CN86101422A - 防污组合物及其应用 - Google Patents
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
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- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
Abstract
防污组合物包含:
(A)一种含有10~100%(重量)的式(I)结构单 元的聚合物,
Description
本发明涉及到防污组合物及赋于基质以防污性能的方法。
常常用防污组合物对塑料、织物、纸等进行处理以提高它们的一些具有一定耐久性的价值。
普通的防污组合物含有硅酮、烃类聚合物或氟代烃类聚合物(参阅日本专利公报№18346/1978及日本专利公开公报(未审查过的)№134786/1978、163269/1980、129281/1981、164181/1982、171762/1982及171790/1982)。
不过,普通的含硅酮或烃类聚合物的防污组合物只能赋于基质以吸水性和防污性能:或者,仅仅赋于基质以防水性。含有氟代烃类聚合物的普通防污组合物则只赋于基质防水及防油特性或者仅赋于它非耐久性的防污性能。
本发明的一个目的是提供一种防污组合物,它可赋于基质耐久的吸水性和防油性,同时还赋于它以防污性能。
本发明的另一目的是提供一种防污组合物,它可赋于基质防水防油特性,同时还赋于基防污特性。
本发明还有一个目的是提供一种用防污组合物来赋于基质以防污性能的方法。
这些及其它一些目的都是借助本发明给出的防污组合物来实现的。组合物包括:
(A)聚合物,它含有化学式为(Ⅰ)的结构单元,其含有重量百分数为10-100%。
式中Rf为C3-C21氟代烷基:R1为氢原子或C2-C4酰基;R2、R3、R4、R5可以相同或不同,每一种可分别是氢原子、甲基或乙基;A为具有下列化学式的一个基团:-CH2CH(OR1)CH2-OCO-,其中R1的规定同上:-CO-;-(CH2)KN(R2)CO-中R2的规定同上,K为1到10的整数;或-(CH2)K-,其中K的规定同上;h为0到5的整数:p为1到40的整数;q和r可以相同或不同,每一种分别为0至40的整数。
(B)亲水树脂
(C)任意一种防水防油剂;(A)∶(B)∶(C)的重量比是5-95∶95-5∶0或1-95∶5-95∶1-50。
当本发明的防污组合物由聚合物(A)及亲水树脂(B)组成而不含防水防油剂(C)时,它可在赋于基质以防污性能的同时赋于吸水性和防油性。当本发明的防污组合物由聚合物(A)、亲水树脂(B)及防水防油剂(C)组成时,它可在赋于基质防污性能的同时亦赋于防水防油性。
含有结构单元(Ⅰ)的聚合物(A)可由具有化学式为(Ⅱ)的不饱和单体均聚制备。
Rf-(CF2)hCH(OR1)CH2-O-(CHR2CH2O)p-
(CHR3CH2O)q-(CHR4CH2O)r-A-CR5=CH2(Ⅱ)
式中Rf、R1-R5、A、h、P、q及r的规定同上所述。或者,单体(Ⅱ)同至少一种其它乙烯类不饱和单体共聚。
化学式中的氟代烷基Rf可以是直链或支链,而且比基中的氟原子数最好多于碳原子数,前者比后者大两倍更佳。在Rf中的碳链里碳原子间至少有一个氧原子。单体(Ⅰ)的一些具体例子是:
C5F11CH2CH(OH)CH2O(CH2CH2O)4COCH=CH2,
C7F15CH2CH(OH)CH2O(CH2CH2O)8COC(CH3)=CH2,
C8F17CH2CH(OH)CH2O(CH2CH2O)5CH2NHCOCH=CH2,
C8F17CH2CH(OH)CH2O(CH2CH2O)8COC(CH3)=CH2,
C8F17CH2CH(OCOCH3)CH2O(CH2CH2O)9COCH=CH2,
C9HF18CH2CH(OH)CH2O(CH2CH2O)10COC(CH3)=CH2,
C9F19CH2CH(OH)CH2O(CH2CH2O)13CH2CH=CH2,
C10F21CH2CH(OH)CH2O(CH2CH2O)16CH2CH(OH)CH2OCOC(CH3)=CH2,
C12F21CH2CH(OCOCH3)CH2O(CH2CH2O)22COC(CH3)=CH2,
C8F17CH2CH(OCOCH3)CH2O(CH2CH2O)10COCH=CH2,
C9F19(CH2)3CH(OH)CH2O(CH2CH2O)5(CH(CH3)CH2O)5COCH=CH2,
C15F31CH2CH(OCOCH2CH3)CH2O(CH2CH2O)13CH2CH=CH2,
C11F23CH2CH(OH)CH2O(CH2CH2O)8CH2CH2NHCOCH=CH2.
用来与单体(Ⅱ)共聚的不饱和烯类单体的例子有氯乙烯、醋酸乙烯酯、苯乙烯、α-甲基苯乙烯、甲基乙烯基甲酮、丙烯酸或甲基丙烯酸,或者它化学式为(Ⅲ)的衍生物:
式中R6为氢原子或甲基;R7为氢原子、钠原子、钾原子、铵基、C1-C18烷基、缩水甘油基,或具有下列化学式的基团:-(CH2CH2O)pR8,式中R8为氢原子、C1-C18烷基,或C2-C18酰基,而p的规定同上;
-(CH2CH2O)p-(CH2CH(CH3)O)q-(CH2CH2O)r-R8,式中R8、p、q及r的规定同上;或者-R9-OH,式中R9为C2-C6亚烷基;还有化学式为(Ⅳ)的丙烯酰胺或甲基丙烯酸胺,或它的衍生物:
式中R6的规定同上;R10为氢原子或具有化学式为-CH2OH或-(CH2)p-N(CH3)2的一个基团,式中p的规定同上。
单体可按已知方法,例如日本专利公开公报(未经审查)№134786/1978及日本粘合剂协会杂志,vol.17,№9(1981)371页介绍的方法均聚或共聚。
亲水树脂包括乙二醛树脂、密胺树脂、聚酰胺树脂、尿烷树脂、丙烯酸树脂、三嗪树脂等。一些亲水树脂有商品出售,其商标为HW-100(大日本墨水与化学品公司),Sumitex树脂901、1000,M-3,NR-2,NS-2,W-2,AR-2和AMH-3000(Sumitomo化学品公司),Blencope PWB-4021,PEB-4001和PEB-4002(日本油脂公司),Teisan尿烷SL-1780和SL-4780(Teikoku化学工业公司)及SR-1000(Takamatsu油脂公司)。
防水防油剂可以是普通使用的那种,但最好是下列单体的共聚物:化学式为(Ⅴ)的丙烯酸衍生物,
式中Rf的规定同上,而x为氧原子或硫原子;和化学式为(Ⅵ)的丙烯酸或甲基丙烯酸或它的衍生物:
式中R6的规定同上,而R11为氢原子、钠原子、钾原子,铵基或C1-C18烷基。化合物(Ⅴ)和(Ⅵ)共聚体的制备,下列专利中已作了介绍,例如日本专利公报№s 851/1969、31202/1971、42880/1972、3433/1975、4300/1975、2993/1973、11324/1932及9666/1984和日本专利公开公报(未经审查)№s 132694/1979及11333/1983。
当本发明的防污组合物由聚合物(A)及亲水树脂组成,但不含防水防油剂(C)时,共聚物(A)中含有的结构单元(I)为10-100%(重量),最好为20-80%(重量),以赋于基质足够的防油性及防污性能。同样,在组合物中,共聚物(A)的重量份数为5-95,最好是20-80。为在赋于基质防污性能的同时赋于耐久的吸水性和防油性,在组合物中,亲水树脂(B)的重量份数为5-95,最好为10-80。
当本发明的防污组合物由聚合物(A)、亲水树脂(B)和防水防油剂(C)组成时,为赋于基质足够的防油性和防污性,结构单元(I)在聚合物(A)中所占的重量百分数为10-100%,最好是20-90%。与上述理由同样,组合物中的聚合体(A)的重量份数为1-95,最好是5-90。为提高防水防油性和防污性的耐久性,亲水树脂(B)在组合物中的重量份数为5-95,最好为10-80。为了在赋于基质防污性能的同时也赋于足够的防水防油性,防水防油剂(C)在组合物中的重量份数为1-50,最好为20-40。
本发明的防污组合物还可含至少一种普通防污组合物中所使用的添加剂。添加剂包括促使亲水树脂(B)固化的催化剂(例如硝酸锌、氯化镁等)。一种普通的、可得到的催化剂是Sumitex促进剂(商标为Sumitomo化学品)。
本发明的防污组合物可以以溶液、分散体、悬浮液、乳化液的形式存在,用普通的方法,如浸涂、喷涂、漂(flow)涂等方法加至基质上。混合所述成分的介质包括水、丙酮、醋酸乙酯、四氢呋喃、三氯三氟乙烷、三氟苯、六氟间二甲苯及其混合物。本发明的组分,一般按每100份重量的介质含0.5-1.0份重量。
现在,用下列实例来进一步详细解释本发明。在这些实例中,防污组合物含有聚合体(A)及亲水树脂(B),而不含防水防油剂(C),对防污组合物的吸水性、防油性和防污性,以及这些性能的耐久性进行检验。对含有聚合物(A)、亲水树脂(B)和防水防油剂(C)的防污组合物,检验其防水性、防油性和防污性以及这些性能的耐久性。在这些实例中,如无另外说明,均指重量份数和重量百分数(%)。
用于实例和对比实例中的共聚物(A1)-(A5)及用于对比的聚合物(ⅰ)-(ⅲ)是按下述制备实例进行制备的。
制备实例1
共聚物(A1)的制备
在带有温度计、冷凝器、搅拌器及氮气导管的200ml四口烧瓶中,加入具有下列化学式的含氟单体混合物(14g):
CF3CF3(CF2CF2)nCH2CH(OH)CH2-O-Z-COC(CH3)=CH2
式中Z为聚氧化乙烯基团,其平均分子量为400。此混合物中包含的上述化学式的化合物其n为2、3、4、5或6,各自相应的量为3%、55%、28%、12%及3%;还加入下列分子式的甲基丙烯酸酯衍生物(14克),
式中Z的规定同上;再加入异丙醇(112克)及十二碳硫醇(0.4克)。导入氮气,于67℃搅拌30分钟。然后加入新戊酸过丁酯(perbutyl)以引发反应。在同一温度下搅拌6小时进行聚合。从反应混合物中去掉异丙醇后,用苯洗涤残留物,减压干燥,得到共聚物(A1)。
制备实例2-5及对比制备实例1-3
共聚物(A2)-(A5)及聚合物(ⅰ)-(ⅲ)的制备
用与制备实例1同样的方法,但用下列单体进行聚合,制备聚合物。
制备实例2(共聚物(A2))
制备实例1中所用的含氟单体混合物(100份),制备实例1中所用的甲基丙烯酸酯衍生物(100份)及HOCH2-NHCOCH=CH2(20份)。
制备实例3(共聚物(A3))
制备实例1所用的含氟单体混合物(100份),苯乙烯(300份)及甲基丙烯酸缩水甘油酯(100份)。
制备实例4(共聚物(A4))
制备实例1所用的含氟单体混合物(100份)及H-Y-SCH2COOCH2CH(OH)-CH2OCOC(CH3)=CH2,式中Y为平均分子量为1500的聚苯乙烯基团(100份)。
制备实例5
制备实例1所用的含氟单体混合物(100份),制备实例1所用的甲基丙烯酸酯衍生物(80份)及丙烯酸丁酯(20份)。
对比制备实例1(聚合物(ⅰ))
CF3CF2(CF2CF2)3CH2CH2OCOCH=CH2(100份),CH3O-W-COC(CH3)=CH2,式中W为平均分子量660的聚氧化乙烯基团(80份)以及HOCH2NHCOCH=CH2(20份)。
对比制备实例2(聚合物(ⅱ))
H〔SCH2CH(CH3)COO(CH2CH2O)4COC(CH3)CH2〕10SH(10份)及C8H17SO2N(C3H7)CH2CH2OCOC(CH3)=CH2(60份)。
对比制备实例3(聚合物(ⅲ))
C8H17SO2N(C3H7)-W-COC(CH3)=CH2(100份)及CH3O-W-COCH=CH2(100份),式中W的规定同上。
实例1-5及对比实例1-2
防污组合物的配制
共聚物(A)或对比聚合物、亲水树脂及其它添加剂按下列配比加至100份水中,搅拌,配成具有吸水性及防油性的防污组合物。
组合物
实例1和实例2
共聚物(A1)(0.5份);
Sumitex树脂901(0.5份)和Sumitex树脂W-2(0.5份)(亲水树脂);
硝酸锌(0.5份)。
实例3
共聚体(A2)(0.5份);
Blencope PEB-4201(0.5份)(亲水树脂)。
实例4
共聚体(A3)(0.5份);
Sumitex树脂AR-2(0.5份)(亲水树脂)。
实例5
共聚体(A4)(0.5份);
Sumitex树脂AR-2(0.5份)。
对比实例1
聚合物(ⅱ)(0.5份);
Sumitex树脂901(0.5份);
Sumitex树脂W-2(0.5份);
硝酸锌(0.5份)。
对比实例2
聚合物(ⅱ)(0.5份);
Sumitex树脂AR-2(0.5份)。
将实例1-5及对比实例1-2中所制备的每种组合物加至各种基质上,对其吸水性、防油性、防污性以及这些性能的耐久性进行检验。
当基质为纺织物时,将其浸入组合物中5分钟,用滚筒挤压,于80℃下干燥10分钟后,再于150℃加热5分钟。当基质为板材时,将其浸入组合物中5分钟,贴在墙上于80℃下干燥10分钟,随后于150℃加压5分钟。
经过处理的基质性能评价如下:
吸水性
将一滴水滴至处理后的基质表面上,用肉眼确定水完全消失所需的时间(秒数)。
防油性
将一滴直径4mm的下列溶剂混合物滴至基质上,用肉眼观察液滴在三分钟内保持其形状的混合物临界成分,用下列分数表示防油性。分数愈高,防油性愈好。
防污试验
经过处理的基质浸入废摩托油中10小时,用肉眼观察表面条件,判定标准如下:
1、有极脏的沾污残留;
2、有脏的沾污残留;
3、有一些沾污残留;
4、有轻微沾污残留;
5、没有沾污残留。
耐久性
经过处理后的基质,按照日本工业标准(JIS)H 103的规定,用浓度2克/升的洗涤剂清洗10次。所用的洗涤剂为“Super Zabu”(Kao公司生产)。清洗温度为40℃,浸没比为1∶40。洗涤后按前述方法进行吸水试验、防油试验及防污试验。
结果示于表1-1~1-3中。
实例6-15及对比实例3-6
将共聚物(A)或对比聚合物、亲水树脂、防水防油剂及其它添加剂以下述量,按下列组分加至100份水中,搅拌,配成具有吸水性和防油性的防污组合物。
组合物
实例6
共聚物(A1)(0.5份);
Sumitex树脂901(0.5份);
Sumitex树脂W-2(0.5份);
防水防油剂(A)1)(0.1份);
硝酸锌(0.5份)。
实例7
共聚物(A2)(0.5份);
Sumitex树脂M-3(0.5份);
防水防油剂(A)(0.1份);
Sumitex促进剂(0.5份)。
实例8
共聚物(A2)(0.5份);
Teisan尿烷SL-4780(0.5份);
防水防油剂(A)(0.1份)。
实例9
共聚物(A3)(0.5份);
Sumitex树脂M-3(0.5份);
防水防油剂(A)(0.1份);
Sumitex促进剂(0.5份)。
实例10
共聚物(A3)(0.5份);
Serbifan MKP1(0.5份);
防水防油剂(A)(0.05份)及防水防油剂(B)2)(0.2份);
Serbifan KP2(0.2份)。
实例11
共聚物(A4)(0.5份);
Sumitex树脂M-3(0.5份);
防水防油剂(A)(0.1份);
Sumitex促进剂(0.5份)。
实例12
共聚物(A4)(0.5份);
Sumitex树脂NR-2(0.5份);
防水防油剂(A)(0.1份);
硝酸锌(0.5份)。
实例13
共聚物(A5)(0.5份);
Sumitex树脂(0.5份);
防水防油剂(A)(0.2份);
Sumitex促进剂(0.5份)。
实例14
共聚物(A5)(0.5份);
Blencope 4001(0.5份);
防水防油剂(A)(0.2份)。
实例15
共聚物(A5)(0.5份);
Serbifan MKP1(0.5份);
防水防油剂(A)(0.2份);
Serbifan KP2(0.2份)。
对比实例3
聚合物(ⅰ)(1.0份);
Sumitex树脂M-3(0.5份);
防水防油剂(A)(0.2份);
Sumitex促进剂(0.5份)。
对比实例4
聚合物(ⅰ)(0.5份);
Serbifan MKP 1(0.5份);
防水防油剂(A)(0.05份)和防水防油剂(B)(0.2份);
Serbifan KP 2(0.2份)。
对比实例5
聚合物(ⅲ)(0.5份);
Sumitex树脂901(0.5份)和Sumitex树脂W-2(0.5份);
防水防油剂(A)(0.1份);
硝酸锌(0.5份)。
对比实例6
聚合物(ⅲ)(0.5份);
Teisan尿烷SL-4780(0.5份);
防水防油剂(A)(0.1份)。
注:防水防油剂(A):C8F17CH2CH2OCOCH=CH2和甲基丙烯酸十八酰酯的共聚物,其平均分子量为25000。
防水防油剂(B):C8F17CH2CH2SCOCH=CH2和甲基丙烯酸十八酰酯的共聚物,其平均分子量为25000。
将按实例6-15和对比实例3-6制备的每种组合物加至各种基质,检验其防水性、防油性、防污性以及这些性能的耐久性。
组合物加至基质的方法同实例1-5中所述的方法。
防水性按日本工业标准(JIS)L-1005进行评价。防油性及防污性按实例1-5中所用的方法进行评价。这些性能的耐久性也按实例1-5中所用的方法评价。
结果示于表2-1、2-2及2-3中。
Claims (13)
1、防污组合物特征在于包含:
(A)含有化学式(I)结构单元的重量百分数为10-100%的聚合物:
Rf-(CF2)hCH(OR1)CH2-O-(CHR2CH2O)p-(CHR3CH2O)q-(CHR4CH2O)r
式中Rf为C3-C21氟代烷基;R1为氢原子或C2-C4酰基;R2、R3、R4及R5可以相同或不同,其每一个可以是氢原子、甲基或乙基;A为具有下列化学式的基团:-CH2CH(OR1)CH2-OCO-,式中R1的规定同上;-CO-;-(CH2)kN(R2)CO-,式中R2的规定同上,而K为1-10的整数;或者-(CH2)k-,式中k的规定同上;h为0-5的整数;p为1-40的整数;q和r可以相同或不同,它们每个为0-40的整数。
(B)亲水树脂;
(C)任意一种防水防油剂。
(A)∶(B)∶(C)的重量比为5-95∶95-5∶0,或者1-95∶5-95∶1-50。
2、根据权利要求1的防污组合物,它含有5-95份(重量份数)的聚合物(A)及95-5(重量份数)的亲水树脂(B)。
3、根据权利要求2的防污组合物,其中聚合物(A)含有20-80%(重量比)结构单元(Ⅰ)。
4、根据权利要求2的防污组合物,其中聚合物(A)与亲水树脂(B)的重量比为5-80∶95-20。
5、根据权利要求2的防污组合物,其中聚合物(A)和亲水树脂(B)的重量比为20-90∶80-10。
6、根据权利要求1的防污组合物,其中含聚合物(A)的重量份数为1-95,亲水树脂(B)的重量份数5-95,而防水防油剂(C)的重量份数为1-50。
7、根据权利要求6的防污组合物,其中聚合物(A)含有结构单元(Ⅰ)的重量百分数为20-90%。
8、根据权利要求7的防污组合物,其中含聚合物(A)的重量份数为5-90,亲水树脂(B)的重量份数为10-80,而防水防油剂(C)的重量份数为2-40。
9、根据权利要求1的防污组合物,其中Rf基的氟原子数至少大于该基内碳原子数的2倍。
10、根据权利要求1的防污组合物,其中聚合物(A)是结构单元(Ⅰ)的均聚体。
11、根据权利要求1的防污组合物,其中聚合物(A)含有结构单元(Ⅰ)和下述至少一种共聚用单体结构单元的共聚体,后种结构单元包括氯乙烯、醋酸乙烯酯、苯乙烯、α-甲基苯乙烯、甲基乙烯基甲酮、丙烯酸或甲基丙烯酸或者下列化学式的衍生物基团:
式中R6为氢原子或甲基;R7为氢原子、钠原子、钾原子、铵基、C1-C18烷基、缩水甘油基,或具有下列化学式的基团:-(CH2CH2O)pR8,式中R8为氢原子、C1-C18烷基、C2-C18酰基,而p的规定同上;-(CH2CH2O)p-(CH2CH(CH3)O)q-(CH2CH2O)r-R8,式中R8、p、q及r的规定同上;或者,-R9-OH,式中R9为C2-C6亚烷基;用于共聚的还有化学式为(Ⅳ)的丙烯酰胺或甲基丙烯酰胺,或者它的衍生物:
式中R6的规定同上;R10为氢原子或化学式为-CH2OH或-(CH2)p-N(CH3)2基团,式中p的规定同上。
12、根据权利要求6的防污组合物,其中防水防油剂(C)为下列单体的共聚物:化学式为(Ⅴ)的丙烯酸衍生物:
式中Rf的规定同上,而X为氧原子或硫原子;和化学式为(Ⅵ)的丙烯酸或甲基丙烯酸或它的衍生物共聚:
式中R6的规定同上,而R11为氢原子、钠原子、钾原子、铵基或C1-C18烷基。
13、赋于基质以防污性能的方法,它包括将权利要求1的组合物混合在液体介质中,干燥以从基质除去液体介质。
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US3491169A (en) * | 1966-07-22 | 1970-01-20 | Du Pont | Oil and water repellent |
JPS503438B1 (zh) * | 1969-01-17 | 1975-02-04 | ||
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JPS59204144A (ja) * | 1983-04-12 | 1984-11-19 | Daikin Ind Ltd | 新規含フッ素化合物およびその製法 |
US4564561A (en) * | 1985-03-27 | 1986-01-14 | E. I. Du Pont De Nemours And Company | Fluorine-containing polymer compositions and their preparation |
-
1986
- 1986-03-03 US US06/835,754 patent/US4695488A/en not_active Expired - Lifetime
- 1986-03-06 EP EP86103005A patent/EP0195323B1/en not_active Expired - Lifetime
- 1986-03-06 DE DE8686103005T patent/DE3686495T2/de not_active Expired - Fee Related
- 1986-03-10 JP JP61052296A patent/JPS627782A/ja active Granted
- 1986-03-11 KR KR1019860001732A patent/KR950002240B1/ko not_active IP Right Cessation
- 1986-03-12 CN CN86101422.7A patent/CN1004420B/zh not_active Expired
Also Published As
Publication number | Publication date |
---|---|
EP0195323A3 (en) | 1988-11-09 |
KR950002240B1 (ko) | 1995-03-15 |
US4695488A (en) | 1987-09-22 |
JPS627782A (ja) | 1987-01-14 |
EP0195323B1 (en) | 1992-08-26 |
DE3686495T2 (de) | 1993-03-04 |
KR860007340A (ko) | 1986-10-10 |
EP0195323A2 (en) | 1986-09-24 |
DE3686495D1 (de) | 1992-10-01 |
JPH043788B2 (zh) | 1992-01-24 |
CN1004420B (zh) | 1989-06-07 |
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