组成。
短链聚醚多元醇A2)具有约100mg KOH/g至约1250mg KOH/g,更优选约100mg KOH/g至约950mg KOH/g,特别优选地约100mg KOH/g至约500mg KOH/g,最优选约100mg KOH/g至约300mg KOH/g的OH数。
短链聚醚多元醇A2)的数均分子量可为约100至约1000,优选约200至约900,更优选约300至约800,最优选约400至约600。
短链聚醚多元醇A2)的量基于组分A)和B)的总重量可为约1重量%至约20重量%,优选约1%至约10%,更优选约1%至约6%。
在一个优选实施方案中,长链聚醚多元醇A3)由在二羟甲基丙烷、三羟甲基丙烷或甘油上,优选地在甘油上引发的氧化乙烯和/或氧化丙烯,尤其是氧化乙烯和氧化丙烯的反应产物组成。
长链聚醚多元醇A3)具有约10mg KOH/g至约1000mg KOH/g,更优选约20mg KOH/g至约500mg KOH/g,特别优选地约30mg KOH/g至约200mg KOH/g,最优选约40mg KOH/g至约100mg KOH/g的OH数。
长链聚醚多元醇A3)的数均分子量可为大于约1000至约5000,优选约2000至约5000,更优选约3000至约5000,最优选约3000至约4000。
已惊奇地发现当使用长链聚醚多元醇A3)作为原料时,将大大改进所得PIR泡沫的粘附强度。长链聚醚多元醇A3)的量基于组分A)和B)的总重量可为约1%至约20%,优选约1%至约10%,更优选约1%至约5%。
聚异氰酸酯组分B)可为单体聚异氰酸酯或聚异氰酸酯预聚物。单体聚异氰酸酯可为例如脂族、环脂族或芳族异氰酸酯。实例为二苯基甲烷-2,2'-二异氰酸酯、二苯基甲烷-2,4-二异氰酸酯和二苯基甲烷-4,4'-二异氰酸酯;单体二苯基甲烷二异氰酸酯的混合物和具有更大数目的环的二苯基甲烷二异氰酸酯同系物(聚合MDI)的混合物;异佛尔酮二异氰酸酯(IPDI)或其低聚物;甲苯二异氰酸酯(TDI),例如甲苯二异氰酸酯异构体如甲苯-2,4-二异氰酸酯或甲苯-2,6-二异氰酸酯或这些的混合物;四亚甲基二异氰酸酯或其低聚物;六亚甲基二异氰酸酯(HDI)或其低聚物;亚萘基二异氰酸酯(NDI)或其混合物。优选单体聚异氰酸酯为MDI。
聚异氰酸酯预聚物可通过使过量聚异氰酸酯与具有至少两个对异氰酸酯呈反应性的基团的化合物反应以产生预聚物来获得。用于制备预聚物的聚异氰酸酯可为例如以上对单体聚异氰酸酯所提及的那些。
本发明聚异氰酸酯预聚物的NCO指数为优选约210至约500,更优选约250至约500,最优选约300至约500。较高NCO指数为改进面板应用中的FR性能的关键技术途径,这将满足面板应用中的FR需求。
制备PIR泡沫的反应有利地在催化剂存在下进行。本发明中可使用的催化剂可为例如碱性胺,例如脂族仲胺、咪唑、脒,还有烷醇胺、路易斯酸或有机金属化合物,特别是基于锡的那些。多元胺如N,N,N',N",N"-五甲基二亚乙基三胺还可任选地与乙酸钾一起使用。
还可使用由各种催化剂的混合物组成的催化剂体系。在一个优选实施方案中,催化剂可额外包含所谓的延迟催化剂。其中优选DBU(1,8-二氮杂双环[5.4.0]十一碳-7-烯)基胺盐催化剂,更优选叔胺。
出人意料地发现,当使用延迟催化剂时,尤其当使用DBU基胺盐作为催化剂时,将大大改进所得PIR泡沫的粘附强度。
催化剂的量在每种情况下基于组分A)和B)的总重量可为约0.1%至约5%,优选约0.1%至约4.5%,更优选约0.1%至约3.0%,甚至更优选约0.15%至约2.5%,最优选约0.2%至约1.0%。
在制备PIR泡沫的本发明方法中,可使用各种助剂和/或添加剂,例如阻燃剂、增塑剂、表面活性剂、发泡剂、稳定剂、泡孔调节剂、填料、颜料、染料、抗氧化剂、水解稳定剂、抗静电剂、抑真菌剂(fungistatic agent)和抑细菌剂(bacteriostatic agent)等。
可使用的阻燃剂可为含磷阻燃剂如i)具有低分子量的含磷阻燃剂。这些化合物优选具有低于300g/mol,尤其是低于300g/mol,优选低于200g/mol,尤其优选150g/mol至190g/mol的摩尔质量,且分子中优选地具有小于4个磷原子,特别是小于3个,更特别是小于2个,尤其是1个磷原子。优选膦酸酯和/或磷酸酯。膦酸酯和/或磷酸酯的分子中可进一步包含卤素原子。尤其优选选自以下的磷酸酯和膦酸酯:乙基膦酸二乙酯(diethylethanephosphonate;DEEP)、丙基膦酸二甲酯(dimethyl propylphosphonate;DMPP)和磷酸三乙酯(triethyl phosphate;TEP),进一步优选选自乙基膦酸二乙酯(DEEP)和磷酸三乙酯(TEP)的那些,ii)不与异氰酸酯反应的另一组含磷化合物具有高分子量,优选具有高于300g/mol的摩尔质量。优选地,其在分子中具有至少1个磷原子。优选膦酸酯和/或磷酸酯,尤其是磷酸酯。这些磷酸酯的优选实例为磷酸二苯基甲苯基酯(DPC)、磷酸三(2-氯异丙基)酯(TCPP)和/或磷酸三苯酯,特别是磷酸二苯基甲苯基酯,
iii)磷酸铵或聚磷酸铵。
在本发明的一个优选实施方案中,阻燃剂选自乙基膦酸二乙酯(DEEP)、丙基膦酸二甲酯(DMPP)、磷酸三乙酯(TEP)和磷酸三(2-氯异丙基)酯(TCPP)。
阻燃剂可单独或以混合物形式使用。
阻燃剂的量在每种情况下基于组分A)和B)的总重量可为0重量%至约10重量%,优选约0.1重量%至约8.0重量%,更优选约0.5重量%至约7.0重量%,甚至更优选约0.8重量%至约6.5重量%,最优选约0.8重量%至约6.0重量%。
已惊奇地发现,当使用TEP与TCPP的组合时,将大大改进所得PIR泡沫的粘附强度。在本发明的一个优选实施方案中,TEP与TCPP的重量比可为约0.1至约10.0,优选约0.2至约5.0,更优选约0.5至约2.0。
可使用的发泡剂为化学发泡剂如水和/或甲酸,这些化学发泡剂与异氰酸酯基反应并消除二氧化碳且分别消除二氧化碳和一氧化碳。称为物理发泡剂的化合物也可与水组合使用或优选地替代水使用。这些化合物为相对于起始组分为惰性的化合物,在室温下大部分为液体,且在氨基甲酸酯反应的条件下汽化。这些化合物的沸点优选低于60℃。在物理发泡剂中,还有在室温下为气态且在压力下引入或溶于起始组分中的化合物,其中实例为二氧化碳、低沸点链烷烃和氟代烷烃。
发泡剂大部分选自链烷烃、甲酸和/或具有至少4个碳原子的环烷烃,二烷基醚,酯,酮,缩醛,具有1-8个碳原子的氟代烷烃,和在烷基链中具有1-3个碳原子的四烷基硅烷,特别是四甲基硅烷。
可提及的实例为丙烷、正丁烷、异丁烷、环丁烷、正戊烷、异戊烷、环戊烷、环己烷、二甲醚、甲基乙基醚、甲基丁基醚、甲酸甲酯、丙酮,还有可在对流层中降解且因此不损害臭氧层的氟代烷烃,例如三氟甲烷、二氟甲烷、1,1,1,3,3-五氟丁烷、1,1,1,3,3-五氟丙烷、1,1,1,2-四氟乙烷、二氟乙烷和七氟丙烷。所提及的物理发泡剂可单独或以任何彼此需要的组合使用。
水的量基于组分A)和B)的重量优选为0.1-2.0重量%。
可借助于Kunststoffhandbuch[塑料手册(Plastics Handbook)],第7卷,“聚氨酯”,Carl-Hanser-Verlag Munich,第3版,1993中的实例发现关于用于实现本发明方法的起始物质的其他细节,例如增塑剂、表面活性剂、发泡剂、稳定剂、泡孔调节剂、填料、颜料、染料、抗氧化剂、水解稳定剂、抗静电剂、抑真菌剂和抑细菌剂等。
根据本发明获得的PIR泡沫显示在低温(≤60℃)下与已商品化的PIR体系相比的改进粘附强度和改进加工性;同时其显示优异阻燃性。
在一个优选实施方案中,聚异氰脲酸酯泡沫可通过使A)多元醇组分与B)具有约210至约500的NCO指数的聚异氰酸酯组分在C1)阻燃剂TEP和TCPP以及C2)呈延迟催化剂包装形式的催化剂包装存在下反应来获得,该多元醇组分包含:A1)聚酯多元醇、A2)短链聚醚多元醇、A3)长链多元醇。
已证明本发明的反应混合物中的组分A3、C1和C2可产生改进粘附性、降低加工温度和改进阻燃性的效果。本发明将3种因素组合在一起以实施有利效应。因此,在一个优选实施方案中,制备聚异氰脲酸酯泡沫的方法可在低温如<60℃下进行。
在一个优选实施方案中,聚异氰脲酸酯泡沫可通过使A)多元醇组分与B)具有约450的NCO指数的聚异氰酸酯组分在C1)量为约0.8%至约6.0%的阻燃剂TEP和TCPP以及C2)量为约0.2%至约1.0%的呈延迟催化剂包装形式的催化剂包装存在下反应来获得,该多元醇组分包含:A1)量为约15%至约25%的聚酯多元醇、A2)量为约1重量%至约20重量%的短链聚醚多元醇、A3)量为约1%至约5%的量的长链多元醇,在每种情况下基于组分A)和B)的总重量。
在一个实施方案中,反应可在约20℃至约60℃,更优选约30℃至约60℃,最优选约40℃至约60℃的温度下进行。
在另一方面中,本发明涉及制备夹心板的方法,其中将产生根据本发明的PIR泡沫的反应混合物施加至面层。方法可连续或非连续地进行。用于连续生产的装置例如由DE 1609 668或DE 1 247 612已知。
在制备夹心板的方法的一个实施方案中,在反应混合物与面层之间不设置增粘剂层。在该情况下,该PIR泡沫的改进粘附性能确保泡沫与面层之间足够的粘附。
面层可由纸张、纤维或金属制成,优选地由金属制成。合适的金属为例如钢或铝。
制备夹心板的方法可呈双带式传送机方法的形式。由于根据本发明的泡沫的粘附性能可省略面层的预处理。这将简化方法。
在本发明方法的另一实施方案中,面层在施加反应混合物时具有≤60℃的温度。该温度可在生产工厂中例如借助前述烘箱设施实现。尤其对于双带式传送机体系而言,温度较低,这就方法管理和经济而言再次带来优势。
在一个替代实施方案中,夹心板可借助模制方法制备。在该情况下,将产生根据本发明的PIR泡沫的预混合反应混合物施加至先前设置于模具中的面层,随后反应,以形成面板。面层可预加热,例如至≤60℃的温度。在反应期间,模具中的温度可通过加热模具来保持恒定。在一定时间如10分钟至2小时的时段后,由模具移除成品面板。
本发明还涉及根据本发明的泡沫在夹心板中的用途,和包含根据本发明的泡沫的夹心板。
本发明的夹心板可供用于建筑中的各种应用如工业建筑物、公共建筑办公室和行政建筑、冷藏室、清洁室、农业建筑、发电厂、住宅和用于运输如冷藏集装箱、拖车等。
附图简述
图1和2说明了实施例中的夹心板的粘附能。
实施例
本发明借助以下实施例详细说明。
除非此外说明,否则实施例中的所有组分量是指重量份。
将下表1中所示的预混合PIR泡沫形成反应物施加至大小为40cm×40cm×9cm且具有预加热至60℃的下部金属片的箱模具且在该箱模具中发泡。在反应期间,模具中的温度恒定地保持在60℃下。在模具中保持30min后,由模具移除成品夹心板。
表1 PIR泡沫的配方
所得夹心板的粘附能根据剥离测试来测量。剥离测试可通过使用Zwick机器(可购自BASF公司)来将底面上的10cm×20cm金属片(对于夹心板而言,底面的粘附性比顶面更差)由一个侧面剥离泡沫表面来进行。计算力和距离以获得粘附能。结果显示于图1和表2中。
表2所得夹心板的粘附能
对照1 | 实施例1 | 实施例2 | 实施例3 | |
粘附能(10<sup>-3</sup>J) | 1926.6 | 2536.6 | 2715.4 | 2480 |
改进 | - | 31.6% | 40.9% | 28.7% |
与对照1相比,当使用长链多元醇(实施例1)、TCPP和TEP组合(实施例2)、延迟催化剂(实施例3)时,粘附能分别改进31.6%、40.9%和28.7%。
在实施例4中,通过分别在60℃、50℃和40℃下使用表3中的配方来重复实施例1至3的程序,同时对照2在60℃下进行。
表3 PIR泡沫的配方
测量所得夹心板的粘附能,且结果显示于图2和表4中,其中实施例-60意指在60℃下,实例4-50意指在50℃下,实施例4-40意指在40℃下。
表4所得夹心板的粘附能
对照2 | 实施例4-60 | 实施例4-50 | 实施例4-40 | |
粘附能(10<sup>-3</sup>J) | 1983 | 2634 | 3421 | 3245 |
改进 | - | 32.8% | 72.5% | 63.6% |
通常较低温对PIR泡沫固化有害,这是因为其将造成更差粘附性。令人惊奇地,实施例显示在显著较低温度(50℃)下粘附增大高达70%。此外,本发明实施例的阻燃性与对照的阻燃性类似。
Claims (26)
1.一种聚异氰脲酸酯泡沫,可通过使A)多元醇组分与B)具有约210至约500的NCO指数的聚异氰酸酯组分反应来获得,所述多元醇组分包含:A1)聚酯多元醇、A2)短链聚醚多元醇和A3)长链聚醚多元醇。
2.根据权利要求1的泡沫,其中所述聚酯多元醇A1)为芳族聚酯多元醇。
3.根据权利要求1或2的泡沫,其中聚酯多元醇A1)优选具有约50mg KOH/g至约750mgKOH/g,更优选约100mg KOH/g至约500mg KOH/g,甚至更优选约150mg KOH/g至约400mgKOH/g,最优选约150mg KOH/g至约300mg KOH/g的羟基数。
4.根据权利要求1-3中任一项的泡沫,其中所述聚酯多元醇A1)的量基于组分A)和B)的总重量可为约1%至约35%,优选约5%至约30%,更优选约15%至约25%。
5.根据权利要求1-4中任一项的泡沫,其中所述短链聚醚多元醇A2)具有约100至约1000,优选约200至约900,更优选约300至约800,最优选约400至约600的数均分子量。
6.根据权利要求1-5中任一项的泡沫,其中所述短链聚醚多元醇A2)由在二羟甲基丙烷、三羟甲基丙烷或甘油或乙二醇上,优选在乙二醇上引发的氧化乙烯和/或氧化丙烯,尤其是氧化丙烯的反应产物组成。
7.根据权利要求1-6中任一项的泡沫,其中所述短链聚醚多元醇A2)的量基于组分A)和B)的总重量为约1重量%至约20重量%,优选约1%至约10%,更优选约1%至约6%。
8.根据权利要求1-7中任一项的泡沫,其中所述长链多元醇A3)具有大于约1000至约5000,优选约2000至约5000,更优选约3000至约5000,最优选约3000至约4000的数均分子量。
9.根据权利要求1-8中任一项的泡沫,其中所述长链聚醚多元醇A3)由在二羟甲基丙烷、三羟甲基丙烷或甘油上,优选在甘油上引发的氧化乙烯和/或氧化丙烯,尤其是氧化乙烯和氧化丙烯的反应产物组成。
10.根据权利要求1-9中任一项的泡沫,其中所述长链多元醇A3)的量基于组分A)和B)的总重量为约1%至约20%,优选约1%至约10%,更优选约1%至约5%。
11.根据权利要求1-10中任一项的泡沫,其中本发明聚异氰酸酯预聚物的NCO指数为约250至约500,更优选约300至约500。
12.根据权利要求1-11中任一项的泡沫,其中所述反应在催化剂存在下进行。
13.根据权利要求12的泡沫,其中所述催化剂包含延迟催化剂。
14.根据权利要求13的泡沫,其中所述延迟催化剂为DBU基胺盐。
15.根据权利要求12-14中任一项的泡沫,其中所述催化剂的量在每种情况下基于组分A)和B)的总重量为约0.1%至约5%,优选约0.1%至约4.5%,更优选约0.1%至约3.0%,甚至更优选约0.15%至约2.5%,最优选约0.2%至约1.0%。
16.根据权利要求1-15中任一项的泡沫,其中在该反应期间使用阻燃剂。
17.根据权利要求16的泡沫,其中所述阻燃剂选自含磷阻燃剂。
18.根据权利要求17的泡沫,其中所述阻燃剂选自:
i)乙基膦酸二乙酯(DEEP)、丙基膦酸二甲酯(DMPP)和磷酸三乙酯(TEP)、磷酸三(2-氯异丙基)酯(TCPP),进一步优选选自乙基膦酸二乙酯(DEEP)和磷酸三乙酯(TEP)的那些;
ii)磷酸三(2-氯异丙基)酯(TCPP)、磷酸二苯基甲苯基酯(DPC)和/或磷酸三苯酯,特别是磷酸二苯基甲苯基酯;
iii)磷酸铵或聚磷酸铵。
19.根据权利要求18的泡沫,其中所述阻燃剂选自TEP与TCPP的组合。
20.根据权利要求16-19中任一项的泡沫,其中所述阻燃剂的量在每种情况下基于组分A)和B)的总重量为0%至约10%,优选约0.1%至约8.0%,更优选约0.5%至约7.0%,甚至更优选0.8%至约6.5%,最优选约0.8%至约6.0%。
21.根据权利要求1-20中任一项的泡沫,其中所述反应在约20℃至约60℃,更优选约30℃至约60℃,最优选约40℃至约60℃的温度下进行。
22.根据权利要求1-20中任一项的泡沫,其中所述聚异氰脲酸酯泡沫可通过使A)多元醇组分与B)具有约450的NCO指数的聚异氰酸酯组分在C1)量为约0.8%至约6.0%的阻燃剂TEP和TCPP以及C2)量为约0.2%至约1.0%的呈延迟催化剂包装形式的催化剂包装的存在下反应来获得,所述多元醇组分包含:A1)量为约15%至约25%的聚酯多元醇、A2)量为约1重量%至约20重量%的短链聚醚多元醇、A3)量为约1%至约5%的长链多元醇,在每种情况下基于组分A)和B)的总重量。
23.根据权利要求1-22中任一项的聚异氰脲酸酯泡沫在夹心板中的用途。
24.一种包含根据权利要求1-22中任一项的聚异氰脲酸酯泡沫的夹心板。
25.一种制备夹心板的方法,包括将产生根据权利要求1-22中任一项的聚异氰脲酸酯泡沫的反应混合物施加至面层的步骤。
26.根据权利要求24的夹心板在建筑和运输中的用途。
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