CN1461320A - 含氟嵌段多异氰酸酯 - Google Patents
含氟嵌段多异氰酸酯 Download PDFInfo
- Publication number
- CN1461320A CN1461320A CN01815988A CN01815988A CN1461320A CN 1461320 A CN1461320 A CN 1461320A CN 01815988 A CN01815988 A CN 01815988A CN 01815988 A CN01815988 A CN 01815988A CN 1461320 A CN1461320 A CN 1461320A
- Authority
- CN
- China
- Prior art keywords
- fluorine
- lacquer
- block
- polyisocyanates
- equivalent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 48
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 48
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 46
- 239000011737 fluorine Substances 0.000 title claims abstract description 45
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 title abstract 2
- 239000004033 plastic Substances 0.000 claims abstract description 6
- 229920003023 plastic Polymers 0.000 claims abstract description 6
- 239000004814 polyurethane Substances 0.000 claims abstract description 4
- 229920002635 polyurethane Polymers 0.000 claims abstract description 4
- 239000004922 lacquer Substances 0.000 claims description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001298 alcohols Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000008393 encapsulating agent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000003373 anti-fouling effect Effects 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- PGRFXXCKHGIFSV-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-iodobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)I PGRFXXCKHGIFSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- UXPOJVLZTPGWFX-UHFFFAOYSA-N pentafluoroethyl iodide Chemical compound FC(F)(F)C(F)(F)I UXPOJVLZTPGWFX-UHFFFAOYSA-N 0.000 claims description 2
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000000470 constituent Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 210000003298 dental enamel Anatomy 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- -1 isocyanuric acid ester Chemical class 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- 238000009736 wetting Methods 0.000 description 8
- 208000028626 extracranial carotid artery aneurysm Diseases 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 3
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 2
- TWXXOQFVDMSLCK-UHFFFAOYSA-N 4-isocyanatobicyclo[2.2.1]heptane Chemical class C1CC2CCC1(N=C=O)C2 TWXXOQFVDMSLCK-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- 229920005789 ACRONAL® acrylic binder Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical compound CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012628 flowing agent Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
-
- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/8087—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing halogen atoms
-
- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/8074—Lactams
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及新颖的含氟嵌段多异氰酸酯，其制备及其用途，用于生产聚氨酯塑料，优选用作烘烤瓷漆、特别是卷材涂料方法的交联剂。
Description
本发明涉及新的含氟嵌段多异氰酸酯、其制备、及其在制备聚氨酯塑料中、优选作为烘烤漆(Einbrennlacke)的交联组分、尤其是用于卷材涂覆工艺的用途。
嵌段多异氰酸酯与含OH的缩聚物或聚合物(聚酯或聚丙烯酸酯)的配制剂产生“一组分”烘烤漆的粘合剂是现有技术。为了获得特殊的防水和防污漆表面而将氟掺入漆粘合剂中也是现有技术。
在各种专利文献出版物中，氟是作为涂料组合物的OH或NCO组分中的改性组分而被提及的。
在例如美国专利说明书5 541 281和5 576 411中描述了具有掺入氟成分的嵌段多异氰酸酯。这涉及具有脲基甲酸酯、异氰脲酸酯和尿烷基团的多异氰酸酯，它们是通过氟取代醇与单体二异氰酸酯反应而制备的。对于熟练技术人员而言可以理解的是，由原料异氰酸酯制备含氟多异氰酸酯是比较昂贵的工艺，这尤其是因为要进行薄膜蒸馏以除去有毒的原料异氰酸酯(纯化)。此外必须考虑的是，这样的含氟异氰酸酯应用领域有限，因此是所谓的小生境产品(Nischenprodukte)。
因此本发明的目的是为制备含氟多异氰酸酯提供另一供选择的解决方案。已知途经的另一供选择的方式是用氟代醇对市售漆多异氰酸酯进行改性。
因此本发明的目的是利用简单方法由常规漆用多异氰酸酯(Lackpolyisocyanaten)开发含氟嵌段多异氰酸酯，其可用于制备聚氨酯塑料，尤其是用于制备具有防水和防污表面的烘烤漆。
用根据本发明的嵌段多异氰酸酯实现这一目的。
本发明的主题是嵌段含氟多异氰酸酯，其包含：
i)100当量％的脂族多异氰酸酯或多异氰酸酯混合物，NCO含量为10-25重量％，官能度为至少2.5，
ii)75-95当量％的异氰酸酯封闭剂，和
iii)5-25当量％的氟化单醇，
其中，iii)和ii)的量之和为100当量％，并且其中基于i+ii+iii的量以F＝19计算的氟含量结果为1.0-20.0重量％，优选4.0-10.0重量％，并任选地包含常规添加剂和辅助物质。
对于本发明重要的是，所述新的嵌段多异氰酸酯是由以下三种组分构成的：
-脂族多异氰酸酯，
-NCO封闭剂，和
-氟化脂族单醇。
另外，还可包含其它的常规添加剂和辅助物质，比如溶剂、流动剂(比如Acronal 4F(BASF)或Tego Protect 5002(Goldschmidt)、防止热泛黄的抗氧化剂或稳定剂，比如EP-A 0 829 500中所述的。
本发明还提供一种制备嵌段含氟多异氰酸酯的工艺方法，特征在于首先在50-70℃的温度下伴随搅拌加入多异氰酸酯(任选地是在溶剂中)，随后加入单官能的氟取代醇，然后在80-110℃进行反应至达到计算的NCO含量，随后使剩余的NCO基团与相应量的封闭剂在70-100℃进行反应。这样，NCO基团不再能被例如红外光谱的手段检测到。
所述本身已知的漆用多异氰酸酯包含缩二脲、异氰脲酸酯、脲基甲酸酯、亚氨基噁二嗪二酮(不对称三聚物)、尿烷和/或尿二酮(Uretdion)基团，并且是基于(环)脂族二异氰酸酯，NCO含量为12-25重量％，这些漆用多异氰酸酯可以用于制备本发明的多异氰酸酯。脂族和环脂族二异氰酸酯的实例是1，6-二异氰酸根络己烷(HDI)，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)，双-(4-异氰酸根合环己基)-甲烷(H12MDI或Desmodur W/Bayer AG)，2，6-和2，5-双异氰酸根合-降莰烷或1，4-双异氰酸根合甲基-环己烷和1，3-或1，4-四甲基亚二甲苯基-二异氰酸酯。优选主要含有异氰酸酯基团且基于1，6-二异氰酸根络己烷、IPDI和Desmodur W的多异氰酸酯。
作为本发明多异氰酸酯的封闭剂可以使用肟(比如丁酮肟)、仲脂族胺(比如二异丙基胺)、CH-酸化合物(比如丙二酸酯或乙酰乙酸酯)、NH-酸杂环化合物(比如1，2，4-三唑、咪唑或3，5-二甲基吡唑)、内酰胺(比如ε-己内酰胺)、醇(比如甲醇、乙醇或正丙醇)、或这些封闭剂的任何所需混合物。特别优选的是ε-己内酰胺、二异丙基胺或乙醇。
分子量为150-500且氟含量为30-80重量％的脂族或环脂族醇原则上被考虑为制备本发明多异氰酸酯的氟单元。优选生成相应氟化醇的全氟乙基碘化物、全氟丁基碘化物或全氟己基碘化物在烯丙基醇上的加成产物，所述氟化醇比如五氟戊-1-醇(M178，氟含量：53％)，九氟庚-1-醇(C7H7F9O，M 278，F＝61.5％)和十一氟壬-1-醇(M 378，F＝55％)。特别优选4，4，5，5，6，6，7，7，7-九氟庚-1-醇，这公开于例如如下参考文献：N.O.Brace，J.Fluorine Chem.1982，20，313-328。
本发明的另一主题是本发明的含氟嵌段多异氰酸酯在聚氨酯塑料制备中作为交联剂的用途。
本发明的含氟嵌段多异氰酸酯优选用作交联剂(组分)，以制备聚氨酯漆的粘合剂。
为了由作为交联剂的本发明的多异氰酸酯和例如OH组分制备储藏稳定的漆粘合剂，优选使用的嵌段NCO基团与OH基团的当量比例为1∶1。可能的OH组分是聚氨酯化学中和优选是在漆技术中常规的含OH和/或含NH的组分，例如含OH基团的聚(甲基)丙烯酸酯、多元醇、聚酯多元醇、聚酯氨基甲酸酯、(聚)氨基醇、多胺等。
因此，本发明的另一主题是漆用粘合剂，其含有本发明的氟化嵌段多异氰酸酯和含OH和/或NH的交联组分及任选的常规添加剂和/或辅助物质。
用本发明的含氟嵌段多异氰酸酯作为交联剂制备的漆赋予得到的漆表面防水并从而自清洁的性能。它们用于涂覆所需的基材，比如石材、砖石建筑、水泥、木材、玻璃、陶瓷、塑料和金属的表面。它们优选用于涂覆金属片材，比如车身元件。
因此本发明的另一主题是用含本发明的嵌段含氟多异氰酸酯的漆涂覆的基材。
另一方面，水湿润角和临界倾斜角被用作评估这些性能的物理测量参数。测量水湿润角的仪器市售可得。
漆表面上水滴的水湿润角提供有关该滴在漆上润湿度的信息。水湿润角本身由向位于平面上的该滴投射一条切线而产生。如果该滴的曲度为半球形，则该切线与漆表面形成90°角(图1)。在防水表面上，相同体积的水滴被表面推开更远，润湿面积变得更小，而测得的水润湿角大于90°。在极端情况下，比如用汞滴的情况下，与表面的接触只在一点发生。这样水润湿角为180°。
小于90°的润湿角(图2)导致流动的水滴，其不再具有球形，而是具有类穹形。
通过实验已经发现，在具有大于90°的水润湿角和最低可能的倾斜角的表面上水滴开始滚开，附着的污垢随着该滚开被带走。
本发明的氟化嵌段多异氰酸酯可以通过简单的方式用工业上大规模可得的漆用多异氰酸酯制备。使用所述新的交联剂，得到了具有良好防水和防污性能的卷材涂料漆，如以下实施例中所详述。
实施例
实施例1
4，4，5，5，6，6，7，7，7-九氟庚-1-醇的制备
这一全氟化醇可以通过文献中已知的方法制备，即通过使市售的全氟丁基碘化物自由基加成到烯丙基醇上，随后用例如氢化锂铝进行加氢脱碘化(N.O.Brace.J.Fluorine Chem.1982，20，313-328)。
这种醇为无色液体(b.p.50mbar 83-85℃)，分子量为278，氟含量为171g或61.5％。
实施例2(根据本发明)
用根据实施例1的全氟化醇制备嵌段多异氰酸酯交联剂
批量：
| 58.8g | (0.3当量) | 含异氰尿酸酯的漆用多异氰酸酯，基于1，6-二异氰酸根络己烷(HDI)，NCO含量为21.4％，23℃时的粘度约为3000mPas，官能度(F)约为3.5 |
| 245.0g | (0.7当量) | 含异氰尿酸酯的漆用多异氰酸酯，基于1-异氰酸根合-3，3，5-三甲基-5-异氰酸根合甲基-环己烷(IPDI)，NCO含量为12.0％，在溶剂石脑油100中溶解70％，F＝3.2 |
| 27.8g | (0.1当量) | 根据实施例1的全氟代醇 |
| 102.0g | (0.9当量) | ε-己内酰胺 |
| 80.0g | 醋酸1-甲氧基-丙基酯(MPA) | |
| 80.0g | 异丁醇 | |
| 593.6g | (0.9当量) | 嵌段NCO基团 |
固体含量(计算)： 60.6％
基于固体的氟含量： 17.1g或4.7％
23℃时的粘度： 约850mPas
嵌段NCO当量(计算)： 660g
程序：
将两种多异氰酸酯、MPA和全氟化醇在搅拌下加热至100℃。随后在100℃下将该混合物搅拌约1小时，直至NCO含量达到计算的9.2％或刚刚低于该水平。然后加入全量的固体己内酰胺，随后在110℃搅拌该混合物，直至在大约2小时后NCO含量不再被例如红外光谱检测到。加入异丁醇，使所述混合物冷却，得到特征如上所述的交联剂溶液，其嵌段NCO当量为660g。
实施例3(对比)
利用实施例2的多异氰酸酯组分和ε-己内酰胺，制备类似的交联剂，但无全氟代醇。这种交联剂的固体含量为65％，嵌段NCO当量为528g。
实施例4(根据本发明)
描述卷材涂料粘合剂和卷材涂料透明漆的制备以及这些烘烤漆的检测。
a)粘合剂
粘合剂I
| 组分 | 当量重量[g] | 固体[g] | 基于固体的F含量[g]/[％] | 漆批料的量[基于100重量％] |
| Alkynol16651)根据实施例2的交联剂 | 1000660 | 650.0360.1 | -17.1/4.7 | 45.530.0 |
| 粘合剂I | 1010.1 | 17.1/1.69 | 75.5 |
粘合剂I包含1.69重量％(基于固体)的掺合形式的氟。
粘合剂II
| 组分 | 当量重量[％] | 固体[g] | 漆批料的量[基于100重量％] |
| Alkynol16651)根据实施例3的交联剂(对比) | 1000528 | 650.0343.2 | 48.025.3 |
1)Alkynol1665，羟基聚酯，65％于溶剂石脑油100/异丁醇中，1.7重量％ OH基团，Bayer AG
粘合剂II不含结合的氟。
b)透明漆的组成
| 透明漆组分 | 漆I | 漆II(对比) |
| Alkynol1665实施例2的交联剂实施例3的交联剂CAB 531-12)10％于SN 200S3)中溶剂石脑油100二丙酮醇醋酸1-甲氧基丙基酯二月桂酸二丁锡4)，10％于SN 100中 | 45.530.0-4.3-9.49.41.4 | 48.0-25.36.119.2--1.4 |
| 总量[重量份]固体含量[％]每漆批量的氟[％] | 100.0约480.85 | 100.0约48- |
2)乙酰丁酸纤维素，Krahn Chemie Hamburg，制造商EastmanChemicals，Kingsport/USA
3)溶剂石脑油，Deutsche Exxon Chemica GmbH，Kln
4)Air Products，USA
用Skandex混和机均匀混和所述透明漆批料。通过加入溶剂石脑油200S将所述漆调至加工粘度(约70秒DIN 4/23℃)。
将所述透明漆用刮刀涂布法涂覆至铬化铝片材(1mm厚度)上。在涂覆该漆后，立即在Aalborg烘箱中的转台(烘箱温度为350℃)上对所述片材/漆进行烘烤。在350℃放置38秒钟后，物体温度(PMT)确定为232℃。在以干层厚度为8-10μm涂覆上述透明漆之前，已经涂覆了一层棕色底漆(19-22μm)。
c)透明漆性能
| 漆I | 漆II(对比) | |
| 水润湿角临界倾斜角炭黑挟带作用2)流[0＝很好；5＝差]层厚[μm](ECCA-T1)1)Gardner光泽20°/60°(ECCA-T2)1)MEK擦拭作用，双击2kg(ECCA-T11和DIN EN 12720)微硬度10-30秒/30秒释放冲击试验，英寸/英磅(ECCA-T5)粘合度，6mm标值#(ECCA-T6)T-弯曲试验粘附标准(ECCA-T7)T-弯曲试验弹性标准(ECCA-T7) | 99.4 °28 °100％0061/90100W6.0/5.08000.5T0.5T | 74.0°36°30％0058/89100W5.9/4.38000.5T0.5T |
1)ECCA：欧洲卷材涂料协会(European Coil Coating Association)方法
2)测试自清洁性能的人工试验
在漆面上喷淋0.1g炭黑(Flammruβ101)(Degussa)。在污垢上施加重约0.1g的水滴，倾斜金属片使水滴移动。
在该滴移动5cm的时间后目测评估炭黑的吸附。
由以上综述可见，所述漆的技术性能对于两种透明漆而言同样良好。这两种漆的差别仅在于防水特性。相对于对比漆，含氟的漆I具有明显较大的水润湿角(即水滴润湿面积较小)和较小的倾斜角(即促进了滚离趋势并从而提高了表面自清洁性)。这可以通过用上述的“测定自清洁性能的人工实验”测定水滴对炭黑的吸附而辅助进行说明。在含氟的漆I上，在5cm的移动时间后全量的炭黑均被夹带(夹带率100％)最高达到水滴饱和。在对比的漆II上，炭黑仍存留，尤其是在移动径迹的边缘处，而夹带率仅为约30％。因此含氟的涂料明显具有自清洁性能。
Claims (10)
1.用于具有防水和防污表面的烘烤漆的嵌段含氟多异氰酸酯，其包含：
i)100当量％的脂族多异氰酸酯或多异氰酸酯混合物，NCO含量为10-25重量％，官能度为至少2.5，
ii)75-95当量％的异氰酸酯封闭剂，和
iii)5-25当量％的氟化单醇，
其中，iii)和ii)的量之和为100当量％，并且其中基于i+ii+iii的量以F＝19计算的氟含量结果为1.0-20.0重量％，优选4.0-10.0重量％，并任选地包含常规添加剂和辅助物质。
2.根据权利要求1的嵌段含氟多异氰酸酯，特征在于全氟乙基碘化物、全氟丁基碘化物或全氟己基碘化物在烯丙醇上的加成产物由随后的加氢脱碘化产生的相应氟化醇被用作氟化单醇。
3.制备嵌段含氟多异氰酸酯的方法，特征在于首先在50-70℃的温度和搅拌下加入多异氰酸酯，任选地是在溶剂中，然后加入单官能的氟取代醇，在80-110℃进行反应至达到计算的NCO含量，随后使剩余的NCO基团与相应量的封闭剂在70-110℃进行反应。
4.权利要求1的嵌段含氟多异氰酸酯在聚氨酯塑料制备中用作交联剂的用途。
5.权利要求1的嵌段含氟多异氰酸酯用于制备聚氨酯漆的粘合剂的用途。
6.含有权利要求1的嵌段含氟多异氰酸酯的漆粘合剂。
7.权利要求1、5和6的用途，用于制备漆。
8.权利要求1和6的漆用粘合剂用于涂覆基材的用途。
9.权利要求1和6的漆用粘合剂的用途，用于涂覆金属、金属片材和车身元件。
10.用权利要求1、6和7的漆粘合剂和漆涂覆的基材。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10046473.4 | 2000-09-20 | ||
| DE10046473A DE10046473A1 (de) | 2000-09-20 | 2000-09-20 | Fluorhaltige blockierte Isocyanate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1461320A true CN1461320A (zh) | 2003-12-10 |
Family
ID=7656885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01815988A Pending CN1461320A (zh) | 2000-09-20 | 2001-09-07 | 含氟嵌段多异氰酸酯 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6509433B2 (zh) |
| EP (1) | EP1325052A1 (zh) |
| JP (1) | JP2004509998A (zh) |
| KR (1) | KR20030045075A (zh) |
| CN (1) | CN1461320A (zh) |
| AU (1) | AU2002212211A1 (zh) |
| CA (1) | CA2422393A1 (zh) |
| DE (1) | DE10046473A1 (zh) |
| WO (1) | WO2002024781A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788321A (zh) * | 2012-10-31 | 2014-05-14 | 福盈科技化学股份有限公司 | 短碳链氟素聚氨酯化合物及含其的拨水拨油剂 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7482420B2 (en) * | 2004-03-24 | 2009-01-27 | Construction Research & Technology Gmbh | Silane-terminated polyurethanes with high strength and high elongation |
| US8563115B2 (en) * | 2008-08-12 | 2013-10-22 | Xerox Corporation | Protective coatings for solid inkjet applications |
| WO2016091633A1 (de) * | 2014-12-08 | 2016-06-16 | Basf Coatings Gmbh | Beschichtungsmittelzusammensetzungen und daraus hergestellte beschichtungen und sowie deren verwendung |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3783197T2 (de) * | 1986-09-16 | 1993-05-06 | Takeda Chemical Industries Ltd | Einkomponenten-harzzusammensetzungen und deren haertung. |
| US5496642A (en) * | 1994-05-09 | 1996-03-05 | Olin Corporation | Low VOC, fluorocompound-containing one-component and two-component coating compositions for slippery coatings |
| US5576411A (en) | 1994-09-14 | 1996-11-19 | Bayer Corporation | Low surface energy polyisocyanates and their use in one-or two component coating compositions |
| US5541281A (en) | 1994-12-20 | 1996-07-30 | Bayer Corporation | Low surface energy polyisocyanates and their use in one- or two-component coating compositions |
| US5777061A (en) * | 1996-02-14 | 1998-07-07 | Bayer Corporation | Blocked polyisocyanate crosslinkers for providing improved flow properties to coating compositions |
-
2000
- 2000-09-20 DE DE10046473A patent/DE10046473A1/de not_active Withdrawn
-
2001
- 2001-09-07 CA CA002422393A patent/CA2422393A1/en not_active Abandoned
- 2001-09-07 CN CN01815988A patent/CN1461320A/zh active Pending
- 2001-09-07 KR KR10-2003-7003967A patent/KR20030045075A/ko not_active Application Discontinuation
- 2001-09-07 WO PCT/EP2001/010306 patent/WO2002024781A1/de not_active Application Discontinuation
- 2001-09-07 EP EP01980346A patent/EP1325052A1/de not_active Withdrawn
- 2001-09-07 AU AU2002212211A patent/AU2002212211A1/en not_active Abandoned
- 2001-09-07 JP JP2002529189A patent/JP2004509998A/ja active Pending
- 2001-09-14 US US09/955,228 patent/US6509433B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788321A (zh) * | 2012-10-31 | 2014-05-14 | 福盈科技化学股份有限公司 | 短碳链氟素聚氨酯化合物及含其的拨水拨油剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| US6509433B2 (en) | 2003-01-21 |
| AU2002212211A1 (en) | 2002-04-02 |
| US20020123642A1 (en) | 2002-09-05 |
| EP1325052A1 (de) | 2003-07-09 |
| KR20030045075A (ko) | 2003-06-09 |
| DE10046473A1 (de) | 2002-03-28 |
| WO2002024781A1 (de) | 2002-03-28 |
| CA2422393A1 (en) | 2003-03-13 |
| JP2004509998A (ja) | 2004-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0339583B1 (en) | Anti-icing coating compositions | |
| DE69613285T2 (de) | Wetter- und verschmutzungsbeständige Silicon enthaltende Beschichtungszusammensetzung | |
| EP3699217A1 (en) | Waterborne antifogging resin and waterborne antifogging coating composition and preparation method therefor | |
| EP2254960A1 (de) | Verfahren zur herstellung eines hoch abriebfesten fahrzeuglackes, fahrzeuglack und dessen verwendung | |
| JP6165419B2 (ja) | 水系２成分型コーティング組成物、インキ組成物、及び接着剤組成物、並びにその使用方法 | |
| JP3482569B2 (ja) | 塗料用樹脂組成物、及び耐汚染性に優れた塗膜の形成方法 | |
| CN1097602C (zh) | 具有异氰酸酯基和封闭的、对异氰酸酯基团呈反应活性的基团的化合物 | |
| RU2378307C2 (ru) | Состав для защитного покрытия | |
| CN1840560A (zh) | 低表面能多异氰酸酯及其在单组分或双组分涂料组合物中的应用 | |
| JP3298363B2 (ja) | 水性塗料組成物 | |
| CN1461320A (zh) | 含氟嵌段多异氰酸酯 | |
| CN1762987A (zh) | 缩二脲化的异氰酸酯和封端的缩二脲化的异氰酸酯 | |
| JP3428370B2 (ja) | 塗料組成物 | |
| CN116194504A (zh) | 涂料组合物及其制备和用途 | |
| CN1494562A (zh) | 单组分聚氨酯烘烤漆及其应用 | |
| JP3104896B2 (ja) | 塗料組成物 | |
| JPH09221630A (ja) | 塗料組成物及びそれを用いて得られる塗膜 | |
| WO2020109125A1 (de) | Polyisocyanatzusammensetzung für beschichtungen | |
| JP2969205B2 (ja) | ポリプロピレン用プライマー | |
| JPH10130353A (ja) | 自己乳化型ポリイソシアネ−ト組成物並びにこれを用いた水系塗料組成物及び水系接着剤組成物 | |
| JP2676429B2 (ja) | 塗料組成物 | |
| JPS6337811B2 (zh) | ||
| JP2002003775A (ja) | 塗料組成物 | |
| JP2628409B2 (ja) | 塗料組成物 | |
| JP4176389B2 (ja) | 表面処理透明樹脂成形品 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1060740 Country of ref document: HK |
|
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1060740 Country of ref document: HK |