CN1762988B - 封端的缩二脲化的异氰酸酯 - Google Patents
封端的缩二脲化的异氰酸酯 Download PDFInfo
- Publication number
- CN1762988B CN1762988B CN2005101162466A CN200510116246A CN1762988B CN 1762988 B CN1762988 B CN 1762988B CN 2005101162466 A CN2005101162466 A CN 2005101162466A CN 200510116246 A CN200510116246 A CN 200510116246A CN 1762988 B CN1762988 B CN 1762988B
- Authority
- CN
- China
- Prior art keywords
- ester
- composition
- polyisocyanates
- butyl
- isocyanate functionality
- 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.)
- Expired - Fee Related
Links
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
- C08G18/70—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
- C08G18/8093—Compounds containing active methylene 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2895—Compounds containing active methylene 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
- C08G18/302—Water
- C08G18/305—Water creating amino end groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8032—Masked aliphatic or cycloaliphatic polyisocyanates not provided for in one single of the groups C08G18/8016 and C08G18/8025
-
- 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
- C09D175/06—Polyurethanes from polyesters
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)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明揭示了一种封端的含有缩二脲基团的多异氰酸酯组合物,其中的封端剂选自丙二酸二C1-C12烷基和/或烷氧基烷基酯和乙酰乙酸C1-C12烷基和/或烷氧基烷基酯。
Description
背景技术
异氰酸酯的缩二脲化在本领域中是已知的。美国专利3903127和3976622描述了各种不同的缩二脲化剂,包括脂族伯胺。加拿大公开申请CA2211025中描述了使用叔醇或水和叔醇的混合物来缩二脲化异氰酸酯。最后,美国专利4220749描述了用一元仲胺作为缩二脲化剂。所有三篇参考文献都描述了用1,6-己二异氰酸酯作为原料异氰酸酯。
将异氰酸酯固化剂用于涂料组合物也是已知的,异氰酸酯官能度为3或更高的多异氰酸酯是特别好的。美国专利申请公开文本2003/0109664中描述了通过缩二脲化含有异氰酸酯基团的多异氰酸酯来生产高官能多异氰酸酯。在所述的原料异氰酸酯中,使用的是1,6-己二异氰酸酯的三聚体。使用的缩二脲化剂是水。该专利申请表明,当与通过叔丁醇或叔丁醇与水的混合物缩二脲化的异氰酸酯相比时,仅用水缩二脲化的含有三聚体的异氰酸酯表现出更好的色彩。该专利申请也广泛地表明,缩二脲化的异氰酸酯的异氰酸酯基团可用醇、酮亚胺或肟等封端。尽管该申请中描述的缩二脲化的异氰酸酯对现有技术的缩二脲化的异氰酸酯是一种改进,但是还是需要提高由此类异氰酸酯制备的涂料的凝胶含量和耐磨损性。
现有技术中已知许多种封端剂(参见,例如“Blocked Isocyanate inCoatings”,Potter等人,于1986年2月在新澳尔良召开的研讨会Water-Borne&Higher-Solids Coating Symposium上的报告)。在所述的封端剂中,有i)苯酚、甲酚和脂族长链取代的苯酚(诸如异壬基苯酚),ii)酰胺(诸如ε-己内酰胺)、iii)肟(诸如丁酮肟)、iv)含有活性亚甲基基团的化合物(诸如丙二酸酯和乙酰乙酸酯和v)亚硫酸氢钠。不同的封端剂也描述在美国专利4324879、4439593、4495229、4518522、4667180、5071937、5705593、5780541、5849855、6051675、6060573、6274693、6368669和6583216中。
更近期以来,如N-苄基-叔丁基胺(已公开的欧洲专利申请1375551,对应于美国专利申请序列号10/459033,于2003年6月提交)和3-叔丁基氨基丙酸甲酯(已公开的PCT专利申请WO 2005/000936,对应于美国专利申请序列号10/874716,于2004年6月提交)之类的仲胺被描述作为有用的封端剂。
发明内容
本发明涉及一种封端的含有缩二脲基团的多异氰酸酯组合物,其中的多异氰酸酯组合物的封端的异氰酸酯官能度至少为4、并且通过包括以下步骤的方法制备:
A)将多异氰酸酯加合物与缩二脲化剂反应以将缩二脲基团引入到所述多异氰酸酯中,其中的多异氰酸酯加合物:
a)由脂族和/或脂环族二异氰酸酯制得,
b)具有的平均异氰酸酯官能度至少为2.5,且
c)含有异氰脲酸酯基团,
以及
B)将含有缩二脲的多异氰酸酯与选自丙二酸二C1-C12烷基和/或烷氧基烷基酯和乙酰乙酸C1-C12烷基和/或烷氧基烷基酯的封端剂反应。
具体实施方式
合适的用于制备本发明的多异氰酸酯的原料多异氰酸酯是符合a)、b)、c)的多异氰酸酯加合物:
a)由脂族和/或脂环族二异氰酸酯制得,优选脂族二异氰酸酯,更优选1,6-己二异氰酸酯,
b)具有的平均异氰酸酯官能度至少为2.5,优选至少为2.8,更优选至少为3.0;和
c)含有异氰脲酸酯基团。
原料多异氰酸酯加合物的NCO含量较优的为10至25重量%,更优的为12至25重量%,最优的为15至25重量%;具有的官能度的上限较优的为8,更优的为7,最优的为6。用于制备多异氰酸酯加合物的原料优选含有至少70重量%的,更优的至少80重量%的,最优的90%重量%的脂族二异氰酸酯,最优选的是1,6-己二异氰酸酯。
含有异氰脲酸酯基团的原料多异氰酸酯加合物是已知的,并且可依据美国专利4324879的教导来制备,该专利通过引用包括于此。在本发明中,这些加合物通常是优选的原料。含有异氰脲酸酯基团的此类多异氰酸酯加合物的有用的实例是由脂族和/或脂环族二异氰酸酯形成的三聚体。最优选脂族二异氰酸酯的三聚体,诸如来自Bayer Polymers LLC、以商品名Desmodur N3390出售的1,6-己二异氰酸酯的三聚体。
基本上任何脂族和/或脂环族二异氰酸酯皆可用来形成原料多异氰酸酯加合物。有用的二异氰酸酯包括,但不限于,1,6-己二异氰酸酯、双环己基二异氰酸酯、1,4-环己基二异氰酸酯、双(4-异氰酸基环己基)甲烷、3-异氰酸基甲基-3,5,5-三甲基环己基异氰酸酯(“异佛尔酮二异氰酸酯”)等等。
为了制备依据本发明的含有缩二脲基团的多异氰酸酯,原料多异氰酸酯加合物在本领域中已知的缩二脲化剂存在下反应。此类缩二脲化剂包括水、一元仲胺和叔醇。用水作为缩二脲化剂描述在美国专利3124605和3903127中,其公开内容通过引用包括于此。
使用一元仲胺制备缩二脲化的异氰酸酯描述在美国专利4220749中,其公开内容通过引用包括于此。一般而言,仲胺的通式为:(R1)(R2)NH,其中R1和R2可相同或不同,且代表含有1至20个碳原子的脂族烃基。具体的有用的一元仲胺包括二甲胺、二乙胺、二丙胺、二丁胺、双(2-乙基己基)胺。异氰酸酯和胺以约4:1至约14:1的异氰酸酯对胺的当量比反应,从而将缩二脲基团引入到所述的多异氰酸酯中。反应在约0至140℃、优选60至140℃、更优选70至140℃的温度下进行。
最后,叔醇和叔醇与水的混合物的使用描述在加拿大公开申请CA2211025中,其公开内容通过引用包括于此。
所得的含有缩二脲基团的多异氰酸酯具有的异氰酸酯官能度至少为4,较优的是至少为4.5,更优的是至少为4.8,具有的NCO含量以多异氰酸酯的重量为标准计,约8至约24重量%,较优的是约10至约22重量%,更优的是约10至约20重量%。所得的多异氰酸酯具有的最大官能度较优的为10,更优的为8,最优的为7。产物可在溶剂中适当稀释使用。
产物的分子量用聚苯乙烯作为标准由GPC计算得到。所得的含有缩二脲基团的多异氰酸酯的数均分子量为约500至约10000,约500至约5000为佳,约500至约3000最佳。
使用本发明的方法,含有缩二脲的多异氰酸酯可连续地或分批次地制备。
由本方法得到的产物的杰出性特别在于,它们将较低的粘度和较低的分子量与高异氰酸酯官能度和对于涂料中的粘合剂的高活性结合在一起,所述的粘合剂含有异氰酸酯-活性基团,例如为含有羟基的聚丙烯酸酯类。其他的优越性在于它们易于制备、挥发性的异氰酸酯含量即使在长时间的储存中也不会升高,因为这些化合物较稳定,不会分解为单体;它们含有标准的不需要其它调节性清除的异氰酸酯基团;该产品就粘度升高而言是可稳定保存的、且产品基本上是无色的,这对于透明涂层体系是尤其重要的。
然后,将由本方法得到的产品用选自丙二酸二C1-C12烷基和/或烷氧基烷基酯和乙酰乙酸C1-C12烷基和/或烷氧基烷基酯的封端剂来封端。特别有用的丙二酸酯包括丙二酸二乙酯、丙二酸二甲酯、丙二酸二异丙酯、丙二酸二正丙酯、丙二酸二正丁酯、丙二酸乙基正丁基酯、丙二酸甲基正丁基酯等等。特别有用的乙酰乙酸酯是乙酰乙酸甲酯、乙酯、丙酯、丁酯、戊酯、己酯、庚酯、辛酯、壬酯、癸酯、或十二烷基酯。优选的乙酰乙酸烷基酯和/或烷氧基烷基酯是那些在烷基基团中具有1至6个碳原子的乙酰乙酸烷基酯。丙二酸二乙酯和丙二酸乙酯是最佳的封端剂。有用的丙二酸酯和乙酰乙酸酯的其它例子可在如美国专利4439593、4518522、46771805071937、5780541、5849855、6060573、和6274693中找到。通常,反应在低于120℃下进行,优选在40℃至80℃下进行。加入已知的催化剂以保持微微放热。反应在催化剂加入后进行约2小时至6小时。理想的材料比例是一当量的封端剂对应一当量的异氰酸酯。实际的比例为每当量的异氰酸酯对应1±0.05当量的封端剂。
本发明的产物特别适合在涂料组合物中作为固化剂,特别是在汽车涂料中。本发明的涂料组合物通常含有成膜粘合剂—其包括异氰酸酯-活性的低聚物或聚合物或分散的凝胶聚合物,以及如上所述的封端的含有缩二脲基团的多异氰酸酯固化剂。
如上文所指出,本涂料组合物特别适用于作为汽车整修和终饰中的透明涂层,但是它也可以用常规颜料着色,并且用作单涂层或底层或甚至作为如底漆或封底层之类的内涂层。这些涂料也可以用在非汽车业应用中,诸如在工业和建筑业应用中。
与由其它封端剂制得的相似产品比较,由本发明的封端异氰酸酯制得的涂料表现出更好的固化性能,这一性能通过低固化温度下的凝胶含量的提高表现出来。另外,来自本发明的封端异氰酸酯的涂料表现出改善的耐磨性和耐擦伤性。
在以下的实施例中,除非有相反指示,所有的份数和百分数都是重量份数和重量百分数,使用下列材料:
DESMO800-Desmophen800-一种聚酯,它的OH含量为8.8%,100%固体,粘度为约170000厘泊,可从Bayer MaterialScience购得。
CGL-CGL-052L2-基于羟基官能三嗪的位阻胺光吸收剂,从CibaSpecialty Chemicals购得,以PM乙酸酯(丙二醇单甲醚乙酸酯)中含60%的固体供货。
T-928-Tinuvin-基于羟基苯基苯并三唑的紫外吸收剂,从Ciba SpecialtyChemicals购得。
Bay OL-Baysilone OL-017-聚醚改性过的甲基聚硅氧烷,从Borchers购得,作为流动促进剂销售。
n-BA/PMA/EEP-乙酸正丁酯(CAS#123-86-4)、PM乙酸酯(CAS#108-65-6,也称为丙二醇单甲醚乙酸酯)和来自Eastman的Ekatapro EEP(CAS#763-69-9,也称为3-乙氧基丙酸乙酯)按4:5:6的掺混物。。
实施例
在实施例中,实施例3是对比例。
多异氰酸酯1-向一个5升的配置有搅拌器、氮气进口、热电偶和加热器的圆底烧瓶中加入2550份(13.14当量)的Desmodur N 3300多异氰酸酯(一种NCO含量约为22重量%、25℃下粘度约为2500毫帕·秒的无溶剂型的己烷二异氰酸酯的三聚体,从Bayer MaterialScience LLC购得)、450份的乙酸丁酯、0.128份的磷酸二丁酯催化剂和16.60份(0.92当量)的蒸馏水,混合直至均匀。将反应在65℃加热1小时,然后在90℃加热半小时,然后在120℃加热半小时,最后在140℃下加热7小时。在加热期结束后,将反应冷却到室温。异氰酸酯的含量为14.52重量%(理论值为14.16%)。25℃下的粘度为6800厘泊。官能度约为每个分子中6个异氰酸酯基。
多异氰酸酯2-向一个5升的配置有搅拌器、氮气进口、热电偶和加热器的圆底烧瓶中加入2500份(12.88当量)的Desmodur N 3300多异氰酸酯、700份的乙酸丁酯、5份的磷酸二丁酯催化剂和297份(2.30当量)的N,N-二丁基胺,混合直至均匀。将反应在65℃加热1小时,然后在90℃加热半小时,然后在120℃加热5小时,最后在140℃下加热2小时。在加热期结束后,将反应冷却到室温。异氰酸酯的含量为10.5重量%(理论值为10.0%)。25℃下的粘度为1980厘泊。官能度约为每个分子中6个异氰酸酯基。
封端异氰酸酯1-向一个2升的配置有搅拌器、氮气进口、热电偶、加热器和加料漏斗的圆底烧瓶中加入405.0份(1.40当量)的多异氰酸酯1、104.4份(0.71当量)的丙二酸二乙酯、92.9份(0.71当量)的乙酰乙酸乙酯和142.8份的乙酸丁酯,混合直至均匀。当催化剂(1.72份的、在甲醇中30%的甲醇钠和10份的丙二酸二乙酯)滴入时,将反应混合物加热到50℃。反应放热,结果温度升高到68℃。将反应加热到80℃,并在通过滴定所得的异氰酸酯的含量为零时保持一个半小时。加入142.7份的正丁醇。然后加入4份的磷酸二丁酯来中和溶液。25℃下的粘度为2085厘泊。密度为8.81磅/加仑。计算所得的异氰酸酯含量为7.41%,NCO的当量重量为567。
封端异氰酸酯2-向一个2升的配置有搅拌器、氮气进口、热电偶、加热器和加料漏斗的圆底烧瓶中加入243.4份(0.79当量)的多异氰酸酯2、64.1份(0.4当量)的丙二酸二乙酯、51.4份(0.40当量)的乙酰乙酸乙酯和120份的乙酸丁酯,混合直至均匀。当催化剂(0.96份的、在甲醇中30%的甲醇钠和10.95份的丙二酸二乙酯)滴入时,将反应加热到35℃。反应放热,结果温度升高到68℃。将反应加热到70℃,并在通过滴定所得的异氰酸酯的含量为零时保持二个半小时。加入65份的正丁醇。然后加入4份的磷酸二丁酯来中和溶液。28℃下的粘度为63厘泊。密度为8.36磅/加仑。计算所得的异氰酸酯含量为6.08%,NCO的当量重量为690。
封端异氰酸酯3-Desmodur BL XP2434-市场上可从BayerMaterialScience LLC购得的丙二酸二乙酯封端的三聚体(不含缩二脲基团),封端异氰酸酯基团的含量为7.0%,NCO当量重量为600,65%固体,25℃下粘度为3000厘泊。
下表1列出了所测的涂料组合物,表2至表5列出了所得的结果。组合物用Binks95型虹吸管式枪施涂,形成一厚约为4密耳的湿膜。在除水15分钟后,面板依据其所需的温度范围被固化。
所进行的测试如下:
MEK往返擦洗:2磅的球形斧锤被若干层粗棉布包裹。此布浸透MEK。锤子与表面成90度放置,并且在4″的区域内来回移动。布每摩擦25次,则再浸透一次MEK。测试一直进行,直到涂层被破坏或摩擦达到200次。记录下使涂层损坏所需的摩擦次数。
凝胶含量:将已知重量的未涂敷的膜置于不锈钢金属丝网筛中。然后将它们在沸腾的丙酮放置7小时以除去任何可提取的材料。然后将涂层膜重新称重,以确定和报告所保留的固体总重。
摆撞硬度:将涂层的玻璃片放置在Koenig摆撞硬度测试仪中,记录下钟锤在其偏斜角度过低之前的摆动回数。所有的涂层与玻璃的硬度(172-185回)相比较。
摩擦和损伤:在CM-5型Atlas AATCC耐摩擦牢度测定器中进行。将一块羊毛布(Atlas14-9956-00)直接放置在丙烯酸指针(acrylic finger)上。然后将Bon Ami清洁剂施涂到涂层面上,轻轻拍去多余的量。对涂层面来回摩擦十次,再清洗后干燥。抗擦伤性通过从与摩擦方向垂直的方向读到的20%光泽保留的百分数来确定。
表1
实施例 | 1 | 2 | 3 |
异氰酸酯 | 封端异氰酸酯1 | 封端异氰酸酯2 | 封端异氰酸酯3 |
重量份数,异氰酸酯 | 468.79 | 440.85 | 392.52 |
重量份数,Desmo800 | 143 | 154.32 | 128.78 |
重量份数,CGL6.74 | 6.74 | 6.77 | 6.89 |
重量份数,T-92840.42 | 40.42 | 40.6 | 41.33 |
重量份数,Bay OL | 4.17 | 4.19 | 4.26 |
重量份数,n-BA/PMA/EEP | 159.48 | 190.56 | 249.12 |
表2
实施例 | 1 | 2 | 3 |
固化温度,℉,往返擦洗 | |||
175 | 11 | 5 | 4 |
194 | 22 | 11 | 18 |
212 | 57 | 28 | 43 |
230 | 22 | 29 | 36 |
248 | 66 | 57 | 65 |
[0053]
表3
实施例 | 1 | 2 | 3 |
固化温度,℉,凝胶 | |||
175 | 58.4 | 0 | 0.7 |
194 | 79.8 | 56.8 | 47.2 |
212 | 87.7 | 81.6 | 75.9 |
230 | 94.5 | 87.3 | 75.9 |
248 | 94.7 | 94 | 77 |
表4
实施例 | 1 | 2 | 3 |
固化温度,℉,硬度 | |||
175 | 胶粘的 | 2 | 9 |
194 | 5 | 4 | 32 |
212 | 7 | 4 | 66 |
230 | 22 | 5 | 81 |
248 | 31 | 17 | 74 |
表5
实施例 | 1 | 2 | 3 |
固化温度,℉,摩擦 | |||
175 | 21.9 | 0.9 | 6.7 |
194 | 79.2 | 82.9 | 36.6 |
212 | 99.4 | 95.2 | 78.6 |
230 | 99.8 | 93.8 | 82.8 |
248 | 99 | 99.3 | 79.3 |
Claims (7)
1.一种封端的含有缩二脲基团的多异氰酸酯组合物,其中多异氰酸酯组合物的封端的异氰酸酯官能度至少为4、并且通过以下方法制备,包括:
A)将多异氰酸酯加合物与缩二脲化剂反应,以将缩二脲基团引入到所述多异氰酸酯中,所述多异氰酸酯加合物:
a)由脂族和/或脂环族二异氰酸酯制得,
b)具有的异氰酸酯官能度至少为2.5,且
c)含有异氰脲酸酯基团,以及
B)将含有缩二脲的多异氰酸酯与选自丙二酸二C1-C12烷基或烷氧基烷基酯和乙酰乙酸C1-C12烷基或烷氧基烷基酯的封端剂反应。
2.如权利要求1所述的组合物,其特征在于,所述加合物具有的异氰酸酯官能度至少为2.8。
3.如权利要求2所述的组合物,其特征在于,所述加合物具有的异氰酸酯官能度至少为3.0,具有的异氰酸酯官能度至多为8。
4.如权利要求1所述的组合物,其特征在于,组分A)a)是脂族二异氰酸酯。
5.如权利要求1所述的组合物,其特征在于,所述缩二脲化剂选自水、一元仲胺和叔醇。
6.如权利要求1所述的组合物,其特征在于,所述封端剂是选自丙二酸二乙酯、丙二酸二甲酯、丙二酸二异丙酯、丙二酸二正丙酯、丙二酸二正丁酯、丙二酸乙基正丁基酯、丙二酸甲基正丁基酯的丙二酸酯。
7.如权利要求1所述的组合物,其特征在于,所述封端剂是选自乙酰乙酸的甲酯、乙酯、丙酯、丁酯、戊酯、己酯、庚酯、辛酯、壬酯、癸酯、或十二烷基酯的乙酰乙酸酯。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/970,771 | 2004-10-21 | ||
US10/970,771 US20060089481A1 (en) | 2004-10-21 | 2004-10-21 | Blocked biuretized isocyanates |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1762988A CN1762988A (zh) | 2006-04-26 |
CN1762988B true CN1762988B (zh) | 2010-07-28 |
Family
ID=35542839
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2005101162466A Expired - Fee Related CN1762988B (zh) | 2004-10-21 | 2005-10-21 | 封端的缩二脲化的异氰酸酯 |
Country Status (15)
Country | Link |
---|---|
US (1) | US20060089481A1 (zh) |
EP (1) | EP1650244B1 (zh) |
JP (1) | JP4947953B2 (zh) |
KR (1) | KR20060054132A (zh) |
CN (1) | CN1762988B (zh) |
AT (1) | ATE365181T1 (zh) |
CA (1) | CA2523905A1 (zh) |
DE (1) | DE602005001432T2 (zh) |
ES (1) | ES2289636T3 (zh) |
HK (1) | HK1087397A1 (zh) |
MX (1) | MXPA05011282A (zh) |
NZ (1) | NZ543093A (zh) |
PL (1) | PL1650244T3 (zh) |
PT (1) | PT1650244E (zh) |
RU (1) | RU2005132378A (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2024455B1 (en) | 2006-05-16 | 2018-04-04 | Coatings Foreign IP Co. LLC | Highly productive coating composition for automotive refinishing |
JP5837054B6 (ja) * | 2011-04-08 | 2018-06-27 | 関西ペイント株式会社 | 複層塗膜形成方法、及び塗装物品 |
US20150232693A1 (en) * | 2012-10-01 | 2015-08-20 | Kansai Paint Co., Ltd. | Process for forming multilayer coating film |
TR201906000T4 (tr) * | 2015-05-06 | 2019-05-21 | Basf Se | Kompozit materyallerin üretimi için metot. |
EP3348593B1 (en) * | 2015-09-11 | 2019-08-21 | Asahi Kasei Kabushiki Kaisha | Blocked polyisocyanate composition, one-component coating composition, coating film, and coated article |
CN111247189B (zh) * | 2017-11-21 | 2022-03-08 | 三井化学株式会社 | 封端异氰酸酯组合物及涂覆剂 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4332965A (en) * | 1976-03-25 | 1982-06-01 | Hoechst Aktiengesellschaft | Blocked polyisocyanates formed from a polyisocyanate containing biuret groups and from an acetoacetic acid alkyl ester |
RU2148061C1 (ru) * | 1998-04-09 | 2000-04-27 | Институт проблем химической физики РАН | Блокированные полиизоцианаты, способ их получения, применение их в качестве компонента защитных и декоративных покрытий и магнитная регистрирующая среда на основе блокированных полиизоцианатов |
CN1477137A (zh) * | 2002-06-27 | 2004-02-25 | 包含封端多异氰酸酯的组合物 | |
JP4108844B2 (ja) * | 1998-10-30 | 2008-06-25 | 株式会社東芝 | Atm中継装置 |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US418522A (en) * | 1889-12-31 | Type-writer cabinet | ||
US3862973A (en) * | 1970-03-07 | 1975-01-28 | Bayer Ag | Process for the preparation of polyisocyanates containing biuret groups |
DE2308015B2 (de) * | 1973-02-17 | 1980-07-31 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Polyisocyanaten mit Biuretstruktur |
US3976622A (en) * | 1973-02-17 | 1976-08-24 | Bayer Aktiengesellschaft | Process for the production of polyisocyanates with a biuret structure |
DE2730513A1 (de) * | 1977-07-06 | 1979-01-25 | Bayer Ag | Verfahren zur herstellung von modifizierten polyisocyanaten |
CA1112243A (en) * | 1978-09-08 | 1981-11-10 | Manfred Bock | Process for the preparation of polyisocyanates containing isocyanurate groups and the use thereof |
US4495229A (en) * | 1982-06-08 | 1985-01-22 | Chemische Werke Huls A.G. | One-component, heat-curing polyurethane-coatings, stable in storage |
US4439593A (en) * | 1983-05-26 | 1984-03-27 | Mobay Chemical Corporation | Polyurethane compositions with improved storage stability |
US5986033A (en) * | 1984-02-29 | 1999-11-16 | The Baxenden Chemical Co. | Blocked isocyanates |
US4659770A (en) * | 1986-02-03 | 1987-04-21 | E.I. Du Pont De Nemours And Company | Coating composition of an amine polymer and a blocked polyisocyanate |
US4677180A (en) * | 1986-07-16 | 1987-06-30 | Mobay Corporation | Polyurethane compositions with improved storage stability |
US4788262A (en) * | 1986-12-08 | 1988-11-29 | Mobay Corporation | Polyisocyanate blends with improved compatibility with coreactants |
US5071937A (en) * | 1987-12-22 | 1991-12-10 | Mobay Corporation | Coating compositions based on blocked polyisocyanates and sterically hindered aromatic polyamines |
DE4240480A1 (de) * | 1992-12-02 | 1994-08-25 | Bayer Ag | Organische Polyisocyanate mit zumindest teilweise blockierten Isocyanatgruppen |
US5370908A (en) * | 1993-05-24 | 1994-12-06 | Olin Corporation | Low VOC, heat-curable, one-component and two-component coating compositions based on organic polyisocyanates |
DE4324947A1 (de) * | 1993-07-24 | 1995-01-26 | Basf Lacke & Farben | Nichtwäßrige Lacke |
DE19534624A1 (de) * | 1995-09-18 | 1997-03-20 | Bayer Ag | Allophanatgruppen aufweisende Polyisocyanate auf Basis Diphenylmethandiisocyanat mit überwiegend oder vollständig blockierten Isocyanatgruppen |
JP3712295B2 (ja) * | 1996-04-12 | 2005-11-02 | 旭化成ケミカルズ株式会社 | ブロックポリイソシアネート組成物及びそれを用いた一液性熱硬化組成物 |
DE19626886A1 (de) * | 1996-07-04 | 1998-01-08 | Huels Chemische Werke Ag | Blockierte Polyisocyanate, ein Verfahren zu ihrer Herstellung sowie deren Verwendung |
DE19738497A1 (de) * | 1997-09-03 | 1999-03-04 | Bayer Ag | Amin-blockierte Polyisocyanate |
DE19748584A1 (de) * | 1997-11-04 | 1999-05-06 | Basf Coatings Ag | Verfahren zur Herstellung einer mehrschichtigen Lackierung und für diese Verfahren geeignete Lacke |
DE19813352A1 (de) * | 1998-03-26 | 1999-09-30 | Bayer Ag | Malonesterblockierte Polyisocyanate mit Formaldehyd gegen Thermovergilbung |
DE19941213A1 (de) * | 1999-08-30 | 2001-03-01 | Bayer Ag | Malonester-blockiertes HDI-Trimerisat mit IPDA- und Formaldehydstabilisierung |
JP2005504137A (ja) * | 2001-09-21 | 2005-02-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 塗料用の架橋剤としてのビウレット含有ポリイソシアネートの調製および用途 |
DE10322911A1 (de) * | 2003-05-21 | 2004-12-16 | Bayer Materialscience Ag | Verfestigungsstabile blockierte Polyisocyanate |
DE10348380A1 (de) * | 2003-10-17 | 2005-06-02 | Bayer Materialscience Ag | Mit sekundären Aminen blockierte Polyisocyanate mit Biuretstruktur |
US7371807B2 (en) * | 2004-10-21 | 2008-05-13 | Bayer Materialscience Llc | Blocked biuretized isocyanates |
-
2004
- 2004-10-21 US US10/970,771 patent/US20060089481A1/en not_active Abandoned
-
2005
- 2005-10-08 PL PL05021979T patent/PL1650244T3/pl unknown
- 2005-10-08 ES ES05021979T patent/ES2289636T3/es active Active
- 2005-10-08 EP EP05021979A patent/EP1650244B1/en active Active
- 2005-10-08 AT AT05021979T patent/ATE365181T1/de active
- 2005-10-08 DE DE602005001432T patent/DE602005001432T2/de active Active
- 2005-10-08 PT PT05021979T patent/PT1650244E/pt unknown
- 2005-10-18 NZ NZ543093A patent/NZ543093A/en unknown
- 2005-10-19 CA CA002523905A patent/CA2523905A1/en not_active Abandoned
- 2005-10-20 RU RU2005132378/04A patent/RU2005132378A/ru not_active Application Discontinuation
- 2005-10-20 JP JP2005305773A patent/JP4947953B2/ja not_active Expired - Fee Related
- 2005-10-20 KR KR1020050098975A patent/KR20060054132A/ko active IP Right Grant
- 2005-10-20 MX MXPA05011282A patent/MXPA05011282A/es active IP Right Grant
- 2005-10-21 CN CN2005101162466A patent/CN1762988B/zh not_active Expired - Fee Related
-
2006
- 2006-07-04 HK HK06107510.0A patent/HK1087397A1/xx not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4332965A (en) * | 1976-03-25 | 1982-06-01 | Hoechst Aktiengesellschaft | Blocked polyisocyanates formed from a polyisocyanate containing biuret groups and from an acetoacetic acid alkyl ester |
RU2148061C1 (ru) * | 1998-04-09 | 2000-04-27 | Институт проблем химической физики РАН | Блокированные полиизоцианаты, способ их получения, применение их в качестве компонента защитных и декоративных покрытий и магнитная регистрирующая среда на основе блокированных полиизоцианатов |
JP4108844B2 (ja) * | 1998-10-30 | 2008-06-25 | 株式会社東芝 | Atm中継装置 |
CN1477137A (zh) * | 2002-06-27 | 2004-02-25 | 包含封端多异氰酸酯的组合物 |
Also Published As
Publication number | Publication date |
---|---|
CA2523905A1 (en) | 2006-04-21 |
RU2005132378A (ru) | 2007-04-27 |
PT1650244E (pt) | 2007-09-21 |
EP1650244B1 (en) | 2007-06-20 |
JP2006117941A (ja) | 2006-05-11 |
ES2289636T3 (es) | 2008-02-01 |
PL1650244T3 (pl) | 2007-11-30 |
KR20060054132A (ko) | 2006-05-22 |
EP1650244A1 (en) | 2006-04-26 |
US20060089481A1 (en) | 2006-04-27 |
DE602005001432D1 (de) | 2007-08-02 |
CN1762988A (zh) | 2006-04-26 |
ATE365181T1 (de) | 2007-07-15 |
DE602005001432T2 (de) | 2008-03-13 |
NZ543093A (en) | 2007-05-31 |
MXPA05011282A (es) | 2006-07-11 |
HK1087397A1 (en) | 2006-10-13 |
JP4947953B2 (ja) | 2012-06-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10093826B2 (en) | Alkoxysilane-functionalized allophanate-containing coating compositions | |
US10336856B2 (en) | Alkoxysilane- and allophanate-functionalized coating materials | |
CN1762988B (zh) | 封端的缩二脲化的异氰酸酯 | |
US20060276611A1 (en) | Polyisocyanates blocked with diisopropyl malonate and their use in one-component coating compositions | |
CN101600750B (zh) | 多异氰酸酯组合物用于具有提高的亮度的涂料的用途 | |
JP2018002718A (ja) | アルコキシシラン官能化アロファネート | |
US10336854B2 (en) | Alkoxysilane-functionalized and allophanate-functionalized urethanes | |
EP1939232A1 (en) | Highly crosslinkable low-viscosity polyisocyanate composition and coating composition containing same | |
KR20080044180A (ko) | 코팅 조성물 | |
CN101896523B (zh) | 含有脂环族结构单元的多异氰酸酯混合物 | |
US20180312713A1 (en) | Coating compositions comprising monoallophanates based on alkoxysilane alkyl isocyanates | |
WO2016146574A1 (de) | Polyisocyanatzusammensetzung auf basis von 1,5-pentamethylendiisocyanat | |
US20080114133A1 (en) | Coating compositions | |
CN100467511C (zh) | 作为封端剂用的环酮 | |
CN101724134B (zh) | 湿固化聚异氰酸酯混合物 | |
CN1762987B (zh) | 缩二脲化的异氰酸酯和封端的缩二脲化的异氰酸酯 | |
MXPA05010730A (es) | Lacas de acabado hibridas. | |
CN1789364A (zh) | 含有二环原酸酯(boe)和/或聚原酸酯基团的粘合剂混合物 | |
US5925711A (en) | Polyamines and their use in aqueous coating compositions | |
US6538096B2 (en) | Storage-stable polyisocyanates | |
US20110151127A1 (en) | Novel mixtures of polyisocyanate compositions | |
US20080281025A1 (en) | Hybrid polyisocyanates | |
US20020068171A1 (en) | One-component stoving composition and use thereof | |
JP2022078680A (ja) | ブロックポリイソシアネート組成物、樹脂組成物、樹脂膜及び積層体 | |
WO2021230352A1 (ja) | ブロックポリイソシアネート組成物、樹脂組成物、樹脂膜及び積層体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1087397 Country of ref document: HK |
|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1087397 Country of ref document: HK |
|
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100728 Termination date: 20141021 |
|
EXPY | Termination of patent right or utility model |