CN102223953B - 用于异氰酸酯和醇之间的反应的新的催化剂 - Google Patents
用于异氰酸酯和醇之间的反应的新的催化剂 Download PDFInfo
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- CN102223953B CN102223953B CN200980146920.1A CN200980146920A CN102223953B CN 102223953 B CN102223953 B CN 102223953B CN 200980146920 A CN200980146920 A CN 200980146920A CN 102223953 B CN102223953 B CN 102223953B
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- 101000879121 Pyrococcus furiosus (strain ATCC 43587 / DSM 3638 / JCM 8422 / Vc1) Sulfide dehydrogenase subunit alpha Proteins 0.000 description 1
- 101000879118 Pyrococcus furiosus (strain ATCC 43587 / DSM 3638 / JCM 8422 / Vc1) Sulfide dehydrogenase subunit beta Proteins 0.000 description 1
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- 150000004696 coordination complex Chemical class 0.000 description 1
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- 150000004985 diamines Chemical class 0.000 description 1
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- 229910000071 diazene Inorganic materials 0.000 description 1
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
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- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 125000001518 isoselenocyanato group Chemical group *N=C=[Se] 0.000 description 1
- 238000012933 kinetic analysis Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
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- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
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- 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
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
本发明涉及用于异氰酸酯和醇之间的反应的新的催化剂,该反应是用于制备聚氨酯聚合物的关键步骤。本发明更具体地涉及非基于锡的新的催化剂的用途。
Description
技术领域
本发明涉及用于异氰酸酯和醇之间的反应的新的催化剂,该反应是用于制备聚氨酯聚合物的关键步骤。本发明更具体地涉及非基于锡的新的催化剂的用途。
背景技术
聚氨酯最初用于塑料化合物和泡沫的制造中。此后,这些聚合物已开发于很多应用领域中,例如弹性体、热塑性塑料、热固性树脂、膨胀体系,织物纤维和涂料体系(用于纸的涂料浴、木材涂料、机动车油漆、粘合剂等)。
聚氨酯是包含至少一个尿烷(也称为氨基甲酸酯)基团的聚合物。该基团来自于醇基团和异氰酸酯基团之间的反应。
通常,通过异氰酸酯与伯醇或仲醇之间的未催化反应合成聚氨酯在50至100℃之间进行。已提出了多种催化剂以优化该反应,例如路易斯酸和碱,以及多种金属盐。这些催化剂的实例记载于下列文章中:
-Gambiroza-Jukic et al.,Kinetic analysis of bulkpolymerization of diisocyanate and polyol;J.Appl.Polym.Sci.,1993,第47卷,第513-519页,
-Wong et al.,Catalysis in competing isocyanate reactions,Competing phenyl isocyanate reaction catalyzed with N,N’,N”-五甲基二亚丙基三胺;J.Polym.Sci.;A部分,Polym.Chem.Ed.,1986,第24卷,第2877-2890页,以及
-Okada,H.et al.,The kinetics of the polyurethane-formingreaction between organic diisocyanates and glycols;Makromol.Chem.,1963,第66卷,第91-101页。
最广泛使用的金属催化剂是烷基锡羧酸酯,其中最为人所知的是二丁基锡二月桂酸酯。然而,基于烷基锡的催化剂虽然非常有效,但是存在具有毒性的缺点(CMR-2:生殖毒性)。
因此,正在进行研究来在多种应用中将其用不具有这些缺点的化合物代替。此外,工业上一直在寻找具有至少和二丁基锡二月桂酸酯一样的活性但是不基于锡的化合物。
发明内容
本发明的主要目标因此是提供用于异氰酸酯和醇之间的反应的催化剂,该催化剂具有至少和二丁基锡二月桂酸酯一样的活性但是不基于锡。
本发明的另一个主要目标是提供可以用于聚氨酯的合成的催化剂。
现已发现,并且构成本发明的主题的是,用于制备具有至少一个尿烷官能团的化合物A的新方法,其包含步骤1),该步骤在于使具有至少一个异氰酸酯官能团的化合物B与具有至少一个羟基官能团的化合物D在催化有效量的至少一种催化剂C的存在下反应,其特征在于所述催化剂C是下式(1)的金属盐或配合物:
[Zn(L1)l1(L2)l2(Y)x](1)
其中:
-l1≥1并且l2=0或1;其中l1+l2=2,x=0、1或2,
-符号L1代表配体,它是β-二羰基阴离子(anion β-dicarbonylato)或者β-二羰基化化合物的烯醇盐阴离子或者衍生自β-酮酯的乙酰乙酸酯根阴离子,
-当l1=2时,符号L1可以是相同或不同的,
-符号L2代表不同于L1的阴离子配体,
-符号Y代表中性配体,并且
-附加条件是式(1)的金属盐或配合物C不是二乙酰丙酮锌化合物或者[Zn(acac)2]。
中性配体Y的种类不重要,本领域技术人员将使用适合于锌的任何类型的中性配体以遵守锌的化合价。作为实例可以提及胺、二胺等。
根据一种优选的变化方案,所述催化剂C是下式(1)的金属盐或配合物:
[Zn(L1)l1(L2)l2](1)
其中:
-l1≥1并且l2=0或1;其中l1+l2=2,
-符号L1代表配体,它是β-二羰基阴离子或者β-二羰基化化合物的烯醇盐阴离子或者衍生自β-酮酯的乙酰乙酸酯根阴离子,
-当l1=2时,符号L1可以是相同或不同的,
-符号L2代表不同于L1的阴离子配体,并且
-附加条件是式(1)的金属盐或配合物C不是二乙酰丙酮锌化合物或者Zn(acac)2。
为了实现该目标,发明人已完全令人惊讶且出人意料地发现,式(1)的基于锌的金属盐或配合物的使用使得可以催化异氰酸酯和醇之间的反应,该反应是用于制备聚氨酯聚合物的关键步骤。
应当注意,本发明的独创性的至少一部分是由于根据本发明用作催化剂的金属化合物C的规定组合的明智且有利的选择。
根据本发明的一种优选实施方案,上述式(1)的符号L1是衍生自下式(2)的β-二酮的β-二酮根阴离子:
R1COCHR2COR3(2)
其中:
-基团R1和R3,相同或不同,各自代表C1-C30的取代或未取代的线性或支化烃基,
-基团R2为氢或者烃基,优选C1-C4烷基;并且
-基团R1和R2可以连接以使得β-二酮形成环。
根据本发明的另一种优选实施方案,β-二羰基配体L1是选自下列化合物的衍生物阴离子的β-酮酯根阴离子:乙酰乙酸的甲酯、乙酯、正丙酯、异丙酯、正丁酯、仲丁酯、异丁酯、叔丁酯、异戊酯、正己酯、正辛酯、1-甲基庚酯、正壬酯、正癸酯和正十二烷基酯,或者专利申请FR-A-1435882中记载的那些。
本发明还涉及用于制备具有至少一个尿烷官能团的化合物A的方法,其包含步骤1),该步骤在于使具有至少一个异氰酸酯官能团的化合物B与具有至少一个羟基官能团的化合物D在催化有效量的至少一种催化剂C的存在下反应,其特征在于所述催化剂C是下式(1)的金属盐或配合物:
[Zn(L1)l1(L2)l2(Y)x](1)
其中:
-l1≥1并且l2=0或1;其中l1+l2=2,x=0、1或2,
-符号L2代表不同于L1的阴离子配体,
-符号Y代表中性配体,并且
-符号L1是衍生自式R1COCHR2COR3(2)的β-二酮的β-二酮根阴离子,并且所述β-二酮选自以下的β-二酮:2,4-己烷二酮;2,4-庚烷二酮;3,5-庚烷二酮;3-乙基-2,4-戊烷二酮;5-甲基-2,4-己烷二酮;2,4-辛烷二酮;3,5-辛烷二酮;5,5-二甲基-2,4-己烷二酮;6-甲基-2,4-庚烷二酮;2,2-二甲基-3,5-壬烷二酮;2,6-二甲基-3,5-庚烷二酮;2-乙酰基环己酮(Cy-acac);2,2,6,6-四甲基-3,5-庚烷二酮(t-Bu-acac);2,2,7-三甲基-3,5-辛烷二酮;1,1,1,5,5,5-六氟-2,4-戊烷二酮(F-acac)];苯甲酰丙酮;二苯甲酰甲烷;3-甲基-2,4-戊二酮;3-乙酰基-戊烷-2-酮;3-乙酰基-2-己酮;3-乙酰基-2-庚酮;3-乙酰基-5-甲基-2-己酮;硬脂酰苯甲酰甲烷;辛酰苯甲酰甲烷;4-叔丁基-4’-甲氧基-二苯甲酰甲烷;4,4’-二甲氧基-二苯甲酰甲烷;4,4’-二叔丁基-二苯甲酰甲烷和2,4-十一烷二酮。
根据一种优选的实施方案,所述催化剂C是下式(1)的金属盐或配合物:
[Zn(L1)l1(L2)l2](1)
其中:
-l1≥1并且l2=0或1;其中l1+l2=2,
-符号L1是衍生自式R1COCHR2COR3(2)的β-二酮的β-二酮根阴离子,并且所述β-二酮选自以下的β-二酮:2,4-己烷二酮;2,4-庚烷二酮;3,5-庚烷二酮;3-乙基-2,4-戊烷二酮;5-甲基-2,4-己烷二酮;2,4-辛烷二酮;3,5-辛烷二酮;5,5-二甲基-2,4-己烷二酮;6-甲基-2,4-庚烷二酮;2,2-二甲基-3,5-壬烷二酮;2,6-二甲基-3,5-庚烷二酮;2-乙酰基环己酮(Cy-acac);2,2,6,6-四甲基-3,5-庚烷二酮(t-Bu-acac);2,2,7-三甲基-3,5-辛烷二酮;1,1,1,5,5,5-六氟-2,4-戊烷二酮(F-acac)];苯甲酰丙酮;二苯甲酰甲烷;3-甲基-2,4-戊二酮;3-乙酰基-戊烷-2-酮;3-乙酰基-2-己酮;3-乙酰基-2-庚酮;3-乙酰基-5-甲基-2-己酮;硬脂酰苯甲酰甲烷;辛酰苯甲酰甲烷;4-叔丁基-4’-甲氧基-二苯甲酰甲烷;4,4’-二甲氧基-二苯甲酰甲烷;4,4’-二叔丁基-二苯甲酰甲烷和2,4-十一烷二酮。
为了更详细地说明构成根据本发明的式(1)金属盐或金属配合物的元素的种类,重要的是指出L2是可以选自以下阴离子的阴离子配体:氟根(F-)、氯根(Cl-)、三碘根(l-)(I3)-,二氟氯酸根(l-)[ClF2]-、六氟碘酸根(l-)[IF6]-、氧氯酸根(l-)(ClO)-、二氧氯酸根(l-)(ClO2)-、三氧氯酸根(l-)(ClO3)-、四氧氯酸根(l-)(ClO4)-、氢氧根(OH)-、硫氢根(SH)-、硒氢根(SeH)-、过氧根(O2)-、臭氧根(O3)-、氢氧根(OH)-、氢二硫根(HS2)-、甲氧根(CH3O)-、乙氧根(C2H5O)-、丙氧根(C3H7O)-、甲硫根(CH3S)-、乙硫根(C2H5S)-、2-氯乙氧根(C2H4ClO)-、苯氧根(C6H5O)-、苯硫根(C6H5S)-、4-硝基苯氧根[C6H4(NO2)O]-、甲酸根(HCO2)-、乙酸根(CH3CO2)-、丙酸根(CH3CH2CO2)-、叠氮根(N3)-、氰根(CN)-、氰酸根(NCO)-、硫氰酸根(NCS)-、硒氰酸根(NCSe)-、氨根(NH2)-、膦根(PH2)-、氯氨根(ClHN)-、二氯氨根(Cl2N)-、[甲氨根(l-)](CH3NH)-、二亚胺根(HN=N)-、联氨根(H2N-NH)-、二磷烯根(HP=P)-、亚膦酸根(H2PO)-、亚磷酸根(H2PO2)-、羧酸根、烯醇根和氨基化物(amidures)、烷基根(alkylato)和芳基根(arylato)。
根据一种特别优选的实施方式,L2是选自以下阴离子的阴离子配体:乙酸根、草酸根、丙酸根、丁酸根、异丁酸根、二乙基乙酸根、苯甲酸根、2-乙基己酸根、硬脂酸根、甲氧根、乙氧根、异丙氧根、叔丁氧根、叔戊氧根、8-羟基喹啉根、环烷酸根、芳庚酚酸根(tropolonate)和氧阴离子O2-。
根据另一种优选实施方案,催化剂C是选自下式(3)至(9)的化合物的金属盐或配合物:
(3):[Zn(t-Bu-acac)2],其中(t-Bu-acac)=2,2,6,6-四甲基-3,5-庚烷二酮根阴离子或者2,2,6,6-四甲基-3,5-庚烷二酮的烯醇盐阴离子,
(4):[Zn(EAA)2],其中EAA=乙酰乙酸乙酯根阴离子或者乙酰乙酸乙酯的烯醇盐阴离子,
(5):[Zn(iPr-AA)2],其中iPr-AA=乙酰乙酸异丙酯根阴离子或者乙酰乙酸异丙酯的烯醇盐阴离子,以及
(6):[Zn(TMOD)2],其中(TMOD)=2,2,7-三甲基-3,5-辛烷二酮根阴离子或者2,2,7-三甲基-3,5-辛烷二酮的烯醇盐阴离子,
(7):[Zn(UDD)2],其中(UDD)=2,4-十一烷二酮根阴离子或者2,4-十一烷二酮的烯醇盐阴离子,
(8):[Zn(TMOD)2(N,N’-二甲基乙二胺)],其中(TMOD)=2,2,7-三甲基-3,5-辛烷二酮根阴离子或者2,2,7-三甲基-3,5-辛烷二酮的烯醇盐阴离子,以及
(9):[Zn(TMOD)2(N-丙基乙二胺)],其中(TMOD)=2,2,7-三甲基-3,5-辛烷二酮根阴离子或者2,2,7-三甲基-3,5-辛烷二酮的烯醇盐阴离子。
有利地确定催化剂的量以使得Zn/异氰酸酯官能团的摩尔比(Zn/NCO)在1/1000和1/50000之间,优选在1/5000和1/30000之间,并且更优选在1/8000和1/20000之间。
根据一种优选实施方案,根据本发明的方法特别适合用于聚氨酯聚合物的制备。因此,根据本发明的一种优选的变化方案,具有至少一个尿烷官能团的化合物A是聚氨酯,具有至少一个异氰酸酯官能团的化合物B是二异氰酸酯,并且具有至少一个羟基官能团的化合物D是多元醇。
根据另一种优选实施方案,根据本发明的方法的特征在于,步骤1)在于在不存在水分且存在有效量的上述根据本发明的催化剂C的情况下使至少一种化合物B与至少一种化合物D反应,所述化合物B是选自单异氰酸酯、二异氰酸酯、多异氰酸酯及其混合物的异氰酸酯,所述化合物D是选自单醇、二醇、多元醇及其混合物的醇。
作为根据本发明使用并具有至少一个异氰酸酯官能团的化合物B的示例,可以提及芳族、饱和环状或脂族的本领域技术人员所公知的单异氰酸酯、二异氰酸酯或多异氰酸酯,以及这些化合物的混合物。
根据在化学中的标准用法,当将官能团的名称给与一类化合物时(换言之,当官能团与一类产物同名时,如在异氰酸酯的情况下),芳族或脂族性质根据所考虑的官能团的连接点进行定义。
当异氰酸酯位于脂族性质的碳上时,那么认为该异氰酸酯化合物本身是脂族性质的。类似地,当异氰酸酯官能团通过芳族性质的碳连接到骨架上时,那么整个单体将用芳族异氰酸酯的称谓表示。因此:
-氮的连接点是芳环成员的任何异氰酸酯官能团被认为是“芳族”的;并且
-氮的连接点是sp3杂化碳的任何异氰酸酯官能团被认为是“脂族”的。
作为芳族异氰酸酯的实例,可以提及二苯基甲烷二异氰酸酯(MDI)、特别是二苯基甲烷-4,4’-二异氰酸酯、二苯基甲烷-2,4’-二异氰酸酯,甲苯二异氰酸酯(TDI),特别是甲苯-2,4-二异氰酸酯和甲苯-2,6-二异氰酸酯。
作为脂族异氰酸酯的实例,可以提及六亚甲基二异氰酸酯(HMDI)、1,3-四甲基亚二甲苯基二异氰酸酯、异佛尔酮二异氰酸酯和二环六甲基甲烷(dicyclohexaméthylméthane)二异氰酸酯。
作为环脂族异氰酸酯的实例,可以提及异佛尔酮二异氰酸酯(IPDI)。
因而,对于线性聚氨酯聚合物的制备,可以常规地使二异氰酸酯与二醇反应。涉及的反应可以根据多种替代形式进行:必须包括不同类型(异氰酸酯/醇)的至少两种反应物,这些反应物可以是单官能或双官能的。
作为具有至少一个羟基官能团的化合物D的实例,并且不希望限于此,可以提及多元醇例如甘油、聚甘油,二醇,丙二醇,包含2至10个碳原子、优选2至6个碳原子的二醇,例如乙二醇、二乙二醇、1,4-丁烷二醇、1,5-戊烷二醇、1,6-己烷二醇、1,10-癸烷二醇、1,3-丙烷二醇、二丙醇醚、聚乙二醇、聚丙二醇、新戊二醇、季戊四醇、新戊二醇羟基新戊酸酯、双季戊四醇酯、三羟甲基丙烷、2-丁基-2-乙基-1,3-丙烷二醇、山梨醇、甘露醇、木糖醇和中赤藓糖醇。也可以使用这些二醇的酯或者聚酯多元醇以及聚醚多元醇。
以已知的方式,聚酯多元醇通常选自脂族和芳族聚酯多元醇以及这些化合物的混合物。
作为实例,可以提及由脂族、环状或芳族多元醇与二羧酸的缩合得到的聚酯多元醇,所述多元醇例如为1,2-乙烷二醇、1,2-丙烷二醇、1,3-丙烷二醇、甘油、三羟甲基丙烷、1,6-己烷二醇、1,2,6-己烷三醇、丁烷二醇、蔗糖、葡萄糖、山梨醇、季戊四醇、甘露醇、三乙醇胺、N-甲基-二乙醇胺以及这些化合物的混合物,所述二羧酸例如为1,6-己烷二酸、十二烷二酸、壬二酸、癸二酸、己二酸、1,18-十八烷二酸、邻苯二甲酸、琥珀酸以及这些二酸的混合物,不饱和酸酐例如马来酸酐或邻苯二甲酸酐,或者内酯的均聚物例如ε-己内酯。
聚酯多元醇通常通过在二官能或多官能醇与二羧酸或羧酸酐的聚酯化中使用过量的二官能或多官能醇而获得。
聚醚多元醇通常通过环状单体例如环氧乙烷、环氧丙烷或四氢呋喃的阴离子或阳离子加聚而获得。
在聚氨酯的合成中使用的聚醚多元醇的摩尔质量通常在250至8000之间变化。它们的官能度可以从2到7变化,这取决于用作引发剂的分子的性质。这些聚醚二元醇的端基可以是一级的或二级的。
根据另一种优选的实施方案,根据本发明的方法的特征在于步骤1)在发泡剂的存在下进行。
多种发泡剂是现有技术中公知的,并且它们根据最终产物(该产物为聚氨酯泡沫)中期望的泡孔尺寸以不同的量使用。这些发泡剂中最经济的是水,但是经常单独地或者与水混合地使用带有氯和/或氟的卤化短链烷烃。发泡剂经常以最高达多元醇的50重量%的量使用。
本发明还涉及式(7)至(9)的新的化合物:
(7):[Zn(UDD)2],其中(UDD)=2,4-十一烷二酮根阴离子或者2,4-十一烷二酮的烯醇盐阴离子,
(8):[Zn(TMOD)2(N,N’-二甲基乙二胺)],其中(TMOD)=2,2,7-三甲基-3,5-辛烷二酮根阴离子或者2,2,7-三甲基-3,5-辛烷二酮的烯醇盐阴离子,以及
(9):[Zn(TMOD)2(N-丙基乙二胺)],其中(TMOD)=2,2,7-三甲基-3,5-辛烷二酮根阴离子或者2,2,7-三甲基-3,5-辛烷二酮的烯醇盐阴离子。
当然,本领域技术人员可以向刚刚仅以非限制性实例的方式说明的方法中引入多种修改而不偏离本发明的范围。
通过阅读以下实施例,本发明的其它优点和特征将变得显而易见,这些实施例以示例的方式给出而不表示限制。
具体实施方式
实施例
1-根据本发明的催化剂
-催化剂(5):[Zn(乙酰乙酸异丙酯根)2]或[Zn(iPr-AA)2],其中iPr-AA=乙酰乙酸异丙酯根阴离子或者乙酰乙酸异丙酯的烯醇盐阴离子
将97%的100mmol甲醇钠(6.12g)在100ml异丙醇中的溶液通过蒸馏浓缩20%,然后加入95%的100mmol乙酰乙酸异丙酯(15.93g),并将溶液在80℃下加热1小时,获得橙色的均匀溶液。然后在70℃下在1小时内加入氯化锌(50mmol,7g)在50ml异丙醇中的溶液。在80和90℃之间保持加热3小时30分钟,然后在冷却后将形成的氯化钠过滤。将醇溶液蒸发至干,得到25.3g糊状物,将其溶解于200ml乙醇中。在热过滤并蒸发至干后,获得17.2g白色固体(产率98%)。
Zn计算值:18.59重量%,测定值(ICP):18.57重量%
IR(nm):2989,1617,1514,1246,1170。
-催化剂(6):[Zn(TMOD)2],其中(TMOD)=2,2,7-三甲基-3,5-辛烷二酮根阴离子或者2,2,7-三甲基-3,5-辛烷二酮的烯醇盐阴离子
将0.21mol 95%的2,2,7-三甲基-3,5-辛烷二酮在20℃下在1小时内加入0.21mol氢氧化钾在88g乙醇中的溶液中。然后在1小时内向该均匀溶液中加入0.105mol无水氯化锌在16g乙醇中的溶液。将混合物在30℃下搅拌3小时,然后加入23g庚烷并将悬浮液冷却至6℃,然后过滤。将固体用100g庚烷润洗,并将滤液在4mbar下蒸发直到90℃,得到46g浓稠蜂蜜状的双(2,2,7-三甲基-3,5-辛烷二酮)锌。
Zn计算值:15.14重量%,Zn测定值:14.50重量%
IR(nm):2953,1574,1509,1410,1162。
-催化剂(7):[Zn(UDD)2],其中(UDD)=2,4-十一烷二酮根阴离子或者2,4-十一烷二酮的烯醇盐阴离子
将30mmol 2,4-十一烷二酮加入30mmol甲醇钠在10g乙醇中的70℃溶液中,然后在1小时后加入15mmol无水氯化锌在2.5g乙醇中的溶液。将混合物在70℃搅拌3小时,然后加入20g庚烷并将悬浮液冷却至6℃,然后过滤。将固体用20g庚烷润洗,并将滤液在4mbar下蒸发直到90℃,得到6.2g低粘度浅黄色液体形式的双(2,4-十一烷二酮)锌。
Zn计算值:15.14重量%,Zn测定值:15.74重量%
IR(nm):2992,1575,1511,1389,1015,774。
以及Zn(TMOD)2与乙二胺衍生物的2种配合物:
-[Zn(TMOD)2(N,N’-二甲基乙二胺)](8),根据以下方式制备:
将1摩尔当量的N,N’-二甲基乙二胺(例如10mmol=0.9g)在5分钟内加入1摩尔当量Zn(TMOD)2(例如10mmol=4.4g)在二异丙基醚(例如30ml)中的溶液中。在30分钟后,将澄清的溶液蒸发以得到粘稠的油状物,其对应于期望的配合物(例如10mmol=5.2g,100%)。
1H NMR(C6D14):5.23(s,2H),2.77(s,4H),2.41(s,6H),2.04(m,2H),1.94(d,4H),1.08(s,18H),0.94(d,12H)。
-[Zn(TMOD)2(N-丙基乙二胺)](9),根据以下方式制备:
将1摩尔当量的N-丙基乙二胺(例如10mmol=1.02g)在5分钟内加入1摩尔当量Zn(TMOD)2(例如10mmol=4.4g)在二异丙基醚(例如30ml)中的溶液中。在30分钟后,将混浊的溶液蒸发以得到白色固体,其对应于期望的配合物(例如10mmol=5.4g,100%)。
1H NMR(C6D14):5.23(s,2H),2.86(m,2H),2.74(m,2H),2.62(t,2H),2.03(m,2H),1.93(d,4H),1.56(sext,2H),1.07(s,18H),0.92(d,12H),0.86(t,3H),以及
-催化剂(3):[Zn(t-Bu-acac)2],其中(t-Bu-acac)=2,2,6,6-四甲基-3,5-庚烷二酮根阴离子或者2,2,6,6-四甲基-3,5-庚烷二酮的烯醇盐阴离子,CAS 14363-14-5,由Sigma-Aldrich公司提供,MW=431.9g/mol,加热后乙酸丁酯或乙酸乙酯中的30%溶液的形式。
2-操作条件:
2.1第一系列试验
制备由2,4-TDI(2,4-二异氰酸根合-1-甲基苯)和质量为2000g/mol的聚丙二醇组成的配制剂,其中OH/NCO摩尔比等于0.5。将催化剂加入该配制剂中。在60℃下在氮气保护下在夹套反应器中进行试验。
为了能够与对比催化剂(锡催化剂,二丁基锡二月桂酸酯或DBTL)形成比较,使用等当量的金属进行操作。因而以Zn/NCO摩尔比=0.008%使用催化剂(3)。
通过根据标准AFNOR NF T 52-132(1988年9月)(有时也称为二丁基胺方法)以通常方式定量测定-N=C-O(NCO)官能团而进行动力学监视。该定量测定的原理基于异氰酸酯基团与过量的二(正丁基)胺的反应。将该胺引入甲苯溶液中(1N)。反应时间为在环境温度下15分钟。然后通过用盐酸(1N)滴定定量测定过量的二(正丁基)胺。将溴甲酚绿用作指示剂。
由于在1小时30分钟后达到50%的异氰酸酯官能团-N=C=O转化率,注意到催化剂(3)的效果。
在40分钟后达到50%的对照催化剂(对照1=二丁基锡二月桂酸酯或DBTL)转化率。
在不存在催化剂的情况下进行第三测试(对比2),在此为了达到相同的50%转化率,需要等待6小时的反应。
获得的分子量分布以及使用凝胶渗透色谱或GPC(折射计(RI)和UV)的双重检测使得可以确认根据本发明的催化剂的效果。
该结果是令人满意的,并且表现了根据本发明的不含锡的催化剂的可行性。此外,由于使用根据本发明的催化剂的聚氨酯聚合物形成动力学略微较慢,这具有为聚氨酯聚合物的形成阶段提供更多的时间的优点。
2.2第二系列试验
制备了由六亚甲基二异氰酸酯预聚物组成的配制剂,其中0.522molNCO/100g。将25g二甲苯中的10g该聚合物(预先制备的溶液的形式)加入反应器中,然后加入6.8g 2-乙基己醇(1mol OH/mol NCO)。
加热,当反应介质温度达到40℃时,加入:
-二甲苯5g,用于未催化反应,
-或者选择的催化剂在二甲苯中的溶液5g,
其对应于反应的t=0(秒表的开始)。
测试了根据本发明的多种催化剂:
-[Zn(TMOD)2],其中(TMOD)=2,2,7-三甲基-3,5-辛烷二酮根阴离子或者2,2,7-三甲基-3,5-辛烷二酮的烯醇盐阴离子,(6)
-[Zn(UDD)2],其中(UDD)=2,4-十一烷二酮根阴离子或者2,4-十一烷二酮的烯醇盐阴离子,(7)
以及Zn(TMOD)2与乙二胺衍生物的2种配合物:
-[Zn(TMOD)2(N,N’-二甲基乙二胺)](8),
-[Zn(TMOD)2(N-丙基乙二胺)](9)。
作为比较,还测试了两种基于锡的催化剂:
-二丁基锡二月桂酸酯(DLDBE),
-二辛基锡二月桂酸酯(DLDOE),以及
-[Zn(acac)2]或者二乙酰丙酮锌。
将新的催化剂的活性与二丁基锡二月桂酸酯进行比较。在下表中,一当量的二丁基锡二月桂酸酯对应于1.58×10-5mol锡每10g六亚甲基二异氰酸酯预聚物。通过在t=10分钟时异氰酸酯官能团的转化率评价催化能力。通过红外分析监视异氰酸酯官能团的消失。
使用的催化剂的量以及获得的结果详细记载于下表中:
表1
根据本发明的催化剂使得可以在反应10分钟后获得异氰酸酯官能团的良好转化率。它们表现出比[Zn(acac)2]大22%(对于[Zn(TMOD)2])至46%(对于[Zn(TMOD)2(N,N’-二甲基乙二胺)])的活性。
对于异氰酸酯和醇之间的反应,根据本发明的催化剂因而构成对基于锡的催化剂的有效替代。
Claims (13)
1.用于制备具有至少一个尿烷官能团的化合物A的方法,其包含步骤1),该步骤在于使具有至少一个异氰酸酯官能团的化合物B与具有至少一个羟基官能团的化合物D在催化有效量的至少一种催化剂C的存在下反应,其特征在于所述催化剂C是下式(1)的金属盐或配合物:
[Zn(L1)l1(L2)l2(Y)x](1)
其中:
-l1≥1并且l2=0或1;其中l1+l2=2,x=1或2,
-符号L1代表配体,它是β-二羰基阴离子或者β-二羰基化化合物的烯醇盐阴离子或者衍生自β-酮酯的乙酰乙酸酯根阴离子,
-当l1=2时,符号L1可以是相同或不同的,
-符号L2代表不同于L1的阴离子配体,
-符号Y代表中性配体,并且
-附加条件是式(1)的金属盐或配合物C不是二乙酰丙酮锌化合物或者[Zn(acac)2]。
2.用于制备具有至少一个尿烷官能团的化合物A的方法,其包含步骤1),该步骤在于使具有至少一个异氰酸酯官能团的化合物B与具有至少一个羟基官能团的化合物D在催化有效量的至少一种催化剂C的存在下反应,其特征在于所述催化剂C是下式(1)的金属盐或配合物:
[Zn(L1)l1(L2)l2(Y)x](1)
其中:
-l1≥1并且l2=0或1;其中l1+l2=2,x=1或2,
-符号L2代表不同于L1的阴离子配体,
-符号Y代表中性配体,并且
-符号L1是衍生自式R1COCHR2COR3(2)的β-二酮的β-二酮根阴离子,并且所述β-二酮选自以下的β-二酮:2,4-己烷二酮;2,4-庚烷二酮;3,5-庚烷二酮;3-乙基-2,4-戊烷二酮;5-甲基-2,4-己烷二酮;2,4-辛烷二酮;3,5-辛烷二酮;5,5-二甲基-2,4-己烷二酮;6-甲基-2,4-庚烷二酮;2,2-二甲基-3,5-壬烷二酮;2,6-二甲基-3,5-庚烷二酮;2-乙酰基环己酮(Cy-acac);2,2,6,6-四甲基-3,5-庚烷二酮(t-Bu-acac);2,2,7-三甲基-3,5-辛烷二酮;1,1,1,5,5,5-六氟-2,4-戊烷二酮(F-acac)];苯甲酰丙酮;二苯甲酰甲烷;3-甲基-2,4-戊二酮;3-乙酰基-戊烷-2-酮;3-乙酰基-2-己酮;3-乙酰基-2-庚酮;3-乙酰基-5-甲基-2-己酮;硬脂酰苯甲酰甲烷;辛酰苯甲酰甲烷;4-叔丁基-4’-甲氧基-二苯甲酰甲烷;4,4’-二甲氧基-二苯甲酰甲烷;4,4’-二叔丁基-二苯甲酰甲烷和2,4-十一烷二酮。
3.根据以上权利要求任意之一的方法,其特征在于具有至少一个尿烷官能团的化合物A是聚氨酯,具有至少一个异氰酸酯官能团的化合物B是二异氰酸酯,并且具有至少一个羟基官能团的化合物D是多元醇。
4.根据权利要求1至2任意之一的方法,其中步骤1)在于在不存在水分且存在催化有效量的根据权利要求1的催化剂C的情况下使至少一种化合物B与至少一种化合物D反应,所述化合物B是选自单异氰酸酯、二异氰酸酯及其混合物的异氰酸酯,所述化合物D是选自单醇、二醇、多元醇及其混合物的醇。
5.根据权利要求1或2的方法,其特征在于化合物B是选自下列化合物的二异氰酸酯:二苯基甲烷二异氰酸酯(MDI),甲苯二异氰酸酯(TDI),六亚甲基二异氰酸酯(HMDI)、1,3-四甲基亚二甲苯基二异氰酸酯、异佛尔酮二异氰酸酯、二环六甲基甲烷二异氰酸酯和异佛尔酮二异氰酸酯(IPDI)。
6.根据权利要求1或2的方法,其特征在于化合物B是选自下列化合物的二异氰酸酯:二苯基甲烷-4,4’-二异氰酸酯或二苯基甲烷-2,4’-二异氰酸酯。
7.根据权利要求1或2的方法,其特征在于化合物B是选自下列化合物的二异氰酸酯:甲苯-2,4-二异氰酸酯或甲苯-2,6-二异氰酸酯。
8.根据权利要求1或2的方法,其特征在于化合物D是聚酯多元醇。
9.根据权利要求1的方法,其特征在于符号L1是衍生自下式(2)的β-二酮的β-二酮根阴离子:
R1COCHR2COR3(2)
其中:
-基团R1和R3,相同或不同,各自代表C1-C30的取代或未取代的线性或支化烃基,
-基团R2为氢或者烃基。
10.根据权利要求9的方法,其特征在于基团R1和R2连接以使得β-二酮形成环。
11.根据权利要求1或2的方法,其特征在于催化剂C是选自下式(8)至(9)的化合物的金属盐或配合物:
(8):[Zn(TMOD)2(N,N’-二甲基乙二胺)],其中(TMOD)=2,2,7-三甲基-3,5-辛烷二酮根阴离子或者2,2,7-三甲基-3,5-辛烷二酮的烯醇盐阴离子,以及
(9):[Zn(TMOD)2(N-丙基乙二胺)],其中(TMOD)=2,2,7-三甲基-3,5-辛烷二酮根阴离子或者2,2,7-三甲基-3,5-辛烷二酮的烯醇盐阴离子。
12.根据权利要求1或2的方法,其特征在于步骤1)在发泡剂的存在下进行。
13.根据权利要求12的方法,其中发泡剂为水。
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