CN1127537C - 硅氧烷体系的紫外稳定剂 - Google Patents
硅氧烷体系的紫外稳定剂 Download PDFInfo
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000012963 UV stabilizer Substances 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 24
- 239000004417 polycarbonate Substances 0.000 claims abstract description 24
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical class OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003973 paint Substances 0.000 claims abstract description 13
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 20
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 229910000077 silane Inorganic materials 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000011236 particulate material Substances 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 150000004756 silanes Chemical class 0.000 abstract description 2
- 239000004922 lacquer Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- -1 siloxanes Chemical class 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
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- 239000004575 stone Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
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- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WEZYFYMYMKUAHY-UHFFFAOYSA-N tert-butyl 2,4-dibenzylpiperazine-1-carboxylate Chemical compound C1C(CC=2C=CC=CC=2)N(C(=O)OC(C)(C)C)CCN1CC1=CC=CC=C1 WEZYFYMYMKUAHY-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
- C09K15/328—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing boron, silicon, selenium or tellurium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
- C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract
本发明涉及硅氧烷漆体系的不挥发的紫外稳定混合物,该混合物的紫外稳定活性结构为羟基苯并三唑,所以它们尤其适合热塑性塑料,特别是芳族聚碳酸酯的紫外稳定作用。
Description
本发明涉及硅氧烷漆体系的不挥发的紫外稳定混合物,该混合物的紫外稳定活性结构为羟基苯并三唑,所以它们尤其适合热塑性塑料,特别是芳族聚碳酸酯的紫外稳定作用。
经常要材料为提供一个保护表面以保护它们免受有害的环境影响。硅氧烷基漆已被证明特别适合于这种目的,尤其是为材料提供一种抗刮性表面。
这些漆可含有所谓的紫外稳定物质以保护漆本身和底层材料,即基体免受有害的紫外辐射。除了提供长期的紫外保护外,对这些物质的一个特别要求是它们是不挥发的,以便它们能够均匀地分布在漆层中,并且无论在固化时还是随后的使用中不会从漆层中逸出。紫外稳定物质还必须不会快速地分解,必须经久地与漆均匀相混,并且含有紫外稳定物质的漆应该是透明的。
US-A-4278804和US-A-4051161涉及了紫外稳定活性物质和含有它们的漆。但是其中公开的物质存在一些缺点,它们提供的紫外保护是不充足的,它们分解太快和/或含有该稳定剂的硅氧烷体系带有浅黄色。
US-A-5438142还公开了紫外稳定活性物质,1-(3’-(苯并三唑-2”-基)-4’-羟苯基)-1,1-双(4-羟苯基)乙烷。但是这个活性物质的缺点是不能经久地与硅氧烷基漆相混。
所以本发明的目的是提供一种不具有上述缺点的紫外稳定剂体系。
本发明通过提供含有下面通式(1)的羟基苯并三唑和可水解的含环氧基的硅烷的紫外稳定混合物达到这个目的。
R1:H、C1-C18烷基、C5-C6环烷基或C6-C12芳基,
R2:H、卤素,优选Cl、或C1-C12烷基,
R3:H、C1-C12烷基、卤素,优选Cl或Br、或C6-C12芳基,
R4:H、C1-C18烷基或C6-C18芳基。
本发明还提供紫外稳定混合物,该混合物中硅烷的环氧基与通式(1)的羟基苯并三唑的摩尔比大于2.5,优选大于4,特别优选大于16。
但是硅烷的环氧基与通式(1)的羟基苯并三唑的摩尔比不应超过200∶1。
本发明的混合物适合于硅氧烷体系,特别是抗刮和抗磨的硅氧烷涂料的紫外稳定。这种紫外稳定的涂料,优选为漆,可用作所有类制品,如木类、织物类、纸类、石类制品的涂料,但是优选作为塑料、金属、玻璃和陶瓷类制品的涂料,特别优选用于涂敷热塑性塑料类且非常特别优选用于涂敷聚碳酸酯类。
用于本发明的不挥发紫外稳定混合物的羟基苯并三唑是通式(1)的化合物。
但是优选使用1-(3’-(苯并三唑-2”-基)-4’-羟苯基)-1,1-双(4-羟苯基)乙烷(下文缩写为THPE-BZT)。THPE-BZT的生产方法详述于US-A-5438142,其中通用的合成路线公开于所述专利的图式1。该产物有Hoechst/Celanese公司的市售品。
含有环氧基团的硅烷通常是指这样的化合物,一方面它们具有至少一个环氧环同时含有在水解条件下形成硅醇结构的基团。
R5是具有最多9个碳原子的二价烃基或具有最多9个碳原子的由C、H和O原子组成的二价基团,其中O原子作为醚键基团存在。R5优选-CH2OCH2CH2CH2-。
R6是具有最多4个碳原子的脂族烃基、具有最多4个碳原子的酰基或式(CH2CH2O)nZ的基团,其中n至少为1且Z为具有最多4个碳原子的脂族烃基;
m是0或1。
这些环氧硅烷的制备也描述于US-A-2946701中。所以所述专利列于此作为参考。特别优选的环氧硅烷是其中R6是甲基或乙基的那些化合物。它们都是市售品,特别是来自Union Carbide公司和HlsAG公司的产品如:
A-187或Dynasilan Glymo 3-缩水甘油基氧丙基三甲氧基硅烷
A-186 2-(3,4环氧环己基)乙基三甲氧基硅烷
紫外稳定混合物的制备
紫外稳定混合物是通过将通式(1)的羟基苯并三唑与可水解的含环氧基的硅烷均匀地混合,并加热这些混合物而制备的。加热应该在至少90℃进行至少30分钟。加热时的温度应该优选高于120℃。
已经证明采用这样的混合比是特别有利的,在这个混合比环氧基要比通式(1)的羟基苯并三唑两个自由酚羟基的等化学计量更多,所述两个酚羟基是通式(1)的羟基苯并三唑的紫外稳定作用不需要的。所以,硅烷的环氧单元与通式(1)的羟基苯并三唑的摩尔比应该大于2.5,优选大于4,特别优选大于16。
紫外稳定组分不必分开制备,以便可随后加到要被稳定的硅氧烷体系中,但也可以在合成硅氧烷体系/硅氧烷涂料时,作为一个辅助步骤被就地合成。
硅氧烷体系/硅氧烷涂料
硅氧烷体系基本上是热固化体系,它优选通过编合反应产生-Si-O-Si-链接而交联。其他的交联历程可以平行地进行。这种体系描述于例如
US-A 3 790 527,3 865 755,3 887 514,4 243 720,4 278 804,4 680232,4 006 271,4 476 281,DE-A 4 011 045,4 122 743,4 020 316,3 917 535,3706 714,3 407 087,3 836 815,2 914 427,3 135 241,3 134 777,3 100 532,3 151350,DE-A 3 005 541,3 014 411,2 834 606,2 947 879,3 016 021,2 914 427和4 338 361,并且应该认为是本公开内容的一部分。
本发明也提供根据本发明的紫外稳定的硅氧烷体系。
优选使用的硅氧烷体系是那些含有颗粒材料的体系,所述颗粒材料选自Si、Al、Sb和B以及过渡金属,优选Ti、Ce、Fe和Zr的氧化物、氧化水合物、氮化物和碳化物,并且粒度为1-100nm,优选2-50nm。
本发明的紫外稳定混合物加到硅氧烷体系中的量,相对于硅氧烷体系的固含量,应该是这样的,即相对于硅氧烷体系的固含量,羟基苯并三唑的比例为0.3-20,优选3-15,特别优选为5-10%(重量)。
有关硅氧烷基抗刮涂料体系的制备方法及其组分可以参考DE-A-2914427和DE-A-4338361,这些文献因而是本说明书的一部分。
基体,材料
含有本发明的紫外稳定混合物的硅氧烷体系可以用作本体材料和用作涂敷材料。对于选择要涂敷的基体材料没有限制。这些紫外稳定的涂料优选适合于涂敷木类、织物类、纸类、石类制品、金属、玻璃、陶瓷和塑料且特别优选用于涂敷热塑性塑料类,见述于Becker/Braun Kunststoffhandbuch,Carl Hanser Verlag,Munich,Vienna,1992。它们非常特别适合于涂敷透明的热塑性塑料,优选聚碳酸酯。
可以采用常规的涂敷方法进行涂敷,例如浸涂、溢涂、倾涂、旋涂、喷涂或刷涂。
施涂膜厚例如为2-200μm,优选2-30μm,特别优选5-15μm。基体在涂敷涂料之前可以任选用偶联剂或底涂打底。
漆优选在>90℃温度下固化。
对本发明来说,热塑性的芳族聚碳酸酯包括均聚碳酸酯和共聚碳酸酯两者;该聚碳酸酯按已知的方式可以是线性的或支化的。
在适合的聚碳酸酯中,一部分,最多80%(摩尔),优选20-50%(摩尔),碳酸酯基团可被芳族二羧酸酯基所代替。这种聚碳酸酯,其中含有进入分子链的碳酸的酸根和芳族二羧酸的酸根两者,更精确地应称为聚酯碳酸酯。它们包含在术语“热塑性、芳族聚碳酸酯”的总概念中。
在过去约40年内,详细描述聚碳酸酯制备的专利已有几百篇。仅作为例子,可以参考的文献有:“Schnell,聚碳酸酯的化学和物理”,Polymer Reviews,第9卷,Interscience出版社,纽约,伦敦,悉尼1964;D.C.Prevosek,B.T.Debona & Y.Kesten,企业研究中心,联合化学公司,Morristown,New Jersey07960,“聚(酯碳酸酯)共聚物的合成”发表在Journal of Polymer Science,PolymerChemistry edition,第19卷,75-90(1980);D.Freitag,U.Grigo,P.R.Muller,N.Nouvertne’,拜尔公司,“聚碳酸酯”,聚合物科学和工程大全,第11卷,第2版1988,648-718页;最后U.Grigo博士,K.Kircher博士和P.R.Muller博士,“聚碳酸酯”,见Becker/Braun Kunststoff-Handbuch,volume3/1,聚碳酸酯,聚缩醛,聚酯,纤维素酯,Carl Hanser Verlag,Munich,Vienna,1992,117-299页。
热塑性聚碳酸酯的平均分子量
(通过测定25℃在CH2Cl2中的相对粘度确定,浓度为每100ml CH2Cl2 0.5g聚合物)为12000-400000,优选18000-80000,特别是22000-60000。
所以本发明也提供涂敷的材料,优选为聚碳酸酯且特别优选为具有抗刮涂层的聚碳酸酯。
实施例
实施例1:
a)THPE-BZT和3-缩水甘油基氧丙基三甲氧基硅烷(Glymo)的紫
外稳定的混合物
将50gTHPE-BZT和450g3-缩水甘油基氧丙基三甲氧基硅烷导入一个容器中,并在氮气氛下加热到140-150℃,同时进行搅拌并在这个温度下保持1小时。
可将这个混合物(混合物1)作如下变动:
混合物:
2 100gTHPE-BZT 400g Glymo
3 150g ″ 350g ″
4 200g " 300g ″
5 100gTHPE-BZT 400g α-(3,4-环氧基环己基)乙基
三甲氧基硅烷
b)根据DE-OS2914427制备硅氧烷涂料(涂敷溶胶I)
α)将19.8g冰醋酸,210g蒸馏水和227g异丙醇加到300g SiO2含量为30%(重量)的硅溶胶中。充分混合后,加入900g甲基三乙氧基硅烷,在搅拌下将该混合物加热到60℃。让混合物在此温度下保持4小时,然后再往混合物中加入1200g异丙醇。一旦产物被冷却到室温,过滤稍浑浊的溶液。
β)将340g异丙醇、190g四乙氧基硅烷和360g甲基三乙氧基硅烷导入装有搅拌器和回流冷凝器的容器中。将此混合物与180g的0.05n盐酸合并,并回流5小时进行共水解。反应后混合物被冷却到室温。得到的溶液是四乙氧基硅烷的部分水解物(按SiO2计算为5.1%)和甲基三乙氧基硅烷的部分水解物(按CH3SiO1.5计算为12.6%)。
用作涂敷材料之前,将α)和β)两组分按1∶1的比例混合在一起,并且溶解于由60份(重量)正丁醇、40份(重量)乙酸和20份(重量)甲苯组成的混合物中。
c)根据DE-OS4338361制备硅氧烷涂料(涂敷溶胶II)
通过将12.82g乙酸稳定的(6.4%(重量)乙酸)勃姆石粉末与104.62g0.1n盐酸合并制备勃姆石溶胶。随后超声(20分钟)制成透明的无色溶液,将24.3g该溶液与由118.17g GPTS(3-缩水甘油基氧丙基三甲氧基硅烷)和62.50g TEOS(原硅酸四乙酯)制成的混合物合并。反应混合物在室温下搅拌2小时,然后在用冰冷却的同时与18.93g三丁氧基乙酸铝化合。产生的透明溶胶在室温下搅拌2小时,然后在用冰冷却的同时与93.14g上述勃姆石溶胶和79.30g丁氧基乙醇合并。
d)紫外稳定的涂敷溶胶I和II
将75g份的本发明紫外稳定混合物2加到各为1000g份的涂敷溶胶I和II中。用Beckmann DU光度计在波长250-600nm范围内测定涂敷了这些组合物的硅玻璃的紫外光的透过性。涂膜的厚度为5μm,吸收了>98%波长<350nm的对聚碳酸酯是临界的辐射。
e)基体的涂敷和涂层性能的测试
将尺寸为105x150x4mm的双酚A聚碳酸酯板(Tg=147℃,17500)用异丙醇洗净并通过浸入由3%(重量)氨基丙基三甲氧基硅烷和97%(重量)乙二醇单丁醚制备的混合物中打底,随后在130℃下热处理30分钟。然后将该板以浸入速度V=100cm/min涂上一层20μm的涂敷溶胶I或II的膜。在室温下闪蒸10分钟后使涂敷的板在130℃下干燥1小时。干燥后抗刮漆膜的厚度约为5μm。完全固化后,涂敷板在室温下储存2天,然后暴露在定义量的紫外辐射下。
紫外基露试验
根据DIN53387-1-A-X,将聚碳酸酯板暴露在带有喷水循环的过滤的氙弧辐射中,试验的条件如下:
耐候试验设备: Xenon-WOM
在340nm的辐射强度: 0.35W/m2(优选)
过滤器组合: 内部:Pyrex(耐热玻璃),外部:Pyrex
黑板温度: 60℃±5℃
黑体标准温度 65℃±3℃
运行模式: 恒定
喷水循环: 102∶18
空气相对湿度: 60-80%
随暴露时间而变的泛黄情况可以用作为涂敷漆板的耐侯性的评定标准。板的相应黄度可以根据ASTM D 1925-70规定的黄度指数(Y.I.)确定。
在Xenon-WOM 102∶18的耐候试验后的Y.I.值 试样 0h 1000h 2000h 3000h 5000h涂敷了紫外稳定的涂敷 2.1 2.3 2.7 2.9 4.3溶胶I(混合物2)的聚碳酸酯涂敷了紫外稳定的涂敷 2.4 2.6 3.1 3.2 4.9溶胶II(混合物2)的聚碳酸酯
对比例涂敷了实施例1e的涂敷1.9 2.6 6.3a) 7.9a) -b)溶胶II(无紫外稳定)的聚碳酸酯
a)开裂,漆膜脱离。
b)无漆膜剩留。
Claims (15)
2.如权利要求1所述的紫外稳定剂混合物,其特征在于所述R3基团是氯或溴。
3.根据权利要求1的紫外稳定剂混合物,其特征在于硅烷的环氧基与通式(1)的羟基苯并三唑的摩尔比大于2.5。
4.根据权利要求1-3之一的紫外稳定剂混合物,其特征在于通式(1)的羟基苯并三唑是1-(3’(苯并三唑-2″-基)-4’-羟苯基)-1,1-双(4-羟苯基)乙烷。
5.制备根据权利要求1-3之一的紫外稳定剂混合物的方法,其特征在于将通式(1)的羟基苯并三唑与可水解的含环氧基的硅烷混合,并加热到至少90℃,加热至少30分钟。
6.含有根据权利要求1-3之一的紫外稳定剂混合物的硅氧烷体系。
7.含有根据权利要求5得到的紫外稳定剂混合物的硅氧烷体系。
8.根据权利要求6或7的硅氧烷体系,其特征在于羟基苯并三唑相对于硅氧烷体系固含量的比例是0.3-20。
9.含有根据权利要求6-8之一的硅氧烷体系和任选的颗粒材料的硅氧烷涂料,所述颗粒材料选自Si、Al、Sb和B以及过渡金属的氧化物、氧化水合物、氮化物和碳化物,其中的材料的粒度是1-100nm。
10.如权利要求9所述的硅氧烷涂料,其特征在于所述过渡金属选自Ti、Ce、Fe和Zr。
11.根据权利要求9或10的硅氧烷涂料在涂敷任何一种基体材料方面的应用。
12.如权利要求11所述的应用,其特征在于所述基体材料是热塑性塑料。
13.如权利要求11或12所述的应用,其特征在于所述基体材料是聚碳酸酯。
14.被涂敷材料,其特征在于至少是暴露于辐射中的材料表面是用根据权利要求9或10的涂料涂敷的。
15.如权利要求14所述的被涂敷材料,其特征在于该材料是聚碳酸酯。
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- 1997-06-10 DE DE19724396A patent/DE19724396A1/de not_active Ceased
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- 1998-05-15 TW TW087107509A patent/TW459012B/zh active
- 1998-05-28 AU AU81073/98A patent/AU728989B2/en not_active Ceased
- 1998-05-28 WO PCT/EP1998/003156 patent/WO1998056852A1/de active IP Right Grant
- 1998-05-28 AT AT98930746T patent/ATE309297T1/de not_active IP Right Cessation
- 1998-05-28 DE DE59813180T patent/DE59813180D1/de not_active Expired - Fee Related
- 1998-05-28 CN CN98806100A patent/CN1127537C/zh not_active Expired - Fee Related
- 1998-05-28 KR KR1019997011581A patent/KR100543156B1/ko not_active IP Right Cessation
- 1998-05-28 ES ES98930746T patent/ES2252844T3/es not_active Expired - Lifetime
- 1998-05-28 JP JP50143399A patent/JP4246269B2/ja not_active Expired - Fee Related
- 1998-05-28 BR BR9810611-2A patent/BR9810611A/pt not_active IP Right Cessation
- 1998-05-28 IL IL13279498A patent/IL132794A0/xx unknown
- 1998-05-28 US US09/445,233 patent/US6288150B1/en not_active Expired - Fee Related
- 1998-05-28 ID IDW991376A patent/ID23376A/id unknown
- 1998-05-28 EP EP98930746A patent/EP0991709B1/de not_active Expired - Lifetime
- 1998-05-28 CA CA002293619A patent/CA2293619C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1993015063A1 (en) * | 1992-02-03 | 1993-08-05 | Hoechst Celanese Corporation | Uv light stabilizing, antioxidant and colorant compounds |
US5556936A (en) * | 1994-11-17 | 1996-09-17 | General Electric Company | Aromatic polycarbonates having polyfunctional UV screening units, method for making and use |
EP0732355A1 (en) * | 1995-03-18 | 1996-09-18 | General Electric Company | Coated polycarbonate articles |
Also Published As
Publication number | Publication date |
---|---|
TW459012B (en) | 2001-10-11 |
IL132794A0 (en) | 2001-03-19 |
CA2293619C (en) | 2007-07-24 |
AU728989B2 (en) | 2001-01-25 |
EP0991709A1 (de) | 2000-04-12 |
JP2002504165A (ja) | 2002-02-05 |
ATE309297T1 (de) | 2005-11-15 |
DE59813180D1 (de) | 2005-12-15 |
EP0991709B1 (de) | 2005-11-09 |
ES2252844T3 (es) | 2006-05-16 |
ID23376A (id) | 2000-04-20 |
CN1259972A (zh) | 2000-07-12 |
WO1998056852A1 (de) | 1998-12-17 |
CA2293619A1 (en) | 1998-12-17 |
KR100543156B1 (ko) | 2006-01-20 |
KR20010013574A (ko) | 2001-02-26 |
US6288150B1 (en) | 2001-09-11 |
AU8107398A (en) | 1998-12-30 |
BR9810611A (pt) | 2000-09-12 |
JP4246269B2 (ja) | 2009-04-02 |
DE19724396A1 (de) | 1998-12-24 |
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