CN1120189C - 辐射固化聚合物和包含该聚合物的组合物 - Google Patents
辐射固化聚合物和包含该聚合物的组合物 Download PDFInfo
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- CN1120189C CN1120189C CN99808285A CN99808285A CN1120189C CN 1120189 C CN1120189 C CN 1120189C CN 99808285 A CN99808285 A CN 99808285A CN 99808285 A CN99808285 A CN 99808285A CN 1120189 C CN1120189 C CN 1120189C
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/065—Polyamides; Polyesteramides; Polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及一种含至少一个衍生自由羟基烷基酰胺和α，β-烯属不饱和羧酸构成的羧酸酯的基团的聚合物，和含该聚合物的辐射固化组合物。含上述组合物的涂料组合物具有高的聚合速度，并能形成具有所要求的化学和机械性能的涂层。
Description
本发明涉及辐射固化聚合物和包含该聚合物的组合物。
在辐射固化过程中，流体涂膜转变成固体交联网状结构的过程，可认为是通过三个不同的步骤进行的，即，诱导、聚合和最大固化平坦区的获得(紫外和电子束配制物化学和工艺学(Chemistry and Technologyof UV and EB formulations)第IV卷，Oldring，1991，第8～12)。
改善或抑制固化速率的因素是，例如，灯系统(紫外剂量、强度、波长、红外含量)和化学系统(反应性、吸收、涂布重量、颜料淀积、温度、氧阻聚和基材)。
对于大规模涂布操作，涂料必须在几秒或更短时间内形成不发粘表面，因为涂料的涂布和涂层基材的层叠或重绕的时间间隔很短。涂料不能在该短时间间隔形成不粘表面的缺点，会导致涂层基材层(堆垛或成卷)粘连在一起(“结块”)。
本发明的目的是提供一种具有高固化速度或聚合速度的、形成具有所需要的化学性能和机械性能的涂层的涂料组合物。
按照本发明的辐射固化组合物包含，一种含至少一个衍生自由羟基烷基酰胺和α，β-烯属不饱和羧酸构成的羧酸酯的基团的聚合物，其中聚合物是按照通式(I)的官能团聚合物：其中：
P是聚合物基团，
Y是氢、(C1～C8)烷基或下述通式基团，
R1、R2、R3和R4是相同或不同的，为氢或线形、支化或环状(C1～C8)烷基链，
R5是氢、(C1～C5)烷基、-CH2OH或CH2COOX，
R6、R7是氢、(C1～C8)烷基、或COOX，
X是氢或(C1～C8)烷基，
n为1～1000和
m为1～4。
按照本发明的组合物具有高的最大聚合速度。
在通式中，R1、R2或R3可以形成环烷基基团部分。
优选，Y是氢或甲基。
更优选，Y是氢。
优选，R1、R2、R3和R4是氢或甲基。
更优选，R1、R2和R3是氢。
优选，R5是氢或(甲)乙基。
优选，R6和R7是氢。
优选n＝1～100，更优选n＝2～20。
优选m＝1～2，更优选m＝1。
适宜的羟基酰胺是，例如，β-羟基烷基酰胺、γ-羟基烷基酰胺、δ-羟基烷基酰胺和ε-羟基烷基酰胺。
优选，羟基酰胺是β-羟基烷基酰胺。
适宜的聚合物P是，例如，加成聚合物和缩合聚合物，其分子量(Mw)至少为400。
这些聚合物能够是，例如，线形聚合物、支化聚合物、梳形聚合物、星形聚合物、梯形聚合物、树枝状聚合物和高支化聚合物。
适宜的加成聚合物P包括衍生自下述单体的聚合物，例如，(甲基)丙烯酸酯、丙烯酰胺、苯乙烯、乙烯、丙烯、马来酸、氰基丙烯酸酯、乙烯基乙酸酯、乙烯基醚、氯乙烯、乙烯基硅烷和它们的混合物。
适宜的缩合聚合物P包括，例如，聚酯、聚内酯、聚酰胺、聚酯酰胺、聚醚、聚酯醚、聚氨酯和聚氨酯-脲。
适宜的线形聚合物P包括，例如，衍生自二醇的聚醚、聚乙烯、聚MMA、衍生自二醇和二官能酸和/或单羟基酸的聚酯。
适宜的支化聚合物P包括，例如，包含至少一个三官能醇单元的聚醚、包含至少一个三或四官能醇单元和/或一个三/四官能酸单元的聚酯。
适宜的树枝状聚合物公开在，例如，EP-A-575596、EP-A-707611、EP-A-741756、EP-A-672703，应用化学国际版，英文(Angew.Chem.Int.Ed.Eng)1994，33，2413；应用化学国际版，英文，1990，29，138；应用化学国际版，英文，1993，32，1308和应用化学国际版，英文，1992，31，1200。
适宜的高支化聚合物包括，例如，含β-羟基烷基酰胺基团的、重均分子质量为≥800g/mol的缩合聚合物。聚合物能够包含至少两个按照通式(II)的基团：
其中Y是
H，和(C1～C20)环烷基或(C6～C10)芳基，
B是(C2～C20)任选取代的芳基或(环)烷脂族二基，和
R1、R2、R3、R4、R5和R6，彼此无关，可以是相同或不同的，是H、(C6～C10)芳基或(C1～C8)(环)烷基。
适宜的高支化聚合物的其它例子公开在WO-A-9612754、WO-A-9613558、WO-A-9619537和WO-A-9317060。
在P和官能基之前能够存在连接基团S：适宜的基团S包括，例如，烷基、氧烷基(oxyalkyl)、氨基甲酸酯烷基、脲烷基、羧烷基、氨烷基或酰氨烷基基团。
按照通式(I)的官能化聚合物的制备方法，包括，例如，使含有羟基烷基酰胺单元的聚合物与不饱和羧酸在例如80℃～140℃下进行酯化反应。
羟基烷基酰胺单元能在链中，在侧链中或在聚合物末端。
优选每摩尔氢氧化物使用1～1.5mol酸。
优选，反应在有机溶剂存在下进行，例如，二甲苯、甲苯或四氢呋喃。
优选，反应在稳定化合物存在下进行，以防不饱和酯基团在进行该反应所使用的条件下发生聚合。稳定化合物或稳定化合物混合物的一般用量为约50～约2000ppm，优选75～1000ppm。取决于稳定化合物，能够在有氧或无氧条件下使用它们。
适宜的稳定化合物包括，例如对苯二酚、单甲基对苯二酚、蒽醌、β-硝基苯乙烯、吩噻嗪和2，6-二叔丁基-4-甲基酚(BHT)。
酯化反应可以在催化剂存在下进行。适宜的催化剂包括强酸，例如，含硫有机酸如链烷烃磺酸和甲磺酸。
适宜的不饱和羧酸包括，例如，(甲基)丙烯酸及其衍生物、巴豆酸、衣康酸(半酯)、马来酸、柠康酸、中康酸和富马酸。优选使用(甲基)丙烯酸。
官能化聚合物也能够通过羟基烷基酰胺和不饱和羧酰氯、酐或酯进行反应得到，或者通过含噁唑啉的聚合物和不饱和羧酸进行反应得到。
酰胺和不饱和酰氯或酐的反应，优选在0～30℃下，在溶剂中、在碱存在下进行。适宜的溶剂包括，例如，四氢呋喃、水、二氯甲烷或二乙基醚。适宜的碱包括，例如，吡啶或三乙胺。
适宜的酰氯、酐或酯包括，前述羧酸的酰氯、酐和酯。
酰胺和不饱和酯的反应，优选在路易斯酸存在下，在80℃～140℃下进行。
优选，过量使用不饱和酯。酯起着溶剂和反应物两种作用。
适宜的路易斯酸是，例如，钛酸四烷基酯和硫酸。
适宜的不饱和羧酯包括，例如，(甲基)丙烯酸及衍生物、巴豆酸、衣康酸(半酯)、马来酸、柠康酸、中康酸和富马酸。优选使用甲基丙烯酸和丙烯酸。
官能聚合物能够借助于自由基反应进行固化。在这类反应中，自由基能够通过在光引发剂存在下辐照官能聚合物得到。
辐射固化优选借助于光化学方法如紫外辐射(UV)或者辐射化学方法如电子束(EB)进行。
UV和EB辐射更详细地说明在，例如，Bett等的论文题目“UV和EB固化”(Jocca 1990(11)，第446～453页)。
按照本发明官能聚合物用量能够为按照本发明组合物的0.01wt％～100wt％。
一般说，按照本发明的辐射固化组合物基本上不含溶剂。
按照本发明组合物能够应用在例如涂料组合物、油墨和粘合剂中。
如果需要，并取决于应用，官能聚合物能够与以下述单元为基础的低聚物或单体混合，例如，(甲基)丙烯酸酯单元、马来酸酯单元、富马酸酯单元、衣康酸酯单元、乙烯基酯单元和/或乙烯基醚单元。
按照本发明的涂料固化之后，具有许多理想的性能，例如，良好的化学性能(耐溶剂、耐酸、耐碱和耐水性)、良好的光学性能和外观、良好的机械性能(如硬度、挠性、粘合性、耐磨性、强度和耐用性)、良好的热稳性和良好的耐候性。
包含辐射固化基料组合物的组合物可以还含有颜料、稳定剂和其它添加剂。
辐射固化配制物一般由预聚合物、活性稀释剂和添加剂组成。取决于配制物类型的固化机理，还有两种其它可能的组分是颜料和光引发剂系统。
该组合物能够应用于，例如，水基涂料组合物、溶剂基涂料组合物、高固体分涂料组合物、100％固化分涂料和粉状漆组合物中。
最优选的辐射源是紫外光。优选紫外光是高强度光，以便提供达到适当的固化速度的剂量。万一施加了较低能量的光，那末需要使组合物还经受高温，以便减少满足要求的聚合进行的时间。
关于UV固化设备，我们参考了，例如，UV和EB配制物化学和工艺学，第1卷，第161～234页，Oldring，1991。
为提供所要求的高强度、可用波长和光谱分布而使用的适宜的灯包括，例如，Fusion Systems公司所出品的灯。
按照本发明的组合物能够涂布在诸如塑料、纸、木板、皮革、玻璃、木材和金属等基材上。
优选该组合物在光引发剂存在下进行聚合，但是也能够在不存在光引发剂下进行聚合。
适宜的光引发剂便于采用波长约200nm～约600nm的光引发固化反应。适宜的光引发剂具有酮官能基，能够是芳族化合物，例如二苯甲酮。Darocur 1173(汽巴公司)是适宜的以苄基-缩酮为基础的光引发剂，其含有2-羟基-2-甲基-1-苯基丙烷-1-酮作活性组分。Irgacure 184(汽巴公司)是含有羟基环己基·苯基酮作活性组分的芳基酮，是一种适宜的光引发剂。Irgacure 369(活性组分2-苄基-2-二甲氨基(aminol)-1-(4-吗啉代苯基)-丁酮-1)也是适宜的。也能应用酰基膦，例如，2，4，6-三甲基苯甲酰二苯基氧化膦(phosphoneoxide)(Lucerine TPO，BASF公司)，含有1-氯-4-丙氧基噻吨酮作活性组分的Quantacure CPTX(Octel化学公司)也能够应用。这些光引发剂的化学衍生物是适宜的，这些光引光剂的混合物也是适宜的。一种适宜的光引发剂组合是Irgacure 1800TM(汽巴公司)，它是由75wt％Irgacure 184TM和25wt％双-(2，6-二甲氧基苯甲酰)-2，4，4-三甲基苯基氧化膦(fosfine oxide)组成的。其它适宜的光引发剂能够是Norrish-II-型，例如，二苯甲酮与胺的组合、马来酰亚胺与胺的组合、噻吨酮与胺的组合以及蒽醌(antrachinon)与胺的组合。
现参考如下非限制性实例说明本发明。
实例1
树脂I的合成
将由20.1g羟基乙基甲基丙烯酰胺、40.3g丙烯酸乙基己酯、40.0g丙烯酸异癸酯和6.2g叔丁基过氧-2-乙基己酸酯组成的反应混合物，用2.5h缓缓加入到在装有搅拌器、回流冷凝器、温度计和氮气入口的圆底烧瓶中的140g加热了的丁酮中，同时进行回流。随后，用1h加入2.6g叔丁基过氧-2-乙基己酸酯在29.1g丁酮中的溶液。向热聚合物溶液加入木炭，并经Celite过滤。在蒸发出溶剂之后，得到羟值为30meqKOH/g的羟基酰胺官能聚合物。
将10.4g丙烯酰氯缓缓加入到0～5℃搅拌着的100g上述制备的羟基酰胺官能聚合物和12.4g吡啶在200ml干四氢呋喃的溶液中。加完之后，使温度缓缓升至室温，并将反应混合物在该温度下搅拌18hr。
过滤反应混合物除去吡啶-HCl盐，用饱和碳酸钠溶液洗涤、用水洗涤、经硫酸钠干燥和随后蒸发出溶剂，得到丙烯酸系官能树脂(I)。
实例II
树脂II的合成
将390g熔融六氢邻苯二甲酸酐(60℃)，在70℃氮气氛围下，加到于1.51反应烧瓶中的455g熔融二异丙胺中。在加完之后，进行放热反应，反应温度升高到180℃，将反应混合物在180℃下搅拌3hr。随后减压自大气压至20mbar，再继续进行反应1hr，此后制得含有β-羟基酰胺端基的高支化聚合物，其性能为：Mn＝1160，分散性D＝2.1，Tg＝57.5℃和羟值为365 meq KOH/g。
向所得树脂中加入446g甲基丙烯酸和0.4g吩噻嗪。使干燥空气经反应混合物进行鼓泡，此后，将反应混合物加热至110℃，6hr之后，减压至20mbar，蒸馏出少量甲基丙烯酸，此后得到甲基丙烯酸系官能聚合物(树脂II)，其性能为：Mn＝1800、D＝2.0、每不饱和度重量(wpu)＝260，羟值为60meq KOH/g。
实例III
含树脂I的涂层的固化
将50mg Darocure 1173TM溶解在5g树脂I中。将100μm厚该混合物薄膜涂敷在玻璃板上，随后在氮气氛围中固化，所用总剂量为1J/cm2(灯：Fusion F600，装有D-Bulb)。辐照之后，得到固化涂层。进行丙酮双擦试验，涂层能经100次丙酮双擦，而不受损伤。
实例IV
含树脂I和丙烯酸月桂酯的涂层的固化
将5g树脂I溶解在2.4g丙烯酸月桂酯中，向其中加入74mgIrgacure184TM。将所得溶液的100μm厚薄膜涂敷在玻璃板上，随后在氮气氛围中采用1J/cm2总剂量(灯：Fusion F600，装有D-Bulb)进行固化。
在辐照之后，得到固化涂层。进行丙酮双擦试验，涂层能经100次丙酮双擦，而不受损伤。
实例V
含树脂II和甲基丙烯酸甲酯的涂层的固化
将5g树脂II溶解在1.9g甲基丙烯酸甲酯中，向其中加入69mgIrgacure184TM。将所得溶液的100μm厚薄膜涂敷在玻璃板上，随后在氮气氛围下采用1J/cm2总剂量(灯：Fusion F600，装有D-Bulb)进行固化。
在辐照之后，得到固化涂层。进行丙酮双擦试验，涂层能经100次丙酮双擦，而不受损伤。
实例VI
含树脂II和丙烯酸异癸酯的涂层的固化
将5 g树脂II溶解在4.1g丙烯酸异癸酯中，向其中加入91mgIrgacure184TM。将所得溶液的100μm厚薄膜涂敷在玻璃板上，随后在氮气氛围中采用1J/cm2总剂量(灯：Fusion F600，装有D-Bulb)进行固化。
在辐照之后，得到固化涂层。进行丙酮双擦试验，涂层能经100次丙酮双擦，而不受损伤。
实例VII
含树脂II和二缩三乙二醇二乙烯基醚的涂层的固化
将5g树脂II溶解在1.9g二缩三(乙二醇)二乙烯基醚中，向其中加入69mg Irgacure184TM。将所得溶液的100μm厚薄膜涂敷在玻璃板上，随后在氮气氛围中采用1J/cm2总剂量(灯：Fusion F600，装有D-Bulb)进行固化。
在辐照之后，得到固化涂层。进行丙酮双擦试验，涂层能经100次丙酮双擦，而不受损伤。
实例VIII
含有脂II和二缩三(乙二醇)二(单丁基马来酸酯)的涂层的固化
将5g树脂II溶解在4.4g二缩三(乙二醇)二(单丁基马来酸酯)中，向其中加入94mgIrgacure184TM。将所得溶液的100μm厚薄膜涂敷在玻璃板上，随后在氮气氛围中采用1J/cm2总剂量(灯：FusionF600，装有D-Bulb)进行固化。
在辐照之后，得到固化涂层。进行丙酮双擦试验，涂层能经100次丙酮双擦，而不受损伤。
这些实例证明，按照本发明的UV固化官能聚合物能得到良好涂层。
Claims (4)
1.一种辐射固化涂料组合物，包含具有如下通式(I)的聚合物：其中：
P是聚合物基团，
Y是氢、(C1～C8)烷基或下述通式基团，
R1、R2、R3和R4是相同或不同的，为氢或线形、支化或环状(C1～C8)烷基链，
R5是氢、 (C1～C5)烷基、-CH2OH或CH2COOX，
R6、R7是氢、(C1～C8)烷基、或COOX，
X是氢或(C1～C8)烷基，
n为1～100和
m为1～4。
2.按照权利要求1的组合物，其特征在于Y是氢或甲基，R1、R2、R3和R4为氢或甲基，R5是氢、甲基或乙基，和R6和R7是氢。
3.通过辐射固化按照权利要求1～2中任何一项的组合物所得到的涂层。
4.一种全部或部分涂层的基材，其中按照权利要求3的涂层作为其涂层涂敷。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98202236.0 | 1998-07-06 | ||
| EP98202236A EP0970977A1 (en) | 1998-07-06 | 1998-07-06 | Polymers of acrylic esters containing amide groups |
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| Publication Number | Publication Date |
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| CN1308646A CN1308646A (zh) | 2001-08-15 |
| CN1120189C true CN1120189C (zh) | 2003-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN99808285A Expired - Fee Related CN1120189C (zh) | 1998-07-06 | 1999-06-30 | 辐射固化聚合物和包含该聚合物的组合物 |
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| Country | Link |
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| US (1) | US20010006730A1 (zh) |
| EP (2) | EP0970977A1 (zh) |
| KR (1) | KR20010071728A (zh) |
| CN (1) | CN1120189C (zh) |
| AT (1) | ATE274538T1 (zh) |
| AU (1) | AU748525B2 (zh) |
| CA (1) | CA2336637A1 (zh) |
| DE (1) | DE69919711T2 (zh) |
| ES (1) | ES2226402T3 (zh) |
| NO (1) | NO20010036L (zh) |
| PL (1) | PL345410A1 (zh) |
| WO (1) | WO2000001749A1 (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1116734A1 (en) * | 2000-01-10 | 2001-07-18 | Dsm N.V. | Radiation-curable composition |
| CA3122997A1 (en) * | 2018-12-13 | 2020-06-18 | Ppg Industries Ohio, Inc. | Polyhydroxyalkylamide materials for use as crosslinkers |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3366613A (en) * | 1964-08-17 | 1968-01-30 | Rohm & Haas | Monomers and polymers of n-(acryloxyalkyl)acylamides and methods of making them |
| JPS5241254B1 (zh) * | 1971-04-09 | 1977-10-17 | ||
| CH546798A (de) * | 1971-08-17 | 1974-03-15 | Ciba Geigy Ag | Verfahren zum haerten von acrylsaeureesterderivaten mit ionisierenden strahlen. |
| US4559382A (en) * | 1983-06-06 | 1985-12-17 | Minnesota Mining And Manufacturing Company | Processable radiation curable poly(vinyl chloride) resin compositions |
| JP2640109B2 (ja) * | 1988-01-27 | 1997-08-13 | 富士写真フイルム株式会社 | 電子写真式平版印刷用原版 |
| AUPO093296A0 (en) * | 1996-07-10 | 1996-08-01 | University Of Melbourne, The | Electrophoresis gels and crosslinking agents for their preparation |
-
1998
- 1998-07-06 EP EP98202236A patent/EP0970977A1/en not_active Withdrawn
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1999
- 1999-06-30 PL PL99345410A patent/PL345410A1/xx not_active Application Discontinuation
- 1999-06-30 EP EP99929970A patent/EP1093481B1/en not_active Expired - Lifetime
- 1999-06-30 AT AT99929970T patent/ATE274538T1/de not_active IP Right Cessation
- 1999-06-30 DE DE69919711T patent/DE69919711T2/de not_active Expired - Fee Related
- 1999-06-30 KR KR1020017000085A patent/KR20010071728A/ko not_active Application Discontinuation
- 1999-06-30 CN CN99808285A patent/CN1120189C/zh not_active Expired - Fee Related
- 1999-06-30 WO PCT/NL1999/000406 patent/WO2000001749A1/en active IP Right Grant
- 1999-06-30 ES ES99929970T patent/ES2226402T3/es not_active Expired - Lifetime
- 1999-06-30 AU AU46601/99A patent/AU748525B2/en not_active Ceased
- 1999-06-30 CA CA002336637A patent/CA2336637A1/en not_active Abandoned
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| Publication number | Publication date |
|---|---|
| ES2226402T3 (es) | 2005-03-16 |
| AU4660199A (en) | 2000-01-24 |
| NO20010036D0 (no) | 2001-01-03 |
| NO20010036L (no) | 2001-03-06 |
| PL345410A1 (en) | 2001-12-17 |
| EP0970977A1 (en) | 2000-01-12 |
| ATE274538T1 (de) | 2004-09-15 |
| US20010006730A1 (en) | 2001-07-05 |
| EP1093481A1 (en) | 2001-04-25 |
| WO2000001749A1 (en) | 2000-01-13 |
| DE69919711T2 (de) | 2005-08-18 |
| AU748525B2 (en) | 2002-06-06 |
| CN1308646A (zh) | 2001-08-15 |
| CA2336637A1 (en) | 2000-01-13 |
| DE69919711D1 (de) | 2004-09-30 |
| EP1093481B1 (en) | 2004-08-25 |
| KR20010071728A (ko) | 2001-07-31 |
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