CN108250391A - 一种用于制备聚氨酯的多元醇体系 - Google Patents
一种用于制备聚氨酯的多元醇体系 Download PDFInfo
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- CN108250391A CN108250391A CN201611272597.0A CN201611272597A CN108250391A CN 108250391 A CN108250391 A CN 108250391A CN 201611272597 A CN201611272597 A CN 201611272597A CN 108250391 A CN108250391 A CN 108250391A
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- weight
- polyol
- parts
- isocyanates
- polyol systems
- Prior art date
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 61
- 239000012948 isocyanate Substances 0.000 claims abstract description 69
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 56
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
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- ZFDWWDZLRKHULH-UHFFFAOYSA-N 1,2-dimethyl-5,6-dihydro-4h-pyrimidine Chemical class CN1CCCN=C1C ZFDWWDZLRKHULH-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
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- GEEGPFGTMRWCID-UHFFFAOYSA-N 1-n,1-n,1-n',1-n'-tetramethylbutane-1,1-diamine Chemical compound CCCC(N(C)C)N(C)C GEEGPFGTMRWCID-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical class CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical class CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical class OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
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- 239000000853 adhesive Substances 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
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- 150000001409 amidines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 229940035423 ethyl ether Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 1
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- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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Classifications
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
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Abstract
本发明公开了一种用于制备聚氨酯的多元醇体系，其包含：i)至少一种具有至少两个可与异氰酸酯反应的基团的活性增链剂，其中至少一个可与异氰酸酯反应的基团为游离的伯‑NH2基团；ii)至少一种具有三个可与异氰酸酯反应的基团的活性增链剂，其中至少一个可与异氰酸酯反应的基团为游离的伯‑OH的基团，和iii)至少一种由胺起始的聚醚多元醇。本发明的多元醇体系是相稳定、不分层的，且在与异氰酸酯反应生成聚氨酯产品后能快速脱模。
Description
技术领域
本发明属于聚氨酯技术领域，具体地涉及用于制备聚氨酯的多元醇体系和包含其的聚氨酯体系及由其制备的聚氨酯产品。
背景技术
聚氨酯有多种性质和用途，包括纤维(尤其是弹性纤维)、弹性体、涂料、粘合剂、软、硬泡沫塑料、人造革等等。
由于聚氨酯具有轻质和高刚度的特点，越来越多的聚氨酯复合材料被用作汽车行业中的内部部件。聚氨酯夹层部件早已为人所知，它们通过用增强层覆盖核心层而制得，通常使用增强玻璃纤维作为覆盖材料，使用蜂窝状纸板作为芯材。天然纤维和其它增强材料也可用于增强，硬质泡沫、铝蜂窝板、EPS泡沫等其它材料也可用作芯材。通常将聚氨酯反应混合物施用于“夹层半成品”的一面，并且多数情况下也可以是两面，然后将覆有聚氨酯反应混合物的部件放入具有一定温度的模具中。所述聚氨酯反应混合物在该模具中硬化从而得到制件。然后将由此得到的聚氨酯夹层部件脱模，取出产品。
聚氨酯反应混合物通常包含异氰酸酯组分和可与异氰酸酯反应以生产聚氨酯的多元醇组分。由于供应商希望获得自脱模性能，通常会在多元醇体系中加入脱模剂，因此市场上的大多数多元醇体系是相分离的。这种相分离的多元醇体系给使用者带来了额外的负担，他们必须在使用之前至少花1小时左右的时间来混合该相分离的多元醇体系以确保所得多元醇体系是均匀的。这种额外的混合浪费了时间，降低了生产效率。
因此，需要这样一种用于制备聚氨酯的多元醇体系，其可以避免混合多元醇的额外步骤，并且能够在与异氰酸酯反应生成聚氨酯后快速脱模，不粘膜，在得到高品质产品的前提下，提高生产效率。
发明内容
本发明的目的在于提供一种用于制备聚氨酯的多元醇体系，其在保存期间内可以稳定均相，避免混合多元醇的额外步骤，并且能够在与异氰酸酯反应生成聚氨酯后快速脱模，从而提高生产效率。
本发明的目的是通过以下技术方案来实现的：
根据本发明的第一方面，提供一种用于制备聚氨酯的多元醇体系，其包含：
i)至少一种具有至少两个可与异氰酸酯反应的基团的活性增链剂，其中至少一个可与异氰酸酯反应的基团为游离的伯-NH2基团；
ii)至少一种具有三个可与异氰酸酯反应的基团的活性增链剂，其中至少一个可与异氰酸酯反应的基团为游离的伯-OH的基团，和
iii)至少一种由胺起始的聚醚多元醇。
根据本发明的另一方面，提供一种聚氨酯体系，其包含异氰酸酯组分和多元醇组分，其特征在于，所述多元醇组分为上述的多元醇体系。
根据本发明的另一方面，提供一种聚氨酯产品，其包括使上述聚氨酯体系反应后获得的反应产物。
本发明的多元醇体系是相稳定的，且具有自脱模性能。在与异氰酸酯反应生成聚氨酯后快速脱模。使用者可以直接使用所述多元醇体系而无需额外进一步混合。本发明的聚氨酯体系可以将脱模时间从本领域中通常的大于150秒降低到120秒以下，甚至可达60秒。这种多元醇体系以及包含它的聚氨酯体系可以避免额外的混合步骤，节约劳动成本，同时由于快速脱模而提高生产效率。由于所述多元醇体系是相稳定的，它还可以避免由于相分离，且事先搅拌不充分，而导致的制造不合格部件。本发明的聚氨酯产品由于轻质、强度高，可以广泛用于汽车领域，如用于备胎盖板、天窗拉板等。
具体实施方案
下面对本发明的具体实施方案进行描述。
根据本发明的第一方面，提供一种用于制备聚氨酯的多元醇体系，其包含：
i)至少一种具有至少两个可与异氰酸酯反应的基团的活性增链剂，其中至少一个可与异氰酸酯反应的基团为游离的伯-NH2基团；
ii)至少一种具有三个可与异氰酸酯反应的基团的活性增链剂，其中至少一个可与异氰酸酯反应的基团为游离的伯-OH的基团，和
iii)至少一种由胺起始的聚醚多元醇。
所述多元醇体系还包含基础聚醚多元醇，例如官能度为2-4、优选官能度为2-3的羟值为300～600mgKOH/g的聚醚多元醇，例如可从科思创聚合物(中国)有限公司获得的羟值为475KOH/g的M9158、可从句容宁武新材料公司获得羟值为450KOH/g的NJ4502和可从东昌公司获得羟值为380KOH/g的DC380等。
所述基础聚醚多元醇在本发明的多元醇体系的量为50-80重量份，优选55-75重量份，更优选60-70重量份，以所述多元醇体系的总重量为100重量份计。
所述多元醇体系还可以包含选自以下的一种或多种本领域中常用的添加剂：发泡剂、泡沫稳定剂、催化剂、脱模剂、阻燃剂、色浆、填料、稳定剂、触变剂等。
所述至少一种具有至少两个可与异氰酸酯反应的基团(其中至少一个可与异氰酸酯反应的基团为游离的伯-NH2基团)的活性增链剂除了所述游离的伯-NH2基团以外的可与异氰酸酯反应的基团选自例如伯(仲)氨基、羟基、硫醇基、脲基、环氧基等。
所述至少一种具有至少两个可与异氰酸酯反应的基团(其中至少一个可与异氰酸酯反应的基团为游离的伯-NH2基团)的活性增链剂优选选自具有2-12个碳原子的链烷醇胺，例如乙醇胺、2-氨基丙醇和3-氨基-2，2-二甲基丙醇；具有2-15个碳原子的脂(环)族二胺，例如1，2-乙二胺、1，3-丙二胺、1，3-丁二胺、1，4-丁二胺、1，6-己二胺、异佛尔酮二胺、1，4-环己烷二胺和4，4′-二氨基二环己基甲烷；和具有6-12个碳原子的芳族二胺，例如2，4-和2，6-甲苯二胺；所述链烷醇胺、脂(环)族二胺和芳族二胺中与碳原子相连的一个或更多个氢原子任选被烷基取代，所述烷基包含1-6个碳原子，优选1-4个碳原子。
本发明的多元醇体系中所用的具有至少两个可与异氰酸酯反应的基团(其中至少一个可与异氰酸酯反应的基团为游离的伯-NH2基团)的活性增链剂优选为芳族二胺，例如可从雅保化学公司获得的E100(3，5-二乙基甲苯二胺，DETDA)。
所述至少一种具有至少两个可与异氰酸酯反应的基团的活性增链剂在本发明的多元醇体系中的量为1-25重量份，优选1-20重量份，优选2-15重量份，更优选2-10重量份，最优选2-6重量份，以所述多元醇体系的总重量为100重量份计。
所述至少一种具有三个可与异氰酸酯反应的基团(其中至少一个可与异氰酸酯反应的基团为游离的伯-OH的基团)的活性增链剂除了所述游离的伯-NH2基团以外的可与异氰酸酯反应的基团选自羟基、脲基、硫醇基等。
所述至少一种具有三个可与异氰酸酯反应的基团(其中至少一个可与异氰酸酯反应的基团为游离的伯-OH的基团)的活性增链剂优选选自具有3-8个碳原子的三元醇，例如甘油、1，2，6-己三醇、三羟甲基丙烷。在使用三羟甲基丙烷的情况下，需加热预熔。
所述至少一种具有三个可与异氰酸酯反应的基团的活性增链剂在本发明的多元醇体系中的量为1-20重量份，优选2-15重量份，更优选3-15重量份，以所述多元醇体系的总重量为100重量份计。
所述由胺起始的聚醚多元醇选自由乙二胺起始的羟值为450KOH/g至800KOH/g的聚醚多元醇，例如可从国都公司获得由乙二胺起始的羟值为750KOH/g的ED750，可从科思创聚合物(中国)有限公司获得的由乙二胺起始的羟值为630KOH/g的Desmophen 4050E。
所述由胺起始的聚醚多元醇在本发明的多元醇体系中的量为1-10重量份，优选2-8重量份，更优选2-6重量份，以所述多元醇体系的总重量为100重量份计。
在本发明多元醇体系一个优选实施方案中，按照重量计，所述具有至少两个可与异氰酸酯反应的基团(其中至少一个可与异氰酸酯反应的基团为游离的伯-NH2基团)的活性增链剂、所述至少一种具有三个可与异氰酸酯反应的基团(其中至少一个可与异氰酸酯反应的基团为游离的伯-OH的基团)的活性增链剂和所述由胺起始的聚醚多元醇之间的配比为1∶0.8～8∶0.8～5，优选1∶1～7∶1～3，更优选1∶1～5∶1～2，最优选1∶1～3∶1～2。
所述发泡剂可为已知用于制备聚氨酯的任何发泡剂，包括化学发泡剂和/或物理发泡剂。化学发泡剂是指通过与异氰酸酯反应而生产气体产物的化合物。这类发泡剂的实例有水或羧酸。物理发泡剂是指已乳化或溶解于制备聚氨酯的原料中并在形成聚氨酯的条件下蒸发的化合物。这类发泡剂的实例有烃、卤代烃或其他化合物，例如全氟烷烃如全氟乙烷、氟氯化碳，以及醚、酮、酯和/或缩醛。本发明中优选使用水作为发泡剂。
所述发泡剂在本发明的多元醇体系的量为0-15重量份，优选0-10重量份，更优选0-5重量份，以所述多元醇体系的总重量为100重量份计。
所述泡沫稳定剂选自硅油类物质，例如从赢创公司获得B8411和B8870。
所述泡沫稳定剂在本发明的多元醇体系的量为0-5重量份，优选0.1-4重量份，更优选0.1-3重量份，以所述多元醇体系的总重量为100重量份计。
所述催化剂用于催化多元醇与异氰酸酯反应来制备聚氨酯的任何常规催化剂。所用催化剂的实例为有机金属化合物，优选为以下化合物：有机锡化合物，例如有机羧酸的亚锡(II)盐如乙酸亚锡、辛酸亚锡、乙基己酸亚锡和月桂酸亚锡，和有机羧酸的二烷基锡(IV)盐如二乙酸二丁基锡、二月桂酸二丁基锡、顺丁烯二酸二丁基锡和二乙酸二辛基锡；以及羧酸铋，例如新癸酸铋(III)、2-乙基己酸铋和辛酸铋；或其混合物。其他合适的催化剂有强碱性胺催化剂。所述胺的实例有脒，例如2，3-二甲基-3，4，5，6-四氢嘧啶；叔胺，例如三乙胺、三丁胺、二甲基苄胺、N-甲基吗啉、N-乙基吗啉和N-环己基吗啉、N，N，N’，N’-四甲基乙二胺、N，N，N’，N’-四甲基丁二胺、N，N，N’，N’-四甲基己二胺、五甲基二亚乙基三胺、四甲基二氨基乙基醚、二(二甲基氨基丙基)脲、二甲基哌嗪、1，2-二甲基咪唑、1-氮杂双环[3.3.0]辛烷，并且优选1，4-二氮杂双环[2.2.2]辛烷；和烷醇胺化合物，例如三乙醇胺、三异丙醇胺、N-甲基二乙醇胺和N-乙基二乙醇胺，及二甲基乙醇胺。催化剂可单独使用或作为混合物使用。例如可以使用可从科思创聚合物(中国)有限公司获得的PU1748。
所述催化剂在本发明的多元醇体系的量为0-8重量份，优选0-5重量份，更优选0-3重量份，以所述多元醇体系的总重量为100重量份计。
所述脱模剂选自季戊四醇油酸酯等其他长链脂肪酸类物质，如油酸等例举可以使用的物质。
所述脱模剂在本发明的多元醇体系的量为0-15重量份，优选0-10重量份，更优选0-7重量份，以所述多元醇体系的总重量为100重量份计。
可以添加到本发明的多元醇体系中的其它添加剂如阻燃剂、色浆、填料、稳定剂、触变剂等可以聚氨酯领域中常用的量添加。
根据本发明的另一方面，提供一种聚氨酯体系，其包含异氰酸酯组分和多元醇组分，所述多元醇组分为上述的多元醇体系。
所述异氰酸酯组分具有1.2-3.0、优选1.5-3.0、特别优选2.0-2.8的官能度。
所述异氰酸酯组分选自(i)脂族异氰酸酯，例如六亚甲基二异氰酸酯；(ii)脂环族异氰酸酯，例如异佛尔酮二异氰酸酯、1，4-环己烷二异氰酸酯、1-甲基-2，4-环己烷二异氰酸酯、1-甲基-2，6-环己烷二异氰酸酯，4，4′-二环己基甲烷二异氰酸酯、2，4′-二环己基甲烷二异氰酸酯和2，2′-二环己基甲烷二异氰酸酯；和(iii)芳族异氰酸酯，例如2，4-甲苯二异氰酸酯、2，6-甲苯二异氰酸酯、4，4′-二苯甲烷二异氰酸酯、2，4′-二苯甲烷二异氰酸酯、2，2′-二苯甲烷二异氰酸酯和1，5-萘二异氰酸酯。
在本发明优选使用的异氰酸酯组分为芳族异氰酸酯。优选使用通式为R(NCO)z的芳香族异氰酸酯，其中R为具有一个芳香族体系的多价有机基团，并且z为一个至少为2的整数。所述芳族异氰酸酯的实例有：4，4’-二异氰酸基苯、1，3-二异氰酸基邻二甲苯、1，3-二异氰酸基对二甲苯、1，3-二异氰酸基间二甲苯、2，4-二异氰酸基-1-氯苯、2，4-二异氰酸基-1-硝基苯、2，5-二异氰酸基-1-硝基苯、间亚苯基二异氰酸酯、对亚苯基二异氰酸酯、2，4-甲苯二异氰酸酯、2，6-甲苯二异氰酸酯、由2，4-和2，6-甲苯二异氰酸酯形成的混合物、1，5-萘二异氰酸酯、1-甲氧基-2，4-亚苯基二异氰酸酯、4，4’-二苯基甲烷二异氰酸酯、2，4’-二苯基甲烷二异氰酸酯、4，4’-联苯基二异氰酸酯、3，3-二甲基-4，4’-二苯基甲烷二异氰酸酯，和3，3’-二甲基二苯基甲烷-4，4’-二异氰酸酯；三异氰酸酯，例如4，4’，4”-三苯基甲烷三异氰酸酯和2，4，6-甲苯三异氰酸酯；及四异氰酸酯，例如4，4’-二甲基-2，2’，5，5’-二苯基甲烷四异氰酸酯。特别优选甲苯二异氰酸酯、2，4’-二苯基甲烷二异氰酸酯、4，4’-二苯基甲烷二异氰酸酯、聚亚甲基聚亚苯基聚异氰酸酯，及其混合物。例如可从科思创聚合物(中国)有限公司获得的Desmodur 44V20。
以上的二异氰酸酯可单独或以彼此的混合物形式使用。
本领域技术人员可以根据所述多元醇体系中多元醇的量调节所述异氰酸酯组分的量。例如使得可与异氰酸酯反应的基团与异氰酸酯基团的当量比为1.1∶1至5.0∶1，优选为1.1∶1至3.0∶1。
当本发明的多元醇体系中不包含催化剂时，在制备本发明的聚氨酯体系时根据需要另外添加催化剂。
根据本发明的另一方面，提供一种聚氨酯产品，其包含使上述聚氨酯体系反应后获得反应产物。
可采用是本领域技术人员所熟知的方法制备聚氨酯，例如通过高压或低压机将多元醇体系与异氰酸酯组分混合后，加热固化形成聚氨酯产品。
在本说明中，所有表示数量、百分数、重量份、羟基值、官能度之类的数字在所有情况下都应理解为由术语“大约”加以修饰。
现在参考以下具体实施例中对本发明进行详细说明。然而，本领域技术人员不难理解，此处的实施例仅仅用于示例目的，本发明的范围并不局限于此。
实施例
实施例中所用原料说明如下：
M9158：聚醚多元醇，甘油起始，羟值为475mgKOH/g，从科思创公司购得；
NJ4502：聚醚多元醇，山梨醇起始，羟值为450mgKOH/g，从句容宁武新材料公司购得；
ED750：聚醚多元醇，乙二胺起始，羟值为750mgKOH/g，乙二胺起始，从国都公司购得；
DC380：聚醚多元醇，蔗糖起始，羟值为380mgKOH/g，从东昌公司购购得；
Desmophen 4050E：聚醚多元醇，乙二胺起始，羟值为630mgKOH/g，乙二胺起始，从科思创聚合物(中国)有限公司购得；
PU1748：改性胺类助剂，从科思创聚合物(中国)有限公司购得；
E100：3，5-二乙基甲苯二胺(DETDA)，从雅保化学公司购得；
B8411：硅油，从赢创公司购得；
B8870：硅油，从赢创公司购得；
Desmodur 44V20：多异氰酸酯，从科思创聚合物(中国)有限公司；
季戊四醇油酸酯：内脱模剂，从江苏海安石油化工厂购得。
Black Paste：黑色色浆，从Stahl购得。
以下实施例中，组分含量均以其重量份数计。
实施例1
按照表1中所示重量份数配制本发明的多元醇体系A1-A5：
表1：本发明的多元醇体系A1-A5
按照表2中所示重量份数配制本发明范围之外的的对照多元醇体系B1-B5：
表2：对照多元醇体系B1-B5
| B1 | B2 | B3 | B4 | B5 | |
| M9158 | 54 | 54 | 54 | 54 | 54 |
| NJ 4502 | 10 | 10 | 10 | 10 | 10 |
| ED 750 | 6 | 6 | 6 | 6 | 6 |
| BDO | 3 | 7 | 10 | 12 | 15 |
| E100 | 2 | 2 | 2 | 2 | 2 |
| PU 1748 | 10 | 10 | 10 | 10 | 10 |
| 季戊四醇油酸酯 | 4 | 4 | 4 | 4 | 4 |
| B8411 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 水 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
按照表3中所示重量份数配制本发明范围之外的的对照多元醇体系C1-C5：
表3：对照多元醇体系C1-C5
将所制得的多元醇体系A1-A5和对照多元醇体系B1-B5和C1-C5在室温和大气压下静置，观察相分离状态，并按照以下评价标准进行等级评定：
评价标准：
1：优，一个月以后还未分层；
2：一般：一周后分层
3：差：一周内分层。
等级评价结果如下：
表4：相分离状态等级
| 多元醇体系序号 | A1-A5 | B1-B5 | C1-C5 |
| 等级 | 1 | 3 | 3 |
从表4可以看出可见：使用甘油做扩链剂的多元醇体系A1-A5在一个月的储存时间内都保持不分层，而使用1，4丁二醇或者乙二醇作为扩链剂的对照多元醇体系B1-B5和C1-C5在放置一个星期内分层，即使在添加量很少的情况下也是如此。
实施例2
按照表5和表6所示重量份数配制本发明的聚氨酯体系D1-D4和不属于本发明的对照聚氨酯体系E1，通过留样观察发现D1-D4中的多元醇体系部分不分层。用一个高压喷涂系统将多元醇体系和异氰酸酯混合并喷涂到“夹层半成品”的上下两面的玻纤毡上，然后将该三明治结构放入具有90-140℃的压机中的模具内，加热固化成形后脱模取出夹层部件。
表5：聚氨酯体系D1和对照聚氨酯体系E1
表6：聚氨酯体系D2-D4
从表5和表6可以看出，本发明的聚氨酯体系D1-D4在固化形成聚氨酯产品可以实现120秒以下的快速脱模。在DETDA达到6重量份(聚氨酯体系D1)时，可实现60-70秒的快速脱模。
实施例3
将采用实施例2中对照聚氨酯体系E1和本发明的聚氨酯体系D1制备的夹层部件(备胎盖板)按照测试标准DIN EN/310进行测试，结果汇总于表7和表8：
表7：对照聚氨酯体系E1
| 样品序号 | 样品宽度b0 | 样品厚度a0 | EMod |
| mm | mm | N/mm2 | |
| 1-1 | 50.66 | 19.35 | 1434.89 |
| 1-2 | 51.36 | 19.32 | 1422.98 |
| 1-3 | 52.11 | 19.21 | 1475.36 |
| 1-4 | 48.94 | 19.19 | 1500.94 |
表8：本发明的聚氨酯体系D1
| 样品序号 | 样品宽度b0 | 样品厚度a0 | EMod |
| mm | mm | N/mm2 | |
| 2-1 | 51.27 | 19.45 | 1533.64 |
| 2-2 | 51.45 | 19.39 | 1471.14 |
| 2-3 | 52.57 | 19.25 | 1641.96 |
| 2-4 | 51.47 | 19.31 | 1597.41 |
从测试数据可以看出，采用本发明聚氨酯体系所获得的最终产品的物理性能比采用对照聚氨酯体系所获得的最终产品的物理性能弱好，都可以满足市场对夹层部件的需求。
采用本发明的聚氨酯体系获得的产品由于轻质、强度高，可以广泛用于汽车领域，如用于备胎盖板、天窗拉板等，满足汽车行业对轻质化、高强度的要求。
虽然已经展示和讨论了本发明的一些方面，但是本领域的技术人员应该意识到，可以在不背离本发明原理和精神的条件下对上述方面进行改变，因此本发明的范围将由权利要求以及等同的内容所限定。
Claims (12)
1.一种用于制备聚氨酯的多元醇体系，其特征在于，其包含：
i)至少一种具有至少两个可与异氰酸酯反应的基团的活性增链剂，其中至少一个可与异氰酸酯反应的基团为游离的伯-NH2基团；
ii)至少一种具有三个可与异氰酸酯反应的基团的活性增链剂，其中至少一个可与异氰酸酯反应的基团为游离的伯-OH的基团，和
iii)至少一种由胺起始的聚醚多元醇。
2.根据权利要求1所述的多元醇体系，其特征在于，所述多元醇体系还包含基础聚醚多元醇，其选自羟值为300～600mgKOH/g的聚醚多元醇。
3.根据权利要求1所述的多元醇体系，其特征在于，所述多元醇体系还包含选自以下的一种或多种添加剂：发泡剂、泡沫稳定剂、催化剂、脱模剂、阻燃剂、色浆、填料、稳定剂和触变剂。
4.根据权利要求1-3中任一项所述的多元醇体系，其特征在于，所述至少一种具有至少两个可与异氰酸酯反应的基团的活性增链剂选自具有2-12个碳原子的链烷醇胺、具有2-15个碳原子的脂(环)族二胺和具有6-12个碳原子的芳族二胺，所述链烷醇胺、脂(环)族二胺和芳族二胺中与碳原子相连的一个或更多个氢原子任选被包含1-6个碳原子的烷基取代。
5.根据权利要求1-3中任一项所述的多元醇体系，其特征在于，所述至少一种具有三个可与异氰酸酯反应的基团的活性增链剂选自具有3-8个碳原子的三元醇。
6.根据权利要求1-3中任一项所述的多元醇体系，其特征在于，所述由胺起始的聚醚多元醇选自由乙二胺起始的羟值为450KOH/g至800KOH/g的聚醚多元醇。
7.根据权利要求1-3中任一项所述的多元醇体系，其特征在于，所述至少一种具有至少两个可与异氰酸酯反应的基团的活性增链剂在所述多元醇体系中的量为1-25重量份，优选2-15重量份，更优选2-10重量份，最优选2-6重量份，以所述多元醇体系的总重量为100重量份计。
8.根据权利要求1-3中任一项所述的多元醇体系，其特征在于，所述至少一种具有三个可与异氰酸酯反应的基团的活性增链剂在所述多元醇体系中的量为1-20重量份，优选2-15重量份，更优选3-15重量份，以所述多元醇体系的总重量为100重量份计。
9.根据权利要求1-3中任一项所述的多元醇体系，其特征在于，所述由胺起始的聚醚多元醇在所述多元醇体系中的量为1-10重量份，优选2-8重量份，更优选2-6重量份，以所述多元醇体系的总重量为100重量份计。
10.一种聚氨酯体系，其包含异氰酸酯组分和多元醇组分，其特征在于，所述多元醇组分为根据权利要求1-9中任一项所述的多元醇体系。
11.根据权利要求10所述的聚氨酯体系，其特征在于，所述异氰酸酯组分选自：(i)脂族异氰酸酯，(ii)环脂族异氰酸酯，(iii)芳族异氰酸酯，或其混合物。
12.一种聚氨酯产品，其特征在于，其包含使权利要求10或11所述的聚氨酯体系反应后获得的反应产物。
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| CN101503566A (zh) * | 2008-02-06 | 2009-08-12 | 赢创戈尔德施米特有限公司 | 用于改善多元醇混合物存储稳定性的新型相容剂 |
| WO2011085775A1 (de) * | 2009-12-22 | 2011-07-21 | Byk-Chemie Gmbh | Zusammensetzung umfassend stabile polyolmischungen |
| CN102369228A (zh) * | 2009-04-01 | 2012-03-07 | 陶氏环球技术有限责任公司 | 用于制备硬质多异氰脲酸酯泡沫体的储存稳定的多元醇组合物 |
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| US5208269A (en) * | 1992-07-16 | 1993-05-04 | Basf Corporation | Low-density RRIM using mineral fiber filler |
| US5302303A (en) * | 1993-08-24 | 1994-04-12 | Miles Inc. | Storage stable isocyanate-reactive compositions for use in flame-retardent systems |
| ITMI20101380A1 (it) * | 2010-07-27 | 2012-01-28 | Dow Global Technologies Inc | Pannello composito poliuretanico a basso impatto ambientale |
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2016
- 2016-12-28 CN CN201611272597.0A patent/CN108250391B/zh not_active Expired - Fee Related
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2017
- 2017-12-22 EP EP17821928.3A patent/EP3562855A1/en not_active Withdrawn
- 2017-12-22 US US16/466,221 patent/US11186670B2/en active Active
- 2017-12-22 WO PCT/EP2017/084288 patent/WO2018122144A1/en unknown
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| EP0125677A2 (en) * | 1983-05-16 | 1984-11-21 | Mobay Corporation | Novel polyols for the production of rigid polyurethane foams |
| EP0268906A2 (en) * | 1986-11-26 | 1988-06-01 | The Dow Chemical Company | Compatibilized blends of alpha, omega-alkylene glycols and polyether polyols and process for preparing the same |
| US5614575A (en) * | 1995-04-24 | 1997-03-25 | Rpg. Inc. | Sprayable polyurethane compositions |
| US5750583A (en) * | 1997-05-28 | 1998-05-12 | Bayer Corporation | Process for the production of molded polyurethane products |
| CN101321795A (zh) * | 2005-12-15 | 2008-12-10 | 拜尔材料科学有限公司 | 基于异佛尔酮二异氰酸酯的异氰脲酸酯及其预聚物的rim弹性体 |
| CN101503566A (zh) * | 2008-02-06 | 2009-08-12 | 赢创戈尔德施米特有限公司 | 用于改善多元醇混合物存储稳定性的新型相容剂 |
| CN102369228A (zh) * | 2009-04-01 | 2012-03-07 | 陶氏环球技术有限责任公司 | 用于制备硬质多异氰脲酸酯泡沫体的储存稳定的多元醇组合物 |
| WO2011085775A1 (de) * | 2009-12-22 | 2011-07-21 | Byk-Chemie Gmbh | Zusammensetzung umfassend stabile polyolmischungen |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903457A (zh) * | 2019-12-12 | 2020-03-24 | 山东一诺威聚氨酯股份有限公司 | 一种用于制作快速脱模耐高温透明模特材料的聚氨酯弹性体及其制备方法 |
| WO2021114664A1 (zh) * | 2019-12-12 | 2021-06-17 | 山东一诺威聚氨酯股份有限公司 | 一种用于制作快速脱模耐高温透明模特材料的聚氨酯弹性体及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018122144A1 (en) | 2018-07-05 |
| EP3562855A1 (en) | 2019-11-06 |
| US11186670B2 (en) | 2021-11-30 |
| CN108250391B (zh) | 2021-10-22 |
| US20200062886A1 (en) | 2020-02-27 |
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