CN111479628B - 湿固化型组合物 - Google Patents
湿固化型组合物 Download PDFInfo
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- CN111479628B CN111479628B CN201880082926.6A CN201880082926A CN111479628B CN 111479628 B CN111479628 B CN 111479628B CN 201880082926 A CN201880082926 A CN 201880082926A CN 111479628 B CN111479628 B CN 111479628B
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- Prior art keywords
- polymer
- heptanedione
- bis
- silane
- compound containing
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- 239000000203 mixture Substances 0.000 title claims description 62
- 229920000642 polymer Polymers 0.000 claims abstract description 76
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 239000004814 polyurethane Substances 0.000 claims abstract description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 claims abstract description 20
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 16
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 14
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 239000000853 adhesive Substances 0.000 claims description 21
- 230000001070 adhesive effect Effects 0.000 claims description 21
- -1 dipivalylmethane Chemical compound 0.000 claims description 21
- 230000000052 comparative effect Effects 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- AWSFICBXMUKWSK-UHFFFAOYSA-N ytterbium(3+) Chemical compound [Yb+3] AWSFICBXMUKWSK-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 6
- RYEKDXOACFEXKG-UHFFFAOYSA-N 1,3-dithiophen-2-ylpropane-1,3-dione Chemical compound C=1C=CSC=1C(=O)CC(=O)C1=CC=CS1 RYEKDXOACFEXKG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical group [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 4
- UNLIPKHWLXWFAN-UHFFFAOYSA-N 1,1,1,2,6,7,7,7-octafluoro-2,6-bis(1,1,2,2,3,3,3-heptafluoropropoxy)heptane-3,5-dione Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(C(F)(F)F)C(=O)CC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F UNLIPKHWLXWFAN-UHFFFAOYSA-N 0.000 claims description 3
- UIRWNAVHKJFQQG-UHFFFAOYSA-N 1,1,1,3,3,5,5,5-octafluoropentane-2,4-dione Chemical compound FC(F)(F)C(=O)C(F)(F)C(=O)C(F)(F)F UIRWNAVHKJFQQG-UHFFFAOYSA-N 0.000 claims description 3
- BVPKYBMUQDZTJH-UHFFFAOYSA-N 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(F)(F)F BVPKYBMUQDZTJH-UHFFFAOYSA-N 0.000 claims description 3
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 claims description 3
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 claims description 3
- VYZCZHFSLXQIKL-UHFFFAOYSA-N 1-(furan-2-yl)-3-(4-methylphenyl)propane-1,3-dione Chemical compound C1=CC(C)=CC=C1C(=O)CC(=O)C1=CC=CO1 VYZCZHFSLXQIKL-UHFFFAOYSA-N 0.000 claims description 3
- NDGWHQSOYIQHAS-UHFFFAOYSA-N 1-(furan-2-yl)-3-phenylpropane-1,3-dione Chemical compound C=1C=COC=1C(=O)CC(=O)C1=CC=CC=C1 NDGWHQSOYIQHAS-UHFFFAOYSA-N 0.000 claims description 3
- YBNWENDKCALCRK-UHFFFAOYSA-N 1-(naphthalen-1-yloxymethoxy)naphthalene Chemical compound C(OC1=CC=CC2=C1C=CC=C2)OC1=C2C=CC=CC2=CC=C1 YBNWENDKCALCRK-UHFFFAOYSA-N 0.000 claims description 3
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 claims description 3
- CEGGECULKVTYMM-UHFFFAOYSA-N 2,6-dimethylheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)C CEGGECULKVTYMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 3
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 3
- YIWTXSVNRCWBAC-UHFFFAOYSA-N 3-phenylpentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)C1=CC=CC=C1 YIWTXSVNRCWBAC-UHFFFAOYSA-N 0.000 claims description 3
- WVVLURYIQCXPIV-UHFFFAOYSA-N 4,4,4-trifluoro-1-naphthalen-2-ylbutane-1,3-dione Chemical compound C1=CC=CC2=CC(C(=O)CC(=O)C(F)(F)F)=CC=C21 WVVLURYIQCXPIV-UHFFFAOYSA-N 0.000 claims description 3
- VVXLFFIFNVKFBD-UHFFFAOYSA-N 4,4,4-trifluoro-1-phenylbutane-1,3-dione Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CC=C1 VVXLFFIFNVKFBD-UHFFFAOYSA-N 0.000 claims description 3
- ISLOIHOAZDSEAJ-UHFFFAOYSA-N 4,7,7-trimethyl-2-(2,2,2-trifluoroacetyl)bicyclo[2.2.1]heptan-3-one Chemical compound C1CC2(C)C(=O)C(C(=O)C(F)(F)F)C1C2(C)C ISLOIHOAZDSEAJ-UHFFFAOYSA-N 0.000 claims description 3
- IGMOYJSFRIASIE-UHFFFAOYSA-N 6-Methylheptan-2,4-dione Chemical compound CC(C)CC(=O)CC(C)=O IGMOYJSFRIASIE-UHFFFAOYSA-N 0.000 claims description 3
- 230000005595 deprotonation Effects 0.000 claims description 3
- 238000010537 deprotonation reaction Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- PEWOESYEGLBLNR-XGLFCGLISA-N (1r,4r)-2-(2,2,3,3,4,4,4-heptafluorobutanoyl)-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound C1C[C@@]2(C)C(=O)C(C(=O)C(F)(F)C(F)(F)C(F)(F)F)[C@@H]1C2(C)C PEWOESYEGLBLNR-XGLFCGLISA-N 0.000 claims 2
- SQNZLBOJCWQLGQ-UHFFFAOYSA-N 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(F)(F)C(F)(F)C(F)(F)F SQNZLBOJCWQLGQ-UHFFFAOYSA-N 0.000 claims 2
- KPCZJLGGXRGYIE-UHFFFAOYSA-N [C]1=CC=CN=C1 Chemical group [C]1=CC=CN=C1 KPCZJLGGXRGYIE-UHFFFAOYSA-N 0.000 claims 2
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 28
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- 238000006243 chemical reaction Methods 0.000 description 15
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Classifications
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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
- C08G18/28—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
- C08G18/4825—Polyethers containing two hydroxy 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
-
- 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
-
- 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
-
- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
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Abstract
一种生产含烷氧基硅烷基团的聚氨酯的方法,其包括使含有至少一个NCO基团的化合物与含有至少一个泽尔维季诺夫活性氢原子的化合物在催化剂组分存在下反应的步骤,其中所述含有至少一个NCO基团的化合物和/或含有至少一个泽尔维季诺夫活性氢原子的化合物含有至少一个烷氧基硅烷基团,以获得含烷氧基硅烷基团的聚氨酯。本发明还涉及含烷氧基硅烷基团的聚合物、生产可固化聚合物的方法、可固化聚合物、经固化聚合物及其用途。所述聚合物含有镧系元素与至少一个β‑二酮配体的络合物,优选Yb(acac)3,并且不含有机锡化合物。
Description
本发明涉及一种生产含烷氧基硅烷基团的聚氨酯的方法,其包括使含有至少一个NCO基团的化合物与含有至少一个泽尔维季诺夫(Zerewitinoff)活性氢原子的化合物在催化剂组分存在下反应的步骤,其中所述含有至少一个NCO基团的化合物和/或含有至少一个泽尔维季诺夫活性氢原子的化合物含有至少一个烷氧基硅烷基团,以获得含烷氧基硅烷基团的聚氨酯。本发明还涉及含烷氧基硅烷基团的聚合物、生产可固化聚合物的方法、可固化聚合物、经固化聚合物及其用途。
基于硅烷官能聚合物的湿固化型组合物是已知的并作为弹性密封剂或弹性镶木地板胶粘剂大量用于例如建筑业。
硅烷官能聚合物可分成不同的三类,它们的硅烷基团反应性不同,这体现在由其制成的湿固化型组合物的固化速率中。
通过具有末端双键的聚合物,例如聚(甲基)丙烯酸酯聚合物或聚醚聚合物的氢化硅烷化制成的聚合物是已知的。它们例如描述在US 3,971,751和US 6,207,766中。缺点是这些聚合物具有低反应性,因此具有实际可用的固化时间的湿固化型组合物的生产在许多情况下必需为了生产添加含锡的固化催化剂,它们在毒理学上令人担忧并且市场接受度越来越低。
其中所谓的γ-硅烷基团经氨基甲酸酯或脲基团键合到聚合物骨架上的聚合物明显更具反应性,因此具有实际可用的固化时间的湿固化型组合物的生产在许多情况下不用或者只用少量含锡催化剂是可行的。
第三类聚合物的特点在于其中所谓的α-硅烷基团经氨基甲酸酯或脲基团键合到聚合物骨架上并在一些情况下甚至不用特定的固化催化剂就快速固化。其缺点在于由于它们的高反应性,它们不稳定并且昂贵并且可得性差。
商业硅烷封端的聚氨酯预聚物的生产涉及催化NCO基团与泽尔维季诺夫活性氢原子的反应。二月桂基二丁基锡(DBTL)常用于此。但是,由于DBTL的毒理学性质,需要替代性催化剂。
DBTL也用于制造基于硅烷官能聚合物的可固化组合物。在此也由于DBTL的毒理学性质而需要替代性催化剂。
WO 2013/165552 A1描述了使用镱的特定聚丙烯酸盐作为用于含有反应性硅烷基团的湿固化型组合物的可能的固化催化剂,但是没有给出具体实例。
US 7060778 B2描述了Yb(acac)3作为用于脂族低聚碳酸酯多元醇的酯交换反应催化剂。DE 102004012876 A1描述了Yb(acac)3作为用于NCO/OH反应的催化剂。
许多金属催化剂,特别是有机锡催化剂的另一个缺点是,它们在基于硅烷官能聚合物的可固化组合物中,例如用作建筑密封剂,导致固化后的割线模量显著提高,因此不能达到ISO 11600对于低模量密封剂的要求(根据ISO 8339,在23摄氏度时的割线模量最多0.4 MPa)或必须使用大量增塑剂才能达到标准,但是这增加了因增塑剂迁移进入所接合基底的边缘区域而引起接缝边缘污损的风险(Praxishandbuch Dichtstoffe, IVK, 第4版,从第139页起)。
EP 2 952 533 A1公开了一种湿固化型的密封剂,其包含a)至少一种硅烷官能聚合物和b)至少一种用于使硅烷官能聚合物交联的催化剂,其中该密封剂不含有机锡化合物并且在固化状态下具有根据ISO 8339测定的在100%伸长和23℃下的割线模量小于0.4MPa,根据ISO 7389测定的在100%伸长下的回弹性大于70%。根据该文献,该密封剂特别适合作为根据DIN EN ISO 11600的25LM级的建筑密封剂,特别是作为外立面密封剂。
因此,本发明的目的是提供基于硅烷官能聚合物的湿反应性组合物,该组合物克服了现有技术的缺点,并且在基本上不添加有机锡化合物的情况下完全固化,并且在固化状态下具有低的割线模量。
根据本发明,该目的通过权利要求1 所述的方法,权利要求8所述的含烷氧基硅烷基团的聚氨酯,权利要求10所述的生产可固化聚合物的方法,权利要求12所述的可固化聚合物,权利要求13所述的经固化聚合物和权利要求15所述的用途得以实现。在从属权利要求和说明书中给出了有利的扩展方式。可以将它们任意组合,除非从上下文可以清楚地看出相反的意思。
一种生产含烷氧基硅烷基团的聚氨酯的方法,其包括使含有至少一个NCO基团的化合物与含有至少一个泽尔维季诺夫活性氢原子的化合物在催化剂组分存在下反应的步骤,其中所述含有至少一个NCO基团的化合物和/或含有至少一个泽尔维季诺夫活性氢原子的化合物含有至少一个烷氧基硅烷基团,以获得含烷氧基硅烷基团的聚氨酯。所述催化剂组分包括镧系元素与至少一个β-二酮配体的络合物,并且所述催化剂组分不含有机锡化合物。
已经发现,镧系元素的β-二酮络合物可以用作氨基甲酸酯化催化剂,并且可以保留在含烷氧基硅烷基团的聚氨酯中,以便在随后的硅烷交联中也充当催化剂或至少不出现负面影响。
因此借助这种根据本发明的方法能够生产涂覆剂、胶粘剂、弹性体和密封组合物的前体而不必以DBTL基氨基甲酸酯化催化剂的毒理学缺点为代价。
术语“可固化”通常特别是指该组合物能在外部条件的影响下,特别是在环境中存在的和/或有意供应的湿气的影响下从相对软质的、任选可塑性变形的状态转化成更硬的状态。除上述湿气外,通常还可通过化学和/或物理影响实现交联,即例如还通过以热、光或其它电磁辐射的形式供应能量,以及通过该组合物与空气或反应性组分的简单接触。
在根据本发明的术语烷氧基硅烷中也包括酰氧基硅烷。
在该方法的一个实施方案中,提供聚氨酯的反应至少部分时间在≥50℃(优选≥60℃)的温度下进行≥10分钟(优选≥100分钟至≤500分钟)的时间长度。
催化剂组分不含有机锡化合物在本发明中定义为使得在提供聚氨酯的反应混合物中以及在所得聚氨酯中有机锡化合物的含量基于含烷氧基硅烷基团的聚氨酯的总重量≤0.06重量%,并优选≤0.01重量%。
通过用正己烷萃取样品(任选),用四乙基硼酸钠衍生化(任选)和气相色谱法进行有机锡化合物含量的定量测定,其中优选通过原子发射进行检测。详情可见例如博士论文"Bestimmung von Organozinnverbindungen in Sedimenten mittels GC-AED –Entwicklung von Extraktions- und Derivatisierungsmethoden", Almut Liebich,Technische Universität Berlin 2005 (http://dx.doi.org/10.14279/depositonce-1164)。
因此,特别是在反应中不使用基于有机锡的催化剂,例如DBTL(二月桂酸二丁基锡)。有机锡化合物通常可定义为其中存在共价Sn-C键的所有化合物。
这还包括从可能的前体例如聚氨酯预聚物不将有机锡催化剂残余物携带入用于根据本发明的方法的反应混合物中。
基于反应中使用的组分的总重量,镧系元素-β-二酮络合物的含量可以例如为≥0.0001重量%至≤1重量%。优选的含量是≥0.002重量%至≤0.05重量%,更优选≥0.005重量%至≤0.1重量%。
β-二酮络合物中合适的镧系元素离子特别是铈,镨,钕,钷,钐,铕,钆,铽,镝,钬,铒,铥,镱,镥或其混合物的氧化态(III)的离子。在该方法的一个实施方案中,镧系元素是镱(III)。
在该方法的另一实施方案中,β-二酮配体可通过下面化合物的脱质子化获得:Hacac (乙酰丙酮)、Hacac-F7 (全氟乙酰丙酮)、Hbfa (苯甲酰基-2-呋喃甲酰基甲烷)、Hbpp (l,3-双(3-吡啶基)-l,3-丙二酮)、Hbtfac (苯甲酰基三氟丙酮)、Hbzac (苯甲酰基丙酮)、Hdbbm (二(4-溴)苯甲酰基甲烷)、Hdcm (d,d-二龙脑基甲烷)、Hdmbm (4,4'-二甲氧基二苯甲酰基甲烷)、Hdmh (2,6-二甲基-3,5-庚二酮)、Hdnm (二萘甲酰基甲烷)、Hdpm (二新戊酰基甲烷)、Hdppm (二(全氟-2-丙氧基丙酰基)甲烷)、Hdtp (1,3-二(2-噻吩基)-1,3-丙二酮)、Hfacam (3-(三氟乙酰基)-d-樟脑)、Hfdh (6,6,6-三氟-2,2-二甲基-3,5-己二酮)、Hfhd (l,l,l,2,2,6,6,7,7,7-十氟-3,5-庚二酮)、Hfod (6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5-辛二酮)、Hftac (2-呋喃基三氟丙酮)、Hhfac (六氟乙酰丙酮)、Hhfbc (3-(七氟丁酰基)-d-樟脑)、Hhfth (4,4,5,5,6,6,6-七氟-l-(2-噻吩基)-l,3-己二酮)、Hmfa (4-甲基苯甲酰基-2-呋喃甲酰基甲烷)、Hmhd (6-甲基-2,4-庚二酮)、Hntac (2-萘甲酰基三氟丙酮)、Hpop (3-(5-苯基-l,3,4-噁二唑-2-基)-2,4-戊二酮)、Hppa (3-苯基-2,4-戊二酮)、Hpta (=Htpm) (新戊酰基三氟丙酮)、Hptp (l-苯基-3-(2-噻吩基)-l,3-丙二酮)、H(t-cam) (3-(叔丁基羟基亚甲基)-d-樟脑)、Htfac (三氟乙酰丙酮)、Htfn (l,l,l,2,2,3,3,7,7,8,8,9,9,9-十四氟-4,6-壬二酮)、Hthd (=Hdpm、Htmhd) (2,2,6,6-四甲基-3,5-庚二酮)、Htnb (4,4,4-三氟-l-(2-萘基)-l,3-丁二酮)、Htmod (2,2,6,6-四甲基-3,5-辛二酮)、Htrimh (2,2,6-三甲基-3,5-庚二酮)、Htod (2,2,7-三甲基-3,5-辛二酮)、Htta (2-噻吩甲酰基三氟丙酮) 或其任意混合。其中Hacac是优选的。
在该方法的另一实施方案中,镧系元素与至少一个β-二酮配体的络合物为Yb(acac)3。
在这种方法的另一实施方案中,含有至少一个NCO基团的化合物含有至少一个烷氧基硅烷基团,且含有至少一个泽尔维季诺夫活性氢原子的化合物不含烷氧基硅烷基团。这样的异氰酸根合烷氧基硅烷的合适实例是异氰酸根合甲基三甲氧基硅烷、异氰酸根合甲基三乙氧基硅烷、异氰酸根合甲基三异丙氧基硅烷、2-异氰酸根合乙基三甲氧基硅烷、2-异氰酸根合乙基三乙氧基硅烷、2-异氰酸根合乙基三异丙氧基硅烷、3-异氰酸根合丙基三甲氧基硅烷、3-异氰酸根合丙基三乙氧基硅烷、3-异氰酸根合丙基甲基二甲氧基硅烷、3-异氰酸根合丙基甲基二乙氧基硅烷、3-异氰酸根合丙基乙基二乙氧基硅烷、3-异氰酸根合丙基二甲基乙氧基硅烷、3-异氰酸根合丙基二异丙基乙氧基硅烷、3-异氰酸根合丙基三丙氧基硅烷、3-异氰酸根合丙基三异丙氧基硅烷、3-异氰酸根合丙基三丁氧基硅烷、3-异氰酸根合丙基甲基二丁氧基硅烷、3-异氰酸根合丙基苯基二甲氧基硅烷、3-异氰酸根合丙基苯基二乙氧基硅烷、3-异氰酸根合丙基三(甲氧基乙氧基乙氧基)硅烷、2-异氰酸根合异丙基三甲氧基硅烷、4-异氰酸根合丁基三甲氧基硅烷、4-异氰酸根合丁基三乙氧基硅烷、4-异氰酸根合丁基三异丙氧基硅烷、4-异氰酸根合丁基甲基二甲氧基硅烷、4-异氰酸根合丁基甲基二乙氧基硅烷、4-异氰酸根合丁基乙基二甲氧基硅烷、4-异氰酸根合丁基乙基二乙氧基硅烷、4-异氰酸根合丁基二甲基甲氧基硅烷、4-异氰酸根合丁基苯基二甲氧基硅烷、4-异氰酸根合丁基苯基二乙氧基硅烷、4-异氰酸根合(3-甲基丁基)三甲氧基硅烷、4-异氰酸根合(3-甲基丁基)三乙氧基硅烷、4-异氰酸根合(3-甲基丁基)甲基二甲氧基硅烷、4-异氰酸根合(3-甲基丁基)甲基二乙氧基硅烷和11-异氰酸根合十一烷基三甲氧基硅烷或这些异氰酸根合烷氧基硅烷的任意混合物。
作为泽尔维季诺夫活性化合物可考虑例如聚醚多元醇(特别是聚丙二醇)、聚酯多元醇和OH封端的聚氨酯预聚物。
所得反应产物尤其可具有结构(I):
其中
R1代表具有1至6个碳原子的亚烷基,
R2代表甲基或乙基且
m代表0或1或2。
优选的是,m代表0。
R1优选代表1,3-亚丙基和/或亚甲基(-CH2-)。
在这种方法的另一实施方案中,含有至少一个NCO基团的化合物不含烷氧基硅烷基团,且含有至少一个泽尔维季诺夫活性氢原子的化合物含有至少烷氧基硅烷基团。
合适的单体二异氰酸酯尤其是1,4-二异氰酸根合丁烷(BDI)、1,5-二异氰酸根合戊烷(PDI)、1,6-己二异氰酸酯(HDI)、2-甲基-1,5-二异氰酸根合戊烷、1,5-二异氰酸根合-2,2-二甲基戊烷、2,2,4-或2,4,4-三甲基-1,6-二异氰酸根合己烷、1,10-二异氰酸根合癸烷、1,3-和1,4-二异氰酸根合环己烷、1,4-二异氰酸根合-3,3,5-三甲基环己烷、1,3-二异氰酸根合-2-甲基环己烷、1,3-二异氰酸根合-4-甲基环己烷、1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(异佛尔酮二异氰酸酯;IPDI)、1-异氰酸根合-1-甲基-4(3)-异氰酸根合甲基环己烷、2,4'-和4,4'-二异氰酸根合二环己基甲烷(H12MDI)、1,3-和1,4-双(异氰酸根合甲基)环己烷、双(异氰酸根合甲基)降冰片烷(NBDI)、4,4'-二异氰酸根合-3,3'-二甲基二环己基甲烷、4,4'-二异氰酸根合-3,3',5,5'-四甲基二环己基甲烷、4,4'-二异氰酸根合-1,1'-二(环己基)、4,4'-二异氰酸根合-3,3'-二甲基-1,1'-二(环己基)、4,4'-二异氰酸根合-2,2',5,5'-四甲基-1,1'-二(环己基)、1,8-二异氰酸根合-对薄荷烷、1,3-二异氰酸根合金刚烷、1,3-二甲基-5,7-二异氰酸根合金刚烷、1,3-和1,4-双(异氰酸根合甲基)苯(苯二亚甲基二异氰酸酯;XDI)、1,3-和1,4-双(1-异氰酸根合-1-甲基乙基)苯(TMXDI)、双(4-(1-异氰酸根合-1-甲基乙基)苯基)碳酸酯、2,4-和2,6-二异氰酸根合甲苯(TDI)、2,4'-和4,4'-二异氰酸根合二苯甲烷(MDI)、1,5-二异氰酸根合萘及其混合物。由二异氰酸酯制成的多异氰酸酯,例如具有缩二脲、氨基甲酸酯或异氰脲酸酯结构的那些也是可行的。
在一个优选实施方案中,二异氰酸酯选自1-异氰酸根合-3,3,5-三甲基-5-异氰酸根合甲基环己烷(IPDI)、1,6-己二异氰酸酯(HDI)、2,4-和/或2,6-甲苯二异氰酸酯(TDI)或其混合物。
例如可由含异氰酸酯基团的聚醚,尤其是来自聚醚多元醇与超化学计量的多异氰酸酯的反应的NCO封端的氨基甲酸酯聚醚与氨基硅烷、羟基硅烷或巯基硅烷的反应获得相应的反应产物。这样的硅烷官能聚合物尤其包含式(II)的结构
其中
X代表O或S或NR5,其中R5代表氢原子或具有1至20个碳原子的烃基,该烃基任选包含环状成分并任选包含烷氧基甲硅烷基或一个或多个醚或羧酸酯基团,
R3代表具有1至18个碳原子的二价烃基,该二价烃基任选包含环状和/或芳族成分并任选包含一个或多个杂原子,
R4代表具有1至5个碳原子的烷基,该烷基任选含有醚基团,且
n代表0或1或2。
优选的是,n代表0。
优选的是,R3代表1,3-亚丙基或1,4-亚丁基或3,3-二甲基-1,4-亚丁基且X代表NR5,其中R5优选代表下式的基团
。
进一步优选的是,X代表O且R代表下式的基团
或/>
其中配置这一基团以使X直接键合到环己基环上,并且其中Y代表O或NR7且R6和R7各自互相独立地代表具有1至18个碳原子的一价烃基,该一价烃基可包含醚氧或硫醚硫或叔胺氮形式的杂原子,或R6和R7与Y(或N)一起形成环,特别是吗啉环。
在这种方法的另一实施方案中,含有至少一个泽尔维季诺夫活性氢原子的化合物含有至少一个伯或仲氨基。其优选是N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷、N-环己基-3-氨基丙基三甲氧基硅烷、N-环己基氨基甲基三乙氧基硅烷、3-氨基丙基三乙氧基硅烷、3-(2-氨基甲基氨基)丙基三乙氧基硅烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、3-氨基丙基三甲氧基硅烷、3-脲基丙基三甲氧基硅烷、N-(3-三甲氧基甲硅烷基丙基)天冬氨酸二乙酯或其混合物。含有乙氧基代替甲氧基或含有甲氧基代替乙氧基或含有酰氧基的相应化合物也是合适的。
本发明还涉及一种含烷氧基硅烷基团的聚合物,其中该聚合物包含镧系元素与至少一个β-二酮配体的配合物,并且该聚合物不含有机锡化合物。就镧系元素、β-二酮配体和不存在有机锡化合物而言,适用与上文对NCO基团与泽尔维季诺夫活性氢原子的反应的本发明的方法相同的考量。为避免不必要的赘述,不重复这些。仅应注意,优选的镧系元素络合物同样是Yb(acac)3。
含烷氧基硅烷基团的聚合物,也被称为硅烷官能聚合物,优选是聚烯烃、聚酯、聚酰胺、聚(甲基)丙烯酸酯或聚醚或这些聚合物的混合形式。其硅烷基团可在链中的侧位或末端。特别优选的是,硅烷官能聚合物是聚烯烃或聚酯或聚(甲基)丙烯酸酯或聚醚或这些聚合物的混合形式。
例如,硅烷官能聚合物可以是含硅烷基团的聚醚。其优选包含占多数的氧基亚烷基单元,特别是1,2-氧基亚丙基单元。硅烷基团优选是二烷氧基硅烷基团和/或三烷氧基硅烷基团,特别是二甲氧基甲基硅烷基团或三甲氧基硅烷基团或三乙氧基硅烷基团。
硅烷官能聚合物优选不含异氰酸酯基团。
硅烷官能聚合物平均具有每分子优选1.3至4,特别是1.5至3,特别优选1.7至2.8个硅烷基团。
硅烷官能聚合物优选具有1000至30000 g/mol,特别是2000至20000 g/mol的平均分子量。
硅烷官能聚合物优选在室温下是液体。其特别优选具有低粘度。在20℃下的粘度特别在1至200 Pa s,优选2至100 Pa s,特别优选5至50 Pa s的范围内。
硅烷官能聚合物优选选自
- 由含烯丙基的聚醚与氢硅烷的反应获得的含硅烷基团的聚醚,任选在扩链下,特别是用二异氰酸酯扩链;
- 由环氧烷和环氧硅烷的共聚获得的含硅烷基团的聚醚,任选在扩链下,特别是用二异氰酸酯扩链;
- 由聚醚多元醇与异氰酸根合硅烷的反应获得的含硅烷基团的聚醚,任选在用二异氰酸酯扩链下;和
- 由含异氰酸酯基团的氨基甲酸酯聚醚与氨基硅烷或羟基硅烷或巯基硅烷的反应获得的含硅烷基团的聚醚。
这些硅烷官能聚合物特别易得。
其中优选的是由含烯丙基的聚醚与氢硅烷的反应获得的含硅烷基团的聚醚。这些硅烷官能聚合物具有特别低的粘度并且特别惰性。
其中也优选的是由聚醚多元醇与异氰酸根合硅烷的反应获得的含硅烷基团的聚醚。这些硅烷官能聚合物特别易得,具有极低粘度并且相当惰性。
市售硅烷官能聚合物也合适,特别是以商品名MS Polymer™(来自Kaneka Corp.;尤其是类型S203H、S303H、S227、S810、MA903或S943);MS Polymer™或Silyl™(来自KanekaCorp.;尤其是类型SAT010、SAT030、SAT200、SAX350、SAX400、SAX725、MAX450、MAX602或MAX951);Excestar®(Asahi Glass Co. Ltd.;尤其是类型S2410、S2420、S3430或S3630);SPUR+®(来自Momentive Performance Materials;尤其是类型101 OLM、1015LM或1050MM);Vorasil™(来自Dow Chemical Co.;尤其是类型602或604);Desmoseal®(来自BayerMaterialScience AG;尤其是类型S XP 2458、XP 2636、S XP 2749、S XP 2774或S XP2821);TEGOPAC®(来自Evonik Industries AG;尤其是类型Seal 100、Bond 150或Bond250);或Geniosil® STP(来自Wacker Chemie AG;尤其是类型E15或E35、E10和E-30)获得的产品。
由含烯丙基的聚醚与氢硅烷的反应获得的硅烷官能聚合物(任选用例如二异氰酸酯扩链下)特别具有式(III)的结构
其中
R8代表甲基或乙基且
o代表0或1或2。
优选的是,o代表0或1,特别是1,且R8代表甲基。
由环氧烷和环氧硅烷的共聚获得的硅烷官能聚合物(任选在用例如二异氰酸酯扩链下)特别具有式(IV)的结构
其中
R9代表甲基或乙基且
p代表0或1或2。
优选代表0。
在这种聚合物的一个实施方案中,该聚合物是通过上述方法可获得的聚氨酯。
在一个实施方案中,聚氨酯的粘度(板-锥旋转粘度计,23℃,ISO 3219:1994)为通过相同生产方法但在催化剂组分中用二月桂酸二丁基锡代替镧系元素与至少一个β-二酮配体的络合物制成的对比聚氨酯的粘度的≤ 115%。
本发明的另一方面是一种生产可固化聚合物的方法,其中该方法包括使如上所述的聚合物与硅氧烷缩合催化剂接触的步骤。作为硅氧烷缩合催化剂适用的是全部任意的非有机锡催化剂。
用于硅烷官能聚合物的交联的特别优选的催化剂是包含至少一个脒基的那些。这些尤其是式(V)的化合物:
其中基团R10代表氢原子、具有1至10个碳原子的一价烃基或与R13一起代表具有1至10个碳原子的任选取代的二价烃基。
基团R11代表氢原子、具有1至12个碳原子的一价烃基(任选包含环状或芳族成分并任选包含一个或多个杂原子)、氨基,或与R12一起代表具有1至10个碳原子的任选取代的二价烃基。
基团R12代表氢原子、具有1至12个碳原子的一价烃基(任选包含环状或芳族成分并任选包含一个或多个杂原子),或与R11一起代表具有1至10个碳原子的任选取代的二价烃基。
基团R13代表氢原子、具有1至10个碳原子的一价烃基或与R10一起代表具有1至10个碳原子的任选取代的二价烃基。
具有杂原子的基团R11和/或R12是例如具有硅烷基团的烷基,例如烷基三烷氧基硅烷基团。
包含至少一个脒基的化合物优选是胍、咪唑、咪唑啉、双环脒或这些化合物的衍生物。这样的衍生物是例如取代咪唑类或咪唑啉类,尤其是包含硅烷基团的咪唑类或咪唑啉类。
优选的具有至少一个脒基的化合物是1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)、1,5-二氮杂双环[4.3.0]壬-5-烯(DBN)、6-(二丁基氨基)-1,8-二氮杂双环[5.4.0]十一碳-7-烯、N-甲基三氮杂双环癸烯、四甲基胍、2-胍基苯并咪唑、乙酰丙酮胍、1,3-二-邻甲苯基胍(DTG)、1,3-二苯基胍、邻甲苯基双胍、2-叔丁基-1,1,3,3-四甲基胍或N-(3-三乙氧基甲硅烷基丙基)-4,5-二氢咪唑、N-(3-三甲氧基甲硅烷基丙基)-4,5-二氢咪唑。
硅氧烷缩合催化剂的比例优选为总组合物的0.01重量%至3重量%,特别是0.03重量%至2重量%,优选0.05重量%至0.5重量%。在大于0.5重量%的比例下,可能发生从固化组合物中渗出该化合物,这对某些用途不利(视觉外观、易污损性等)。
脒优选是双环脒,特别在双环成分中具有9、10、11或12个碳原子。这些化合物的优点在于它们具有较高的反应性并且其含量因此可保持相对较低。这又可减少这些化合物从固化组合物中渗出。
同样适合作为硅氧烷缩合催化剂的是含氨基的催化剂,如DABCO(1,4-二氮杂双环[2.2.2]辛烷)。
同样适合作为硅氧烷缩合催化剂的是单体含氨基硅烷,正如它们也用作粘合硅烷。
在这种方法的一个实施方案中,该聚合物进一步与水接触。
本发明进一步涉及通过根据本发明的上述方法可获得的可固化聚合物。该可固化聚合物优选与辅助剂和添加剂一起作为可固化制剂的成分。其例如以基于总组合物计10重量%至80重量%的量,特别是15重量%至50重量%,优选20重量%至40重量%的量使用。这样的制剂可含有下列组分,其中Yb(acac)3可源自用于生产可固化聚合物的反应:
a) 10重量%至50重量%的含烷氧基硅烷基团的聚合物;
b)0.0001重量%至0.1重量%的乙酰丙酮镱(III);
c) 0.001重量%至3重量%的至少一种用于硅烷官能聚合物的交联的催化剂,选自不含锡或锡离子也不含有机锡化合物的化合物;
d) 辅助剂和添加剂。
下列辅助剂和添加剂特别合适:
- 无机和有机填料,特别是天然、研磨或沉淀碳酸钙,其任选用脂肪酸,特别是硬脂酸涂布,氧化钡(重晶石)、滑石、石英粉、石英砂、白云石、硅灰石、高岭土、煅烧高岭土、云母、分子筛、氧化铝、氢氧化铝、氢氧化镁、二氧化硅,包括来自热解工艺的高分散二氧化硅,工业制造的炭黑、石墨、金属粉末如铝、铜、铁、银或钢、PVC粉末或无机或有机材料的中空球体。
- 附着力促进剂和/或交联剂,特别是硅烷,特别例如氨基硅烷,特别例如3-氨基丙基三甲氧基硅烷、3-氨基丙基二甲氧基甲基硅烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-(2-氨基乙基)-N'-[3-(三甲氧基甲硅烷基)丙基]乙二胺或用乙氧基或异丙氧基代替硅上的甲氧基的它们的类似物、N-苯基-、N-环己基-或N-烷基氨基硅烷,还有巯基硅烷、环氧硅烷、(甲基)丙烯酰基硅烷、酸酐基硅烷(Anhydridosilane)、氨基甲酸酯基硅烷、烷基硅烷、乙烯基硅烷或亚氨基硅烷,或这些硅烷的低聚形式或伯氨基硅烷与环氧硅烷或(甲基)丙烯酰基硅烷或酸酐基硅烷的加合物。3-环氧丙氧丙基三甲氧基硅烷、3-氨基丙基三甲氧基硅烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷、N-(2-氨基乙基)-N'-[3-(三甲氧基甲硅烷基)丙基]乙二胺、3-巯丙基三甲氧基硅烷、3-脲基丙基三乙氧基硅烷、乙烯基三甲氧基硅烷或用乙氧基代替甲氧基的相应硅烷或这些硅烷的低聚形式尤其合适。
- 增塑剂,特别是羧酸酯,如邻苯二甲酸酯,特别是邻苯二甲酸二辛酯、邻苯二甲酸二异壬酯或邻苯二甲酸二异癸酯,己二酸酯,特别是己二酸二辛酯,壬二酸酯、癸二酸酯、多元醇,特别是聚氧基亚烷基多元醇或聚酯多元醇、二醇醚、二醇酯、有机磷酸酯或磺酸酯、聚丁烯或衍生自天然脂肪或油的脂肪酸甲基或乙基酯、也称为“生物柴油”,1,2-环己烷二甲酸二烷基酯,如1,2-环己烷二甲酸二异壬酯。
- 任选地,溶剂。
- 干燥剂,特别是四乙氧基硅烷、乙烯基三甲氧基硅烷或乙烯基三乙氧基硅烷或在硅烷基团的α位置具有官能团的有机烷氧基硅烷,特别是N-(甲基二甲氧基甲硅烷基甲基)-O-甲基氨基甲酸酯、(甲基丙烯酰氧基甲基)硅烷、甲氧基甲基硅烷、原甲酸酯或氧化钙或分子筛。
- 抗氧化、热、光或紫外线辐射的稳定剂。
- 颜料,尤其是二氧化钛或氧化铁。
- 流变改性剂,尤其是增稠剂,特别是
- 页硅酸盐,如膨润土、蓖麻油衍生物、氢化蓖麻油、聚酰胺、聚氨酯、脲化合物、热解二氧化硅、纤维素醚或疏水改性的聚氧乙烯。
- 纤维,特别是玻璃纤维、碳纤维、金属纤维、陶瓷纤维或塑料纤维,如聚酰胺纤维或聚乙烯纤维。
- 染料。
- 天然树脂、脂肪或油,如松香、虫胶、亚麻籽油、蓖麻油或大豆油。
- 非反应性聚合物,特别例如不饱和单体的均聚物或共聚物,不饱和单体特别选自乙烯、丙烯、丁烯、异丁烯、异戊二烯、乙酸乙烯酯或(甲基)丙烯酸烷基酯,特别是聚乙烯(PE)、聚丙烯(PP)、聚异丁烯,
- 乙烯乙酸乙烯酯共聚物(EVA)或无规立构聚-α-烯烃(APAO)。
- 阻燃物质,特别是上文提到的填料氢氧化铝或氢氧化镁,或特别是有机磷酸酯,特别例如磷酸三乙酯、磷酸三甲苯酯、磷酸三苯酯、磷酸二苯基甲苯酯、磷酸异癸基二苯酯、磷酸三(1,3-二氯-2-丙基)酯、磷酸三(2-氯乙基)酯、磷酸三(2-乙基己基)酯、磷酸三(氯异丙基)酯、磷酸三(氯丙基)酯、异丙基化的磷酸三苯酯、不同异丙基化程度的磷酸单-、双-或三(异丙基苯基)酯、间苯二酚双(二苯基磷酸酯)、双酚-A-双(二苯基磷酸酯)或多聚磷酸铵。
- 表面活性物质,尤其是润湿剂、流平剂、除气剂或消泡剂。
- 杀生物剂,尤其是杀藻剂、杀真菌剂或抑制真菌生长的物质。
或常用于湿固化型组合物的其它物质。
可能有利的是,在混入组合物之前通过化学或物理方式干燥某些成分。
在一个优选实施方案中,该组合物不含含重金属的有机化合物。其特别不含有机锡化合物。
该组合物优选隔绝湿气生产和储存。该组合物通常在合适的包装或配置,尤其例如桶、袋或筒中在隔绝湿气的情况下储存稳定。
该组合物可以是单组分组合物的形式或双组分组合物的形式。
在本文中,“单组分”被理解为是指该组合物的所有成分混合储存在同一容器中并且可湿固化的组合物。在本文中,“双组分”被理解为是指该组合物的成分在储存在彼此分开的容器中的两个不同组分中的组合物。在该组合物施加前不久或过程中,将这两个组分互相混合以使混合的组合物固化,其中通过湿气的作用才实现或完成固化。
在至少一个物体或制品上施加该组合物的过程中,存在的硅烷基团和任选存在的其它湿反应性基团与湿气接触,由此固化该组合物。根据温度、接触类型、湿气量和可能的催化剂的存在,以不同速率发生固化。在借助大气湿度固化的情况下,最初在组合物的表面结皮。所谓的结皮时间是固化速率的量度。
本发明的另一方面是通过上述可固化聚合物的固化可获得的经固化聚合物。
在固化状态下,该聚合物表现出突出的弹性性质,特别是高强度和高伸展性,以及良的耐热性和在非常多样化的基底上的好附着性质。这使其适合许多用途,特别是作为用于建筑和工业用途的纤维复合材料(复合物)、灌注料、密封剂、胶粘剂、覆盖物、涂料或漆,例如作为电绝缘物料、填缝料、接缝密封剂、焊接或法兰接缝密封剂、镶木地板胶粘剂、装配胶粘剂、车身胶粘剂、窗户胶粘剂、夹层元件胶粘剂、地板覆盖物、地面涂料、阳台涂料、屋顶涂料、混凝土保护涂料、停车楼涂料或作为防腐蚀保护漆、作为密封料、漆、清漆或底漆。其特别适合作为胶粘剂或密封剂或涂料,特别是用于建筑或工业用途中的接缝密封或弹性胶粘剂连接。
在经固化聚合物的一个实施方案中,经固化聚合物具有与对比聚合物相比的至少一个下列性质,其中各自的样品在测量前已在23℃和50%空气相对湿度下储存14天:
肖氏A硬度(DIN 53505): 对比聚合物的≤ 90%(优选≤ 85%,更优选≤ 80%);
断裂伸长百分比值(DIN EN 53504,拉伸速度: 200 mm/min,S2试样): 对比聚合物的百分比值的≥ 101%(优选≥ 105%,更优选≥110%);
割线模量(EN ISO 8339,100%伸长): 对比聚合物的≤ 90%(优选≤ 85%,更优选≤ 80%);
并且其中对比聚合物以与所述经固化聚合物相同的方式但在如上所述的方法中的催化剂组分中用相同摩尔量的二月桂酸二丁基锡代替镧系元素与至少一个β-二酮配体的络合物制造。
本发明进一步涉及如上所述的可固化聚合物和/或如上所述的经固化聚合物作为密封剂、胶粘剂或涂覆材料的用途。
对于用作胶粘剂或密封剂,可固化聚合物优选具有假塑性的糊状稠度。将这样的糊状胶粘剂或密封剂施加到基底上,任选使用涂施机器人,特别是从手动或使用压缩空气操作的市售料筒或从使用传送泵或挤出机的桶或铁皮容器。
可以粘合或密封两个相同基底或两个不同基底。
合适的基底特别是:
- 玻璃、玻璃陶瓷、丝网印刷陶瓷、混凝土、砂浆、砖、瓦、石膏或天然石材,如花岗岩或大理石;
- 金属或合金,如铝、铁、钢或有色金属,或表面精制金属或合金,如镀锌或镀铬金属;
- 皮革、纺织品、纸、木材,用树脂,例如酚醛树脂、三聚氰胺树脂或环氧树脂粘结的木质材料、树脂-织物复合材料或另外所谓的聚合物复合材料;
- 塑料,特别是硬质或软质的PVC、ABS、聚碳酸酯(PC)、聚酰胺(PA)、聚酯、PMMA、环氧树脂、PUR、POM、PO、PE、PP、EPM或EPDM,其中塑料任选使用等离子体、电晕或火焰处理法表面处理;
- 纤维增强塑料,如碳纤维增强塑料(CFK)、玻璃纤维增强塑料(GFK)或片状模塑配混物(SMC);
- 涂布基底,如粉末涂布金属或合金;
- 漆或清漆,尤其是汽车面漆。
如果需要,基底可在施加胶粘剂或密封剂之前预处理,特别是通过物理和/或化学清洁法或施加附着力促进剂、附着力促进剂溶液或底漆。
在粘合或密封两个基底后,获得胶粘或密封的制品。这样的制品可以是建筑结构,特别是高层或低层建筑结构,或工业品或消费品,特别是窗户、家用机器或运输工具,特别例如汽车、公共汽车、载重汽车、轨道车辆、船舶、飞机或直升飞机或其附件。
湿固化型组合物优选含有选自如上所述的填料、交联剂、增塑剂、溶剂、催化剂、附着力促进剂、干燥剂、稳定剂、颜料和流变助剂的至少一种附加成分。所述湿固化型组合物优选具有5重量%至95重量%,特别是10重量%至50重量%的硅烷官能聚合物含量。
实施例
参考下面实施例更详细阐释本发明,但本发明不限于此。
方法和材料:
肖氏硬度、断裂伸长、拉伸强度、在100%伸长下的拉伸应力和回弹性的测定:
在从制成开始算在筒中储存7天后,使用刮刀将湿固化型组合物施加到聚乙烯薄膜上以提供具有2 mm的均匀层厚度的膜,并在23℃和50%空气相对湿度下固化14天,其中在7天后将膜从薄膜上剥离并翻面。随后通过下列方法测定所得膜的性质。
根据DIN ISO 7619-1中的规范在膜上进行肖氏A硬度的测试。为了测定肖氏A硬度,将三个膜彼此叠加放置以确保层厚度为6 mm。
借助根据DIN 53 504中的规范的拉伸试验在由如上所述制成的膜使用定型冲模冲压而得的S2哑铃上测定断裂伸长、拉伸强度和在100%伸长下的拉伸应力。试验速度为200mm/min。
根据ISO 7389在铝试样上测定回弹性(储存方法B)。
在储存7天或60天后测定粘度并根据DIN EN ISO 3219/B3中的规范在40/s的剪切率下进行。
在制成后7天测定湿固化型组合物的结皮时间。使用刮刀(200 μm),将胶粘剂膜施加到预先用乙酸乙酯清洁的玻璃板上并立即置于干燥记录仪(BK 3干燥记录仪BYK-Gardner)中。针载重10 g并在35 cm距离上移动24小时的时期。该干燥记录仪位于23℃和50%空气相对湿度的气候控制室中。针的永久轨迹从膜上消失的时间被规定为结皮时间。
在进行实验时23℃的环境温度被称为RT(室温)。
在制成后7天,在具有楔形凹槽的特氟隆模具中测定湿固化型组合物的充分固化,在其最低点用层厚度测量仪测量并在凹陷开始处做一个标记。将密封剂/胶粘剂无气泡并过量地填充到凹槽中。使用卡片或日本抹刀(Japanspachtel)除去凸出的密封剂或胶粘剂。在气候控制室中在标准气候条件(23℃/50%空气相对湿度)下进行测试。从凹陷开始处的标记开始,在1或3天后小心除去密封剂/胶粘剂层直至在模具中留下未固化的材料。在边缘处标记这一点并将除去的密封剂/胶粘剂再放入模具并轻压到位。用尺子测量凹陷开始处的标记与这一标记之间的距离(相当于密封剂/胶粘剂的已固化长度)。根据下列公式计算充分固化D:D = (l×d)/L,其中l = 密封剂/胶粘剂的已固化长度[mm],L = 凹槽长度[mm]和d = 凹槽的最大深度[mm]。
通过手指轻压评估在固化24小时后的2 mm膜的粘性。评估该膜是否仍具有粘手感。
在可固化组合物的制剂中,添加剂和辅助剂具有如下含义:
名称 | 描述 | 制造商 |
Mesamoll® | 增塑剂 | Lanxess |
Fibadur® Schwarz 400724 | 颜料浆 | Fink |
Tronox® 8300 | 颜料 | Tronox Inc. |
Cab-O-Sil® TS 720 | 流变添加剂 | Cabot Corporation |
Socal® U1S2 | 填料 | Imerys Carbonates |
Dynasilan® VTMO | 干燥剂 | Evonik |
Lupragen® N700 | 催化剂(DBU) | BASF SE |
Tinuvin® 292 | 稳定剂 | BASF SE |
Tinuvin® 1130 | 稳定剂 | BASF SE |
Irganox® 1135 | 稳定剂 | BASF SE |
Dynasilan® 1505 | 附着力促进剂和/或交联剂 | Evonik |
Dynasilan® 1146 | 附着力促进剂和/或交联剂 | Evonik |
Jayflex® DINP | 增塑剂 | Exxon Mobil Chemical |
Dynasilan® 1189 | 附着力促进剂 | Evonik |
含烷氧基硅烷基团的聚氨酯的生产
实施例1-1(本发明):
使1174.0克OH值为13的丙二醇(Acclaim® Polyol 8200 N,CovestroDeutschland AG; Leverkusen DE)与147.2克Mesamoll®(Lanxess AG, Leverkusen, DE)和在63.5克异佛尔酮二异氰酸酯在添加80ppm的乙酰丙酮镱(III)情况下在60℃预聚合直至达到0.84%的理论NCO含量。然后快速滴加102.1g N-(3-三甲氧基甲硅烷基丙基)天冬氨酸二乙酯(根据EP-A 596 360,实施例5制造),搅拌直至在IR光谱中不再可见异氰酸酯谱带。所获得的包含烷氧基甲硅烷基端基的聚氨酯预聚物的粘度为21100 mPas。
实施例1-2(对比例)
重复实施例1中描述的程序,改动之处在于代替80ppm的乙酰丙酮镱(III),使用40ppm的二月桂酸二丁基锡。所获得的包含烷氧基甲硅烷基端基的聚氨酯预聚物的粘度为23500 mPas。
实施例1-3(本发明):
将1200.0g OH值为4.9的聚丙二醇(根据EP-A 0654302的实施例7制造)在80℃下真空干燥六小时。在冷却至60℃后,添加24.36克3-异氰酸根合丙基三甲氧基硅烷(Geniosil® GF40, Wacker AG, Burghausen)和100ppm乙酰丙酮镱(III),将反应预聚合直至达到0.05%的理论NCO含量。然后加入0.4克甲醇以捕获过量的NCO基团。搅拌直至在IR光谱中不再可见异氰酸酯谱带。所获得的包含烷氧基甲硅烷基端基的聚氨酯预聚物的粘度为69400 mPas(23℃)。
实施例1-4(对比例)
重复实施例3中描述的程序,改动之处在于,代替100ppm的乙酰丙酮镱(III),使用50ppm的二月桂酸二丁基锡。所获得的包含烷氧基甲硅烷基端基的聚氨酯预聚物的粘度为62200 mPas。
实施例1-5(对比例)
重复实施例3中描述的程序,改动之处在于,代替100ppm的乙酰丙酮镱(III),使用100ppm的K-Kat XK-614(基于锌的不含锡氨基甲酸酯化催化剂,King Industries公司)。所获得的包含烷氧基甲硅烷基端基的聚氨酯预聚物的粘度为70300 mPas。
湿固化型组合物的配制
根据下列程序制造湿固化型组合物:在带有蝶形搅拌器(Butterflyrührer)(200转/分钟)和溶解器搅拌圆盘(2500转/分钟)的实验室溶解器中在静态真空和冷却下分散表1中所列的除附着力促进剂外的所有组分15分钟。静态真空在此被理解为是指将该装置抽空到200毫巴的压力(动态真空),然后切断与真空泵的连接。选择冷却以在整个制造过程中不超过65℃的温度。然后加入附着力促进剂并在静态真空下分散该混合物另外10分钟。
关于制剂的下列数据以重量份计。
*: 对比例
实施例号 | 2-1 | 2-2* | 2-3 | 2-4* | 2-5* | 2-6* |
实施例1-1的聚合物 | 457.56 | |||||
实施例1-2的聚合物 | 457.56 | |||||
实施例1-3的聚合物 | 128.8 | |||||
实施例1-4的聚合物 | 128.8 | 160 | ||||
实施例1-5的聚合物 | 160 | |||||
Mesamoll® | 436.5 | 436.5 | ||||
Fibadur® Schwarz 400724 | 1.62 | 1.62 | ||||
Tronox® 8300 | 49.32 | 49.32 | 14.30 | 14.30 | ||
Cab-O-Sil® TS 720 | 20.52 | 20.52 | ||||
Socal® U1S2 | 761.76 | 761.76 | 234.1 | 234.1 | 240 | 240 |
Dynasilan® VTMO | 26.82 | 26.82 | 6.45 | 6.45 | 9.6 | 9.6 |
DBU | 1.26 | 1.26 | 0.45 | 0.45 | 0.16 | 0.16 |
Tinuvin® 292 | 10.26 | 2.15 | 2.15 | |||
Tinuvin® 1130 | 11.7 | 2.45 | 2.45 | |||
Irganox® 1135 | 6.12 | 1.30 | 1.30 | |||
Dynasilan® 1505 | 8.28 | 8.28 | ||||
Dynasilan® 1146 | 8.28 | 8.28 | 4.80 | 4.80 | ||
Jayflex® DINP | 106.15 | 106.15 | 96 | 96 | ||
Dynasilan® 1189 | 3.85 | 3.85 | ||||
总计 | 1800.00 | 1800.00 | 500.00 | 500.00 | 510.56 | 510.56 |
表1
实施例号 | 2-1 | 2-2* | 2-3 | 2-4* | 2-5* | 2-6* |
膜干燥 [min] | 45 | 30 | 75 | 65 | 115 | >360 |
粘性 24h | 无 | 无 | 无 | 无 | 无 | 是 |
完全固化 D [mm] 1 d | 4.3 | 3.6 | 4.2 | 4.2 | NB | NB |
完全固化 D [mm] 3 d | 5.6 | 5.3 | 6.0 | 6.3 | NB | NB |
表2; NB:未测定。
已经表明,与基于用二月桂酸二丁锡催化的含烷氧基硅烷基团的聚氨酯相比,根据本发明的组合物显示出在完全固化时可比较的值。膜干燥在每种情况下小于60分钟。对比例2-5*的组合物(含烷氧基硅烷基团的聚氨酯的锌催化)仅缓慢固化,如从长的膜干燥时间和24小时后的残留粘性可见。
从制剂中牵拉出厚度为2mm的膜并进行机械检查
实施例号 | 2-1 | 2-2* | 2-3 | 2-4* | 2-5* | 2-6* |
在14d 23℃/50% r.H.后的肖氏A | 30 | 41 | 13 | 23 | 48 | 45 |
在28d 23℃/50% r.H.后的肖氏A | 30 | 41 | NB | NB | NB | NB |
拉伸强度 [MPa] | 2.5 | 2.9 | 3.5 | 2.7 | 2.7 | 2.1 |
断裂伸长 [%] | 599 | 579 | 997 | 725 | 411 | 632 |
在100%伸长下的割线模量 [MPa] | 0.7 | 0.9 | 0.2 | 0.3 | 1.2 | 1.5 |
回弹性 | 90 | 93 | NB | NB | NB | NB |
表3。
已经表明,经固化的根据本发明的组合物与使用DBTL的各自对比例相比实现显著降低的在100%伸长下的割线模量,这对用作低模量建筑密封剂特别有利。与含锡(2-5)的制剂相比,基于锌化合物的无锡制剂(2-6)在100%伸长下在肖氏硬度和割线模量方面显示出可比较的高数值。
Claims (13)
1.生产含烷氧基硅烷基团的聚氨酯的方法,其包括使
含有至少一个NCO基团的化合物与
含有至少一个泽尔维季诺夫活性氢原子的化合物
在催化剂组分存在下反应的步骤,
其中所述含有至少一个NCO基团的化合物和/或所述含有至少一个泽尔维季诺夫活性氢原子的化合物含有至少一个烷氧基硅烷基团,
以获得含烷氧基硅烷基团的聚氨酯,
其特征在于
所述催化剂组分包括镧系元素与至少一个β-二酮配体的络合物,和
所述催化剂组分不含有机锡化合物,
所述镧系元素是镱(III),
和其中所述β-二酮配体可通过下列化合物脱质子获得:乙酰丙酮、全氟乙酰丙酮、苯甲酰基-2-呋喃甲酰基甲烷、l,3-双(3-吡啶基)-l,3-丙二酮、苯甲酰基三氟丙酮、苯甲酰基丙酮、二(4-溴)苯甲酰基甲烷、d,d-二龙脑基甲烷、4,4'-二甲氧基二苯甲酰基甲烷、2,6-二甲基-3,5-庚二酮、二萘甲酰基甲烷、二新戊酰基甲烷、二(全氟-2-丙氧基丙酰基)甲烷、1,3-二(2-噻吩基)-1,3-丙二酮、3-(三氟乙酰基)-d-樟脑、6,6,6-三氟-2,2-二甲基-3,5-己二酮、l,l,l,2,2,6,6,7,7,7-十氟-3,5-庚二酮、6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5-辛二酮、2-呋喃基三氟丙酮、六氟乙酰丙酮、3-(七氟丁酰基)-d-樟脑、4,4,5,5,6,6,6-七氟-1-(2-噻吩基)-1,3-己二酮、4-甲基苯甲酰基-2-呋喃甲酰基甲烷、6-甲基-2,4-庚二酮、2-萘甲酰基三氟丙酮、3-(5-苯基-l,3,4-噁二唑-2-基)-2,4-戊二酮、3-苯基-2,4-戊二酮、新戊酰基三氟丙酮、l-苯基-3-(2-噻吩基)-l,3-丙二酮、3-(叔丁基羟基亚甲基)-d-樟脑、三氟乙酰丙酮、1,1,1,2,2,3,3,7,7,8,8,9,9,9-十四氟-4,6-壬二酮、2,2,6,6-四甲基-3,5-庚二酮、4,4,4-三氟-1-(2-萘基)-l,3-丁二酮、2,2,6,6-四甲基-3,5-辛二酮、2,2,6-三甲基-3,5-庚二酮、2,2,7-三甲基-3,5-辛二酮、2-噻吩甲酰基三氟丙酮或其任意混合物。
2.根据权利要求1所述的方法,其特征在于所述镧系元素与至少一个β-二酮配体的络合物为乙酰丙酮镱(III),即Yb(acac)3。
3.根据权利要求1或2所述的方法,其特征在于所述含有至少一个NCO基团的化合物含有至少一个烷氧基硅烷基团,且所述含有至少一个泽尔维季诺夫活性氢原子的化合物不含烷氧基硅烷基团。
4.根据权利要求1或2所述的方法,其特征在于所述含有至少一个NCO基团的化合物不含烷氧基硅烷基团,且所述含有至少一个泽尔维季诺夫活性氢原子的化合物含有至少烷氧基硅烷基团。
5.根据权利要求4所述的方法,其特征在于所述含有至少一个泽尔维季诺夫活性氢原子的化合物含有至少一个伯或仲氨基。
6.含烷氧基硅烷基团的聚合物,其特征在于该聚合物包含镧系元素与至少一个β-二酮配体的络合物,并且该聚合物不含有机锡化合物,其中所述镧系元素是镱(III),并且所述β-二酮配体可通过下列化合物脱质子获得:乙酰丙酮、全氟乙酰丙酮、苯甲酰基-2-呋喃甲酰基甲烷、l,3-双(3-吡啶基)-l,3-丙二酮、苯甲酰基三氟丙酮、苯甲酰基丙酮、二(4-溴)苯甲酰基甲烷、d,d-二龙脑基甲烷、4,4'-二甲氧基二苯甲酰基甲烷、2,6-二甲基-3,5-庚二酮、二萘甲酰基甲烷、二新戊酰基甲烷、二(全氟-2-丙氧基丙酰基)甲烷、1,3-二(2-噻吩基)-1,3-丙二酮、3-(三氟乙酰基)-d-樟脑、6,6,6-三氟-2,2-二甲基-3,5-己二酮、l,l,l,2,2,6,6,7,7,7-十氟-3,5-庚二酮、6,6,7,7,8,8,8-七氟-2,2-二甲基-3,5-辛二酮、2-呋喃基三氟丙酮、六氟乙酰丙酮、3-(七氟丁酰基)-d-樟脑、4,4,5,5,6,6,6-七氟-1-(2-噻吩基)-1,3-己二酮、4-甲基苯甲酰基-2-呋喃甲酰基甲烷、6-甲基-2,4-庚二酮、2-萘甲酰基三氟丙酮、3-(5-苯基-l,3,4-噁二唑-2-基)-2,4-戊二酮、3-苯基-2,4-戊二酮、新戊酰基三氟丙酮、l-苯基-3-(2-噻吩基)-l,3-丙二酮、3-(叔丁基羟基亚甲基)-d-樟脑、三氟乙酰丙酮、1,1,1,2,2,3,3,7,7,8,8,9,9,9-十四氟-4,6-壬二酮、2,2,6,6-四甲基-3,5-庚二酮、4,4,4-三氟-1-(2-萘基)-l,3-丁二酮、2,2,6,6-四甲基-3,5-辛二酮、2,2,6-三甲基-3,5-庚二酮、2,2,7-三甲基-3,5-辛二酮、2-噻吩甲酰基三氟丙酮或其任意混合物,
并且其中所述聚合物是聚氨酯,该聚氨酯通过权利要求1至5之一所述的方法获得。
7.生产可固化聚合物的方法,其特征在于所述方法包括使权利要求6所述的聚合物与硅氧烷缩合催化剂接触的步骤。
8.根据权利要求7所述的方法,其特征在于使所述聚合物进一步与水接触。
9.可固化聚合物,其特征在于所述可固化聚合物通过根据权利要求7或8所述的方法获得。
10.经固化聚合物,其特征在于所述经固化聚合物通过固化根据权利要求9所述的可固化聚合物获得。
11.根据权利要求10所述的经固化聚合物,其特征在于所述经固化聚合物具有与对比聚合物相比的至少一个下列性质,其中各自的样品在测量前已在23℃和50%空气相对湿度下储存14天:
肖氏A硬度,根据DIN 53505测得:对比聚合物的≤90%;
断裂伸长百分比值,根据DIN EN 53504使用拉伸速度200mm/min和S2试样测得:对比聚合物的百分比值的≥101%;
割线模量,根据EN ISO 8339在100%伸长情况下测得:对比聚合物的≤90%;
并且其中所述对比聚合物以与所述经固化聚合物相同的方式但用相同摩尔量的二月桂酸二丁基锡代替所述方法中的催化剂组分中所述镧系元素与至少一个β-二酮配体的络合物制造。
12.根据权利要求9所述的可固化聚合物作为密封剂、胶粘剂或涂覆材料的用途。
13.根据权利要求10或11所述的经固化聚合物作为密封剂、胶粘剂或涂覆材料的用途。
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CN104395405A (zh) * | 2011-12-15 | 2015-03-04 | 莫门蒂夫性能材料股份有限公司 | 湿固化的有机聚硅氧烷组合物 |
CN105283484A (zh) * | 2013-06-11 | 2016-01-27 | Sika技术股份公司 | 基于含有硅烷基团的聚合物和锌催化剂的可固化组合物 |
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EP3727686A1 (de) | 2020-10-28 |
KR20200102999A (ko) | 2020-09-01 |
US20200392278A1 (en) | 2020-12-17 |
JP7423529B2 (ja) | 2024-01-29 |
EP3501641A1 (de) | 2019-06-26 |
EP3727686B1 (de) | 2023-05-10 |
WO2019121351A1 (de) | 2019-06-27 |
CN111479628A (zh) | 2020-07-31 |
JP2021507043A (ja) | 2021-02-22 |
US11834545B2 (en) | 2023-12-05 |
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