CN1259973A - 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 27
- 239000012963 UV stabilizer Substances 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 25
- 239000004417 polycarbonate Substances 0.000 claims abstract description 25
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical class OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003973 paint Substances 0.000 claims abstract description 13
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
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- 239000011248 coating agent Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 15
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910000077 silane Inorganic materials 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000005457 optimization Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 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
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 claims 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 6
- 150000004756 silanes Chemical class 0.000 abstract description 2
- 239000004922 lacquer Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- -1 siloxanes Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000004593 Epoxy Substances 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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
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- 239000000047 product Substances 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
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-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
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- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000006750 UV protection Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
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- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 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
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 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
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of 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; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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。
经常要为材料提供一个保护表面，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，即所谓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分的，它们分解太快和/或含有该稳定剂的硅氧烷体带有浅黄色。
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，优选氯、或C1-C12烷基，R3； 一个单键，C1-C12亚烷基、C5-C6环亚烷基或亚苯基，R4： H、碱金属、铵、碱土金属、C1-C12烷基、
烷基、C6-C12-芳基或
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1.4，优选大于2，特别优选大于8。
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1∶100。
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。
优选的式(1)的化合物是： 
式(1)的化合物或者是从文献中已知的，或者是用文献中已知的方法，例如根据EP-0057160公开于第7页的反应图式可以得到的。该专利申请在此引入作为参考，并因而是本发明公开内容的一部分。
含有环氧基团的硅烷通常取是指这样的化合物，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。
本发明优选采用的环氧硅烷为例如US-A-2946701所述者。它们是通式(2)或(3)的化合物：
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是甲基的那些化合物。它们都是市售品，特别是来自Union Carbide公司和Hüls AG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)的化合物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)的羟基苯并三唑的-R3-CO-OR4基的等化学计量更多。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1.4，优选大于2，特别优选大于8。
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，它优选通过缩合反应产生-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 3 790 527，3 865 755，3 887 514，4 243 720，4 278 804，4 680 232，4 006 271，4 476 281，in den DE-A 4 011 045，4 122 743，4 020 316，3 917 535，3 706 714，3 407 087，3 836 815，2 914 427，3 135 241，3 134 777，3 100 532，3 151 350，in den DE-A 3 005 541，3 014 411，2 834 606，2 947 879，3 016 021，2 914 427和4 338 361
和4 338 361，并且应该认为是本公开内容的一部分。
因此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特定材料的体系，所述特定材料选自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、氮化物和碳化物之中，并且颗粒大小的范围是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，例如见述于Becker/BraunKunststoffhandbuch，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℃的温度下固化。
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存在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”中的总概念。
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。不过作为例子，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 Jersey 07960，“聚(酯碳酸酯)共聚物的合成”发表在Journal of Polymer Science，Polymer Chemistry edition，第19卷，75-90(1980)；D.Freitag，U.Grigo，P.R.Muller，N.No紫外ertne’，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”，在Becker/Braun Kunststoff-Handbuch，volume 3/1，聚碳酸酯，聚缩醛，聚酯，纤维素酯，Carl HanserVerlag，Munich，Vienna，1992，117-299页。
热塑性聚碳酸酯的平均分子量
Mw(通过测定25℃在CH2Cl2中的相对粘度确定，浓度为每100ml CH2Cl20.5g聚合物)为12000-400000，优选18000-80000，特别是22000-60000。
本发明所以也提供涂敷的材料，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)紫外吸收原料
a1)2-(2-羟基-3-叔丁基-5-(2-羧乙基)苯基)苯并三唑，m.p.195℃(按EP 0057160，实施例1的方法制备)
a2)2-(2-羟基-3-环己基-5(3-羧丙基)苯基)苯并三唑
α)将132g(0.75 mol)的2-环己基苯酚溶于800ml的干氯苯中。然后在5-10℃加入200g(1.5mol)的AlCl3，随后在0-10℃加入73.5g(0.75mol)的马来酐在400ml氯苯中的溶液。在室温12小时后，将混合物倒入冰水中并用浓盐酸酸化。得到85g熔点为187-190℃的粉末。
β)将34.5g(0.25mol)的邻硝基苯胺在300ml水和69ml浓盐酸中搅拌。然后在5℃滴加入17.3g(0.25mol)的亚硝酸钠在155ml水中的溶液。然后将该溶液在5℃滴加到68.5g(0.25mol)的化合物α和79.5g(0.75mol)的碳酸钠在1升水的溶液中。得到117g熔点为155℃的固体。
γ)将42.5g(0.1mol)的偶氮染料β与200ml的2n氢氧化钠合并。然后加入50g锌粉，在1小时内倒入80ml的10n氢氧化钠，使得温度保持在45℃以下。然后将该混合物加热到90℃并保持4小时，过滤，滤液用盐酸酸化。从环己烷中重结晶后，得到31g 2-(2-羟基-3-环己基-5-(3-羧丙基)苯基)苯并三唑，该产物是无色结晶，熔点165℃。
b)由a1和3-缩水甘油基氧丙基三甲氧基硅烷(Glymo)制备的紫外稳定组合物
将50g a1和450g 3-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℃，同时进行搅拌和在这个温度下保持1小时。
可将这个混合物(混合物1)作如下变动：
混合物：2 100g a1 400g Glymo3 150g ” 350g ”4 200g ” 300g ”5 100g ” 400g α-(3，4-环氧基环己基)乙基
三甲氧基硅烷
c)根据DE-A2914427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)的胶体硅酸中。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，过滤稍混浊的溶液。
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。将这个混合物与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。
d)根据DE-A 4338361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。
e)紫外稳定的涂敷溶胶I和II
将60g份的本发明紫外稳定混合物2加到各为1000g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。
基体的涂敷和涂层性能的测试
将尺寸为105×150×4mm的双酚A聚碳酸酯板(Tg＝147℃，
Mw27500)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。
紫外暴露试验
根据DIN 53387-1-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耐候性的评定标准。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的耐气候试验后的Y.I.值试样 0h 1000h 2000h 3000h 5000h涂敷了紫外稳定的涂敷 2.1 2.2 2.7 2.8 4.3溶胶I(混合物2)的聚碳酸酯涂敷了紫外稳定的涂敷 2.5 2.7 3.2 3.3 4.8溶胶II(混合物2)的聚碳酸酯对比例涂敷了涂敷溶胶I 1.8 2.2 6.4a) 7.6a)-b)(无紫外稳定)的聚碳酸酯涂敷了涂敷溶胶II 1.9 2.6 6.3a) 7.9a)-b)(无紫外稳定)的聚碳酸酯a)开裂，漆膜脱离。b)无漆膜剩留。
Claims (10)
1.紫外稳定剂混合物，该混合物含有：A)通式(1)的羟基苯并三唑：
R1： H、C1-C18烷基、C5-C6环烷基或C6-C12芳基，R2： H、卤素，优选氯、或C1-C12烷基，R3： 一个单键，C1-C12亚烷基、C5-C6环亚烷基或亚苯基，R4： H、碱金属、铵、碱土金属、C1-C12烷基、
烷基、C6-C12-芳基或
芳基。
和
B) 含环氧基的可水解硅烷。
2.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1.4。
3.根据权利要求1或2的紫外稳定剂混合物，其特征在于通式(1)的羟基苯并三唑是采用下列羟基苯并三唑中的一个或几个。
4.制备根据权利要求1-3任一项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。
5.含有根据权利要求1-3任一项的紫外稳定剂混合物的硅氧烷体系。
6.含有根据权利要求4得到的紫外稳定剂混合物的硅氧烷体系。
7.根据权利要求5或6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。
8.含有根据权利要求5-7任一项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，优选Ti、Ce、Fe和Zr的氧化物、氧化水合物、氮化物和碳化物，其中材料的粒度是1-100nm。
9.根据权利要求8的硅氧烷涂料在涂敷任何一种基体材料，优选热塑性塑料，特别优选聚碳酸酯方面的应用。
10.被涂敷材料，优选聚碳酸酯，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8的硅氧烷涂料涂敷的。
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- 1998-05-28 DE DE59802740T patent/DE59802740D1/de not_active Expired - Fee Related
- 1998-05-28 US US09/445,113 patent/US6306512B1/en not_active Expired - Fee Related
- 1998-05-28 DK DK98929392T patent/DK0988340T3/da active
- 1998-05-28 JP JP50143499A patent/JP4228124B2/ja not_active Expired - Fee Related
- 1998-05-28 KR KR1019997011582A patent/KR100541298B1/ko not_active IP Right Cessation
- 1998-05-28 BR BR9810434-9A patent/BR9810434A/pt not_active IP Right Cessation
- 1998-05-28 ES ES98929392T patent/ES2167903T3/es not_active Expired - Lifetime
- 1998-05-28 ID IDW991375A patent/ID23428A/id unknown
- 1998-05-28 EP EP98929392A patent/EP0988340B1/de not_active Expired - Lifetime
- 1998-05-28 CN CN98806105A patent/CN1124309C/zh not_active Expired - Fee Related
- 1998-05-28 WO PCT/EP1998/003157 patent/WO1998056853A1/de active IP Right Grant
- 1998-05-28 AU AU79163/98A patent/AU7916398A/en not_active Abandoned
- 1998-05-28 IL IL13279598A patent/IL132795A0/xx unknown
- 1998-05-28 CA CA002293603A patent/CA2293603C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081900B (zh) * | 2005-06-01 | 2011-07-27 | 信越化学工业株式会社 | 含紫外线吸收性基团的有机聚硅氧烷、该聚硅氧烷的制法、及配合该聚硅氧烷的处理剂 |
| CN104562660A (zh) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | 基于苯并三唑类紫外线吸收剂的聚酯纤维及其制备方法 |
| CN104562302A (zh) * | 2013-10-11 | 2015-04-29 | 中国石油化工股份有限公司 | 一种抗紫外老化聚酯纤维及其制备方法 |
| CN104562302B (zh) * | 2013-10-11 | 2018-05-29 | 中国石油化工股份有限公司 | 一种抗紫外老化聚酯纤维及其制备方法 |
| CN104562660B (zh) * | 2013-10-11 | 2018-06-15 | 中国石油化工股份有限公司 | 基于苯并三唑类紫外线吸收剂的聚酯纤维及其制备方法 |
| WO2016107533A1 (zh) * | 2014-12-31 | 2016-07-07 | 蓝星有机硅（上海）有限公司 | 可固化的聚硅氧烷组合物 |
| CN105802238A (zh) * | 2014-12-31 | 2016-07-27 | 蓝星有机硅（上海）有限公司 | 可固化的聚硅氧烷组合物 |
| CN107345369A (zh) * | 2017-06-26 | 2017-11-14 | 苏州威尔德工贸有限公司 | 一种蚕丝织物用抗紫外线染色剂 |
| CN108486899A (zh) * | 2018-04-21 | 2018-09-04 | 湖南辰砾新材料有限公司 | 一种织物柔软整理剂及其制备方法 |
| CN108486899B (zh) * | 2018-04-21 | 2020-08-07 | 上海鑫妙纺织助剂有限公司 | 一种织物柔软整理剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4228124B2 (ja) | 2009-02-25 |
| AU7916398A (en) | 1998-12-30 |
| DE59802740D1 (de) | 2002-02-21 |
| DE19724397A1 (de) | 1999-01-14 |
| JP2002511894A (ja) | 2002-04-16 |
| EP0988340A1 (de) | 2000-03-29 |
| KR100541298B1 (ko) | 2006-01-12 |
| CA2293603C (en) | 2007-07-31 |
| CA2293603A1 (en) | 1998-12-17 |
| BR9810434A (pt) | 2000-09-19 |
| EP0988340B1 (de) | 2001-11-21 |
| ES2167903T3 (es) | 2002-05-16 |
| TW459011B (en) | 2001-10-11 |
| WO1998056853A1 (de) | 1998-12-17 |
| CN1124309C (zh) | 2003-10-15 |
| DK0988340T3 (da) | 2002-05-21 |
| IL132795A0 (en) | 2001-03-19 |
| US6306512B1 (en) | 2001-10-23 |
| KR20010013575A (ko) | 2001-02-26 |
| US20020002262A1 (en) | 2002-01-03 |
| ID23428A (id) | 2000-04-20 |
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