CN1203245A - 聚合物组合物 - Google Patents

聚合物组合物 Download PDF

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CN1203245A
CN1203245A CN98114949A CN98114949A CN1203245A CN 1203245 A CN1203245 A CN 1203245A CN 98114949 A CN98114949 A CN 98114949A CN 98114949 A CN98114949 A CN 98114949A CN 1203245 A CN1203245 A CN 1203245A
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W·劳
M·J·芬蕾
M·M·威廉姆斯
H·C·莫利斯
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Rohm and Haas Co
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Abstract

公开了用于提高纤维、无纺物、织物和纸张组合物的疏水性和持久性的聚合物组合物。并且公开了在纤维、无纺物、织物和纸张组合物中改进疏水性和持久性的方法。

Description

聚合物组合物
本发明涉及到聚合物组合物，更具体地本发明涉及到可以用作纤维、无纺物、织物和纸张组合物中的粘合剂的聚合物组合物。
纤维、无纺物、织物和纸张组合物典型地被涂以聚合物粘合剂，以提供疏水性和持久性。典型地，将自交联丙烯酸系聚合物和苯乙烯/丙烯酸系聚合物用于这些应用中。在纤维、无纺物、织物和纸张组合物中需要提供改进疏水性和持久性的聚合物粘合剂。
U.S.专利号5,521,266公开了一种从疏水性单体形成聚合物的方法。本公开的方法采用了大分子有机化合物，该化合物具有络合低水溶性单体的疏水空腔。这使得通过乳液聚合从低水溶性单体形成聚合物成为可能。用于该方法中形成聚合物的适当的单体包括甲基丙烯酸十二烷基酯。
U.S.专利号3,915,921公开了通过溶液聚合制备的共聚物。该共聚物含有疏水性单体包括甲基丙烯酸十八烷基酯，和某些羧基单体包括丙烯酸。该共聚物被认为是有效的增稠剂。
尽管有当前公开的这些技术，在纤维、无纺物、织物和纸张组合物中仍继续需要改进疏水性和持久性的聚合物粘合剂。
我们已吃惊地发现应用本发明的聚合物组合物在纤维、无纺物、织物和纸张组合物中提供了改进的疏水性和持久性。
本发明提供了一种包含乳液聚合物的组合物，该乳液聚合物含有作为聚合单元的：
i)a)从9.5到99.9份重量的至少一种C12到C40的(甲基)丙烯酸烷基酯；
b)从0到90份重量的至少一种小于C15的烯属不饱和的非离子型单体；
c)从0到90份重量的至少一种含有烯属不饱和酸的单体或它的盐；和
d)从0.1到10份重量的至少一种交联单体；以及
ii)基于聚合物重量的从0到10份重量的至少一种交联剂，
条件是该组合物含有基于聚合物重量的从0.1到10份重量的交联单体和交联剂。
在另一个具体实施方案中，本发明提供了一种在纤维、无纺物、织物和纸张组合物中改进疏水性和持久性的方法，它包括：
a)提供了一种包含乳液聚合物的组合物，该乳液聚合物含有作为聚合单元的：
i)从9.5到100份重量的至少一种C12到C40的(甲基)丙烯酸烷基酯；
从0到90份重量的至少一种小于C15的烯属不饱和的非离子型单体；
从0到90份重量的至少一种含有烯属不饱和酸的单体或它的盐；和
从0到10份重量的至少一种交联单体；以及
ii)基于聚合物重量的从0到10份重量的至少一种交联剂；
b)提供了从包括纤维、无纺物、织物和纸张的种类中选出的一种基材；
c)用聚合物组合物涂饰基材；以及
d)干燥被涂饰的基材。
本发明也提供了一种制件，它包括：
从包括纤维、无纺物、织物和纸张的种类中选出的一种基材，它涂布了一种乳液聚合物组合物，该组合物含有作为聚合单元的：
i)从9.5到100份重量的至少一种C12到C40的(甲基)丙烯酸烷基酯；
从0到90份重量的至少一种小于C15的烯属不饱和的非离子型单体；
从0到90份重量的至少一种含有烯属不饱和酸的单体或它的盐；和
从0到10份重量的至少一种交联单体；以及
ii)基于聚合物重量的从0到10份重量的至少一种交联剂；
本发明的组合物可以通过一阶段或多阶段法制备。该方法可以是乳液聚合例如在U.S.专利号5,521,266中介绍的方法。该方法也可以通过如在U.S.专利号5,539,021中介绍的溶液聚合接着乳化，或是微乳液聚合或微滴乳液聚合。乳液聚合是优选的。在用于制备本说明书范围内试样的方法中，第一阶段是通过将单体乳液和过硫酸钠加入到含有甲基-β-环糊精(“CD”)、去离子水和表面活性剂的溶液中完成的。第一阶段是在85℃下反应。第二阶段是通过制备第二种单体乳液并将第二种单体乳液和过硫酸钠溶液加入到反应的第一步中来完成的。第二阶段是在85℃下反应的。
本发明的组合物含有作为聚合单元的从9.5到100份重量、优选地从15到80份重量、更优选地从20到70份重量的至少一种C12到C40的(甲基)丙烯酸烷基酯。优选的是(甲基)丙烯酸烷基酯为C12到C30的(甲基)丙烯酸烷基酯。更优选的是(甲基)丙烯酸烷基酯为C12到C18的(甲基)丙烯酸烷基酯。适当的(甲基)丙烯酸烷基酯包括(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸二十二烷基酯和(甲基)丙烯酸二十烷基酯。通过采用多于一种的C12到C40的(甲基)丙烯酸烷基酯可以获得有用的性能。
本发明的组合物也含有作为聚合单元的从0到90份重量、优选地从15到90份重量、更优选地从20到80份重量的至少一种小于C15的烯属不饱和的非离子型单体。用于制备本发明聚合物组合物的适当的小于C15的烯属不饱和的非离子型单体包括，但并不限定于(甲基)丙烯酸酯单体，包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸癸酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸羟乙酯和丙烯酸羟丙酯；丙烯酰胺或取代的丙烯酰胺；苯乙烯或取代的苯乙烯；醋酸乙烯酯或其它乙烯基酯；乙烯基单体例如氯乙烯、偏氯乙烯、N-乙烯基吡咯烷酮；和丙烯腈或甲基丙烯腈。丙烯酸丁酯、甲基丙烯酸甲酯和苯乙烯是优选的。更优选的是丙烯酸丁酯和甲基丙烯酸甲酯。
本发明的组合物也含有作为聚合单元的从0到90份重量、优选地从0.1到50份重量、更优选地从1到10份重量的含有烯属不饱和酸的单体或它的盐。适当的含有烯属不饱和酸的单体包括，但并不限定于丙烯酸、甲基丙烯酸、巴豆酸、甲基丙烯酸磷酸基乙酯、2-丙烯酰胺基-2-甲基-1-丙烷磺酸、乙烯基磺酸钠、衣康酸、富马酸、马来酸、衣康酸单甲基酯、富马酸单甲基酯、富马酸单丁基酯和马来酸酐。丙烯酸和甲基丙烯酸是优选的。甲基丙烯酸是更优选的。
本发明的组合物也含有作为聚合单元的基于聚合物重量的从0.1到10份重量、优选地从0.1到5份重量、更优选地从0.1到3份重量的从交联剂和交联单体中选出的交联体。交联体表示具有至少两个反应性基团的化合物，该反应性基体可以与在本发明的组合物的单体中出现的酸基团反应。用于本发明的交联剂包括多乙烯亚胺、多异氰酸酯、多碳化二亚胺、多元胺和多价金属。交联剂是非必须的，并且可以在聚合反应结束后加入。
交联单体是在聚合反应过程中与本发明组合物的单体结合的交联体。用于本发明的交联单体包括二乙烯基苯、多羟基化合物的(甲基)丙烯酰基聚酯、多羧酸的二乙烯基酯、多羧酸的二烯丙基酯、二烯丙基二甲基氯化铵、对苯二甲酸三烯丙基酯、亚甲基双丙烯酰胺、马来酸二烯丙基酯、富马酸二烯丙基酯、六亚甲基双马来酰胺、磷酸三烯丙基酯、偏苯三酸三乙烯基酯、己二酸二乙烯基酯、三甲基丙烯酸甘油酯、琥珀酸二烯丙基酯、二乙烯基醚、乙二醇或二乙二醇的二乙烯基醚二丙烯酸酯、聚乙二醇二丙烯酸酯或甲基丙烯酸酯、1，6-己二醇二丙烯酸酯、季戊四醇三丙烯酸酯或四丙烯酸酯、新戊基二醇二丙烯酸酯、环戊二烯二丙烯酸酯、丁二醇的二丙烯酸酯或二甲基丙烯酸酯、三甲醇丙烷二或三丙烯酸酯、(甲基)丙烯酰胺、n-羟甲基(甲基)丙烯酰胺、它们的混合物等等。(甲基)丙烯酰胺、n-羟甲基(甲基)丙烯酰胺和它们的混合物是优选的。以交联体不影响膜形成来选择交联体的量。
链转移剂可以用来控制聚合物组合物的分子量。适当的链转移剂包括硫醇，例如十二烷基硫醇。链转移剂可以以基于聚合物组合物总重量的0.1％到10％来采用。
本发明的聚合物组合物可用于纤维、无纺物、织物和纸张组合物。
本发明的聚合物组合物典型地被用于纤维、无纺物、织物和纸张组合物。通过将基材浸入聚合物组合物中或将聚合物组合物喷涂到基材上，可以将聚合物组合物涂饰或处理基材例如纤维、无纺物、织物或纸张。然后涂布的基材在从室温到200℃的温度下干燥。然后基材可以在从室温到200℃的温度下固化。优选的是使用足够的聚合物组合物以达到在涂布的产品重量上的2％到200％的粘合剂添加量。更优选的是使用足够的聚合物组合物以达到在涂布的产品重量上10％到50％的粘合剂添加量。
在整个本发明申请书中，采用下面的缩写：LMA＝甲基丙烯酸十二烷基酯，SMA＝甲基丙烯酸十八烷基酯，St＝苯乙烯，MMA＝甲基丙烯酸甲酯，BA＝丙烯酸丁酯，MMA＝甲基丙烯酸，nDDM＝正十二烷基硫醇，Id.＝试样编号，CD＝甲基-β-环糊精，g＝克，℃＝摄氏温度，(甲基)丙烯酸酯＝甲基丙烯酸酯和丙烯酸酯，cc＝立方厘米，MMAM＝50％甲基丙烯酰胺/50％n-羟甲基甲基丙烯酰胺，cm＝厘米，MAM＝90％n-羟甲基丙烯酰胺/10％丙烯酰胺，mm＝毫米，oz/sq yd＝盎司/平方码，ml＝毫升，psi＝磅每平方英寸，Abs.＝吸收率，RH＝相对湿度，wt＝重量，rpm＝每分钟转数
下表列举了用于本发明申请书中的一些原料和它们的来源：
原料               作用             来源TritonXN-45S      表面活性剂      Union CarbideFC-280            氟代化学品      3M公司Michem Lube743    蜡              McGeeMikonNRW-3        表面活性剂      Sequa化学公司AircelPC-6A       甲基化的蜜胺    Borden(Astro
                                Ind ustries)Cymel303          蜜胺            CytekScotchMagic Tape  胶带            3M公司TritonX-100    表面活性剂    Union Carbide
实施例1
对于第一阶段，在室温下将400克去离子水、11.9克TritonXN-45S阴离子表面活性剂(58％)和CD(表1，53％的水溶液)加入到配以机械搅拌器、温度控制设备、冷凝器、单体和引发剂加料管和氮气入口的4升四颈圆底烧瓶中。在氮气清洗下搅拌的同时将内容物加热到85℃。分别制备31.3克去离子水、0.4克TritonXN-45S阴离子表面活性剂、33.8克LMA、7.5克BA、33克MMA和0.75克MAA的单体乳液。将在25克去离子水中的0.35％重量的碳酸钠(基于第一阶段和第二阶段总的单体重量)溶液和在30克去离子水中的0.35％重量的过硫酸钠(基于第一阶段和第二阶段总的单体重量)加入到反应釜中。在20分钟内加入单体乳液和在210克去离子水中的0.05％的过硫酸钠引发剂溶液(基于第一阶段和第二阶段总的单体重量)。
在第二阶段，用625克去离子水、7.8克TritonXN-45S阴离子表面活性剂和根据表1的单体制备单体乳液。在第一阶段单体乳液加料结束后，立即在3小时内加入第二阶段单体乳液和过硫酸钠引发剂溶液。
                          表1Id.   LMA    SMA  BA     MMA    MAA  MAM  MMAM    CD
1    300    0    525    660    15    0    0    14.3
2    675    0    225    585    15    0    0    14.3
3    780    0     0     705    15    0    0    14.3
4     0    975    0     480    15    0    30   28.6
5     0    975    0     510    15    0    0    28.6
6     0    750   285    450    15    0    0    28.6
7    750    0    435    270    15    30   0    14.3
8     0    975    0     480    15    30   0    28.6
9    750    0    735     0     15    0    0    14.3
10    0    975    0     510    15    0    0    28.6
试样4、7和8是本发明组合物的实施例。所有的试样表明该组合物在纤维、无纺物、织物或纸张应用中的可用性。实施例2-应用测试-冲击渗透测试
冲击渗透测试通过冲击测定纤维对水渗透的抵抗性。(AATCC测试方法42-1989)通过水渗透小于1克表明在测试中表现好的试样被认为是作为无纺物和纸张组合物的涂料/处理剂的好的选择。
为制备用于测试的试样，纸浆材料(Whatman FiIter Paper No：4)被填涂本发明的组合物。槽液固含量为35％并且填涂压力为大约3/4巴。在149℃下试样被干燥/固化3分钟，在涂布产品重量上得到26％的粘合剂添加量。试样被测试3次并且将结果平均。
通过一个喷嘴倾倒500毫升水并且让它以45°角冲击测试纤维，然后测定渗透过丝网并且在测试试样下面的一片吸水纸上收集到的水量来进行冲击渗透测试。结果如表2所示。
         表2
试样    水渗透量(克)
 6        0.3
上面的数据表明以含SAM的组合物键合的纸浆材料可用作无纺物和纸张组合物的涂料。实施例3-应用测试-吸水性
通过测定干燥/固化膜的吸水百分数，进行吸水性测试以评价本发明组合物的疏水性能。用吸水百分数小于35％表明在测试中表现好的试样被认为可用作无纺物和纸张组合物的涂料/处理剂。
通过在一容器中干燥乳胶一个晚上来制膜。然后膜在149℃下完全干燥/固化3分钟。膜厚度在10-15密耳之间。通过使膜浸泡在水中48小时后，对尺寸2.54cm×2.54cm×10密耳的干燥/固化膜试样测定不同聚合物的吸水百分数。试样被测试2次并且将结果平均。通过采用下面的等式测定本发明组合物的吸水百分数：其中Wi＝膜的初始重量
Wf＝在水中浸泡48小时后膜的最终重量。
结果如表3所示。
         表3
试样           吸水百分数
6                14.6
3                12.4
5                7.9
上面的数据表明组合物可用作无纺物、织物和纸张组合物中的涂料/处理剂。实施例4-应用测试-抗张测试和Handle-O-Meter
进行该测试以表明本发明的组合物作为无纺物的涂料/处理剂的应用。已知通过抗张强度表明的具有高强度的聚合物通常不是可接受的柔软。粘合剂的合格性是由大于1,000克的干态抗张；大于600克的湿态抗张；和大于300克的对异丙醇(IPA)抗张的数值来测定的。对Handle-O-Meter可接受的数值为50克力或更小。
填涂饱和性：以粘合剂饱和一1盎司/平方码聚酯网状物并在149℃下干燥/固化3分钟。所有试样具有基于纤维重量的大约40％粘合剂添加量。对这些试样进行抗张和Handle-O-Meter测试。饱和液配方如下(8％槽液固含量)：
211.6克粘合剂
4.8克催化剂  基于总固含量的1.5％固含量(25％NH4NO3)
783.6克水
抗张测试：使试样长轴在与机器交叉方向，采用Intelect 500 ThwingAlbert测试仪评价2.54×12.7厘米的网状物试样。使仪器设定到具有10.2厘米轨距长和30.5厘米/分钟十字头速度。对干、湿和异丙醇抗张测试进行平均至少7个样条。通过将网状物条浸泡在0.1％TritonX-100表面活性剂30分钟来获得湿态抗张。通过将网状物条浸泡在异丙醇中30分钟来获得异丙醇抗张。结果以克/2.54厘米来表示。
Handle-O-Meter：Handle-O-Meter测试是从10.2×10.2厘米网状物试样得到的。采用Thwing Albert Digital Handle-O-Meter(型号211-5)以0.64厘米间隔进行测试。仪器测定弯曲无纺物通过一定宽度窄缝的抵抗性。结果以克力表示。得到至少四个试样各自的机器方向和与机器交叉方向的平均读数。抗张和Handle-O-Meter测试的结果如表4所示：
                                表4
  试样 干态抗张 湿态抗张 IPA抗张 Handle-O-Meter
    5     2092     1339     546     107
90％的7/10％的8(混合)     1155     870     358     42
该组合物具有手可接受的柔软性并具有优良的干态和湿态抗张强度，因此可有效地用作无纺物组合物中的涂料/处理剂。实施例5-应用测试-Mason罐测试斥水性
进行该测试以评价本发明组合物的斥水/阻隔性能。Mason罐测试测定了无纺纤维在静压头下耐氯化钠水溶液的渗透性。该测试可用来测试医用无纺纤维排斥流体是如何的好。当试样显示120分钟或更高的数值时，它们被认为是可以接受的。
通过代替扁平的金属盖放置一测试纤维样板、将510毫升0.9％盐水溶液加入到罐中、将罐倒置(它的底部有一洞以平衡压力)并测定水渗透纤维需要的时间来进行测试。
以下面的方法制备用于Mason罐测试的试样：将一1盎司/平方码聚酯网状物填涂粘合剂/氟代化学品/蜡槽液。槽液的固含量为35％并且填涂压力为3/4巴。评价本发明的组合物。填涂试样在149℃下干燥/固化3分钟。总的粘合剂添加量为大约40％(基于涂布的产品重量)。每个试样以Mason罐测试进行3次测试并平均结果。填涂的配方如下(35％槽液固含量)：
111克粘合剂
8.1克FC-280(基于粘合剂固含量的5.6％固含量)
18.75克Michem Lube743(蜡)(基于粘合剂固含量的12.0％固含量)
1.25克MikonNRW-3(基于粘合剂固含量的2.5％Wet)
30克水
结果如表5所示。
      表5
试样    时间
6    120-300分钟
试样显示了可接受的数值，因此它被认为可用作医用无纺物组合物中的涂料/处理剂。实施例6-应用测试-水汽透过率
进行该测试以测定水汽渗透通过膜的速率。由1克/小时×平方米的WVTR体现的在该测试中表现好的试样被认为可用于无纺物应用中。
采用的测试方法是ASTM E96-80的水杯法。在该方法中，将30毫升的蒸馏水加入到塑料杯中。然后放上一在149℃下干燥/固化3分钟的聚合物膜(15-20密耳厚)并用一螺纹塑料环封闭杯口。然后将杯放置在恒定温度和湿度的室内(24℃/50％相对湿度)并周期性地称量杯重，以测定水运动通过聚合物膜到受控的环境中的速度。以重量损失对时间作图，直到出现公认的稳定状态。直线的斜率为水汽渗透速率。采用下面等式测定水汽渗透速率(WVTR)： WVTR = G ( T × A )
其中：G＝重量变化
      T＝时间
      A＝测试面积(杯口面积)WVTR以克/小时×平方米的单位表示。
结果如表6所示。
              表6
试样                  WVTR
5               0.19克/小时×平方米
该组合物提供了优良的湿气阻隔性，因此被认为可用作无纺物组合物中的涂料/处理剂。实施例7-应用测试-植绒评价
该测试测定本发明组合物用作植绒织物应用的粘合剂的可能性。
植绒配方为与5％粘土和1％硬脂酸铵混合的70％的9/30％的10的混合物。试样被配制成大约43％的固含量和Brookfield LVT粘度19,000毫帕斯卡秒(#4测量杆以6转每分钟)。Osnaburg聚酯棉织物为测试的基材。目标添加量为2.5-3.0盎司/平方码。采用3旦棉绒以交流电流使试样植绒。在150℃下使植绒的织物干燥并固化3分钟。在有或没有2％AircelPC-6A(蜜胺甲醛交联剂)下评价试样。对植绒纤维测定：冲洗稳定性-在5次热冲洗循环后的罗口边缘磨损，可接受的数值在4和5之间；并且用英制的两次折旧(pense)磨损测试评价耐磨性，湿对干磨损的可接受的保持性为大于30％。对磨损测试进行改进以用于植绒织物，直到发现粘结失败时统计磨损需要的次数。进行干态和湿态测试，结果如表7和8所示。
                     表7
               植绒织物评价(冲洗测试)试样                      结果               级别70％9/30％10              移去全部棉绒        170％9/30％10与Cymel 303   保留＞90％的棉绒    4
            表8
               保留的湿态磨损(英制两次折旧测试)试样                                  结果70％9/30％10                          59％70％9/30％10/AircelPC-6A            91％
上面的结果表明该组合物可用作纤维应用的粘合剂。实施例8-应用测试-装饰用层压制件
进行这些测试以表明本发明的组合物在装饰层压制件应用中的使用。
饱和浸透组合物：以乳胶和脲醛树脂的38％的总固含量制备乳胶/脲醛树脂混合物。50份的乳胶固体物结合50份的脲醛树脂固体物混合。
片材的饱和：采用上面的混合物，首先在混合物表面悬浮预先称重的片材20秒种，接着浸入10秒种来饱和纸片。渗透时间被计为从片材的底面完全透过表面浸透需要经过的时间(以秒计)。在浸透结束后，立即将片材以12磅/平方英寸一次通过填涂器除去多余的饱和液。称量湿态片材并计算吸收％。在150℃下将饱和片材固化2分钟。可接受的吸收％数值为20％到60％。
吸水性(Cobb测试)：采用改进的TAPPI测试方法T 441 om-84的过程进行该测试。该方法测定纸在标准条件下在特定的时间内的吸水量。测试12.7×12.7平方厘米的试样。将该过程改进到用25毫升水来代替该方法规定的100毫升，降低压头从1.0厘米到0.25厘米。测试时间从120秒缩短到60秒。一次测定一片纸。以克每平方米的吸水重量来计算吸水率。可接受的数值为小于20克每平方米。
柔韧性：通过在50％相对湿度和21℃下预先调节三个1.5厘米×4厘米试样24小时并将试样快速弯曲在一卷筒上来测定纸的柔韧性。一个测试条应进行至少3个不同卷筒尺寸的测试。不会使试样表面开裂的测定到毫米的卷筒直径被记为合格点。在50％相对湿度下3次合格值的平均被记为柔韧性。较小的卷筒直径对应于柔韧性的增加。通过在85℃的强制空气烘箱中干燥3-1.5厘米×4厘米试样5分钟，然后将试样条快速弯曲在卷筒上来测定在低相对湿度下的柔韧性。在这些条件下不会使纸开裂的平均卷筒直径被计为低湿度下的柔韧性。对于50％相对湿度和低％相对湿度下可接受的数值为小于30毫米。
Scotch胶带抗脱离性：当纸的2.54厘米×2.54厘米表面与ScotchMagic TapeTM在50％相对湿度和21℃的条件下接触5秒钟和24小时时，该测试测定该纸片的纸片脱离的内聚强度。在每次间隔中，从与胶带作用方向相反的方向用手从纸上快速拉起胶带。在没有发现纤维脱离的2.54厘米接触面内胶带面的百分数，被计为立即(5秒)使用胶带和接触24小时后，试样的抗脱离性。可接受的数值为大于50％。这些测试的结果如表9和10所示。
               表9
试样    渗透速度    wt％干态吸收
1         1               46
2         1               46.2
               表10
    Cobb    胶带抗脱离性    卷筒柔韧性(mm)试样    吸水率  初始  24小时   50％相对  低％相对
                             湿度      湿度
1    8.5    100    73        1.75      2.8
2    6.5    97    78         1.5       3.1
上面的数据表明该组合物可用于装饰层压制件的应用中。

Claims (7)

1.一种包含乳液聚合物的组合物，该乳液聚合物含有作为聚合单元的：
i)a)从9.5到99.9份重量的至少一种C12到C40的(甲基)丙烯酸烷基酯；
b)从0到90份重量的至少一种小于C15的烯属不饱和的单体；
c)从0到90份重量的至少一种含有烯属不饱和酸的单体或它的盐；和
d)从0.1到10份重量的至少一种交联单体；以及
ii)基于聚合物重量的从0到10份重量的至少一种交联剂，
条件是组合物含有基于聚合物重量的从0.1到10份重量的交联单体和交联剂。
2.根据权利要求1的组合物，其中的组合物包含：
a)从40到99份重量的至少一种C12到C40的(甲基)丙烯酸烷基酯；
b)从0到50份重量的从包括甲基丙烯酸甲酯和丙烯酸丁酯的种类中选出的至少一种单体；
c)从0到50份重量的甲基丙烯酸；和
d)从0.1到5份重量的从包括(甲基)丙烯酰胺、n-羟甲基(甲基)丙烯酰胺和它们的混合物的种类中选出的至少一种交联单体。
3.根据权利要求1的组合物，其中的组合物包含：
a)从90到98份重量的(甲基)丙烯酸十八烷基酯；
b)从1到20份重量的甲基丙烯酸甲酯；
c)从1到15份重量的甲基丙烯酸；和
d)从0.1到3份重量的n-羟甲基(甲基)丙烯酰胺。
4.一种在纤维、无纺物、织物和纸张组合物中用于改进疏水性和持久性的方法，它包括：
a)提供了一种聚合物组合物，它含有作为聚合单元的：
i)从9.5到100份重量的至少一种C12到C40的(甲基)丙烯酸烷基酯；
从0到90份重量的至少一种小于C15的烯属不饱和的单体；
从0到90份重量的至少一种含有烯属不饱和酸的单体或它的盐；和
从0到10份重量的至少一种交联单体；以及
ii)基于聚合物重量的从0到10份重量的至少一种交联剂，
b)提供了从包括纤维、无纺物、织物和纸张的种类中选出的一种基材；
c)用聚合物组合物涂饰基材；以及
d)干燥涂饰过的基材。
5.根据权利要求4的组合物，其中的聚合物组合物包含：
a)从40到99份重量的至少一种C12到C40的(甲基)丙烯酸烷基酯；
b)从0到50份重量的从包括甲基丙烯酸甲酯和丙烯酸丁酯的种类中选出的至少一种单体；
c)从0到50份重量的甲基丙烯酸；和
d)从0.1到5份重量的从包括(甲基)丙烯酰胺、n-羟甲基(甲基)丙烯酰胺和它们的混合物的种类中选出的至少一种交联单体。
6.一种制件，包括：
从包括纤维、无纺物、织物和纸张的种类中选出的一种基材，该基材被涂以一聚合物组合物，该组合物包含作为聚合单元的：
i)从9.5到100份重量的至少一种C12到C40的(甲基)丙烯酸烷基酯；
从0到90份重量的至少一种小于C15的烯属不饱和的单体；
从0到90份重量的至少一种含有烯属不饱和酸的单体或它的盐；和
从0到10份重量的至少一种交联单体；以及
ii)基于聚合物重量的从0到10份重量的至少一种交联剂，
7.一种根据权利要求6的制件，其中的聚合物组合物包含：
a)从40到99份重量的至少一种C12到C40的(甲基)丙烯酸烷基酯；
b)从0到50份重量的从包括甲基丙烯酸甲酯和丙烯酸丁酯的种类中选出的至少一种单体；
c)从0到50份重量的甲基丙烯酸；和
d)从0.1到5份重量的从包括(甲基)丙烯酰胺、n-羟甲基(甲基)丙烯酰胺和它们的混合物的种类中选出的至少一种交联单体。
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