CN100363427C - 星形支化的硅氧烷聚合物作为涂布应用的防雾添加剂 - Google Patents

星形支化的硅氧烷聚合物作为涂布应用的防雾添加剂 Download PDF

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CN100363427C
CN100363427C CNB2003801088490A CN200380108849A CN100363427C CN 100363427 C CN100363427 C CN 100363427C CN B2003801088490 A CNB2003801088490 A CN B2003801088490A CN 200380108849 A CN200380108849 A CN 200380108849A CN 100363427 C CN100363427 C CN 100363427C
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约翰·A·基尔戈
埃德温·C·库阿
约翰·A·卡明斯
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Abstract

在贵金属氢化硅烷化催化剂存在下制备在柔性支持物的涂布中适合作为防雾添加剂的星形支化的硅氧烷化合物,其为以下物质:M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i和(MjMVi kDlDVi mTnTVi o)pQp)q的反应产物,其中含有氢化物的前体和含有乙烯基的前体的比率通过下列各前体的化学计量下标之间的数学关系(b+d+f-g-h-i)/(((k+m+o)p)q)确定,为4.59~0.25,以及其中化合物:M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i可以通过以下反应获得:MaMH bDcDH dTeTH f+αCH2=CHR1→M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i,其中化合物自身为星形支化的硅氧烷化合物,可用作防雾添加剂。

Description

星形支化的硅氧烷聚合物作为涂布应用的防雾添加剂
技术领域
本发明涉及用硅氧烷组合物涂布柔性材料或支持物如纸张或其它聚合材料,纺织的或非纺织的。本发明还涉及用包含一种或多种可交联的聚有机硅氧烷的液体组合物涂布柔性材料或支持物,其中,该聚有机硅氧烷是通过加成反应、缩合反应、阳离子反应或自由基反应交联的。本发明也涉及星形支化(star-branched)的聚有机硅氧烷(硅氧烷聚合物),其在对柔性材料或支持物涂布硅氧烷组合物(聚有机硅氧烷)期间减少起雾。该柔性支持物可以为纸、纸板、塑料膜、金属膜等。一些示范性的应用有食品包装纸、胶粘标签、胶粘带、密封物等。
背景技术
通常在高速连续操作的涂布设备上用液体硅氧烷进行柔性支持物的涂布。这些设备一般包括由数个辊(特别包括压力辊和涂布辊)构成的涂布头(coating head),这些辊通过一系列相互相邻放置的辊连续输入可交联的或不可交联的硅氧烷组合物。在压力辊和至少一个表面上待涂布的涂布辊之间,高速输入欲涂布所需材料的柔性支持物带。当打算交联硅氧烷涂层时,实施交联反应的装置置于涂布头的下游。例如,实施交联的装置可以是烤箱、辐射(如紫外(UV)辐射)发射器或电子束(EB)发射器。
用硅氧烷高速涂布柔性支持物涉及到从涂布辊传送硅氧烷液体(或流体)至柔性支持物的有关问题,所述硅氧烷液体(或流体)向前移动通过涂布装置。与将硅氧烷液体(或流体)从涂布辊传送至柔性支持物有关的具体问题之一是:在紧靠涂布头的附近和特别接近涂布辊和涂布的柔性支持物之间的接触位置产生雾(fog)、烟雾(mist)或气溶胶(aerosol)。通常,该雾、烟雾或气溶胶的密度随着用装置涂布的柔性支持物的前进速度的增加而增加。
该传送问题的第一个影响是降低了实际传送至柔性支持物的硅氧烷液体的量。第二个影响是包含雾、烟雾或气溶胶的小滴冷凝在涂布辊下游的刚刚涂布的柔性支持物上,产生桔皮效应(orange peel effect)。该桔皮效应,或涂布不均匀引起与覆盖、涂层的机械性质如擦去(ruboff)和耐粘附性有关的问题。
另一个由涂布中不均匀性引起的问题涉及工业卫生和在涂布设备附近操作涂布设备的人员的安全。
发明内容
本发明提供在涂布柔性支持物期间减少起雾的组合物,其包括以下物质的(hydrosilylation)氢化硅烷化反应产物:
a)MaMH bDcDH dTeTH f;和
b)α量的CH2=CHR1
其中,α+1≤b+d+f,且g≤b,h≤d,i≤f,同时1.5≤b+d+f≤100;2≤a+b≤12;0≤c+d≤1000;0≤e+f≤10,且R1是一价基团,其选自卤素、氢、C1~C60一价烃基、C1~C60一价聚酯基团、C1~C60一价腈基、C1~C60一价烷基卤化物基团和C1~C60一价聚醚基团,及其混合物;其中
M=R2R3R4SiO1/2
MH=HR5R6SiO1/2
D=R7R8SiO2/2
DH=HR9SiO2/2
T=R11SiO3/2
TH=HSiO3/2
并且所述反应产物具有通式:
M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i,其中
M′=(CH2CHR1)R5R6SiO1/2
D′=(CH2CHR1)R9SiO2/2;和
T′=(CH2CHR1)SiO3/2
其中各R2、R3、R4、R5、R6、R7、R8、R9和R11独立地选自C1~C60一价烃基,其中下标a、b、c、d、e、f、g、h和i为0或正数,受限于b+d+f-g-h-i>0。
本发明还提供了在涂布柔性支持物期间减少起雾的组合物,其包含以下物质的氢化硅烷化反应产物:
a)M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i
b)(MjMVi kDlDVi mTnTVi o)pQp)q,其中
下标j、k、l、m、n、o和p为0或正数,受限于k+m+o>0,k+m+o<b+d+f-g-h-i,p为0.4~4.0,q不为0且为正数,受限于:
(b+d+f-g-h-i)/(((k+m+o)p)q)为4.59~0.25,其中
MVi=RViR5R6SiO1/2
DVi=RViR10SiO2/2
TVi=RViSiO3/2
Q=SiO4/2;其中
R10独立地选自C1~C60一价烃基团,且各RVi独立地选自C2~C60一价烯烃基团。
具体实施方式
在贵金属氢化硅烷化催化剂存在下,制备本发明的星形支化的硅氧烷化合物,其为以下物质的反应产物:
M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i和(MjMVi kDlDVi mTnTVi o)pQp)q
其中下标a、b、c、d、e、f、g、h、i、j、k、l、m、n、o、p为0或正数,q不为0且为正数,对于化合物的混合物,各下标的平均值最可能为非整数;对于特定的化合物,下标将是整数,其中k+m+o>0,且k+m+o<b+d+f-g-h-i,p为0.4~4.0,优选为0.5~3.0,更优选为0.5~2.5,最优选为0.5~1.5,以及介于其间的所有子区间,而q为1~200,优选为1~100,更优选为1~75,最优选为1~50,以及介于其间的所有子区间,其中含有氢化物的前体和含有乙烯基的前体的比率通过下列各前体的化学计量下标之间的数学关系(b+d+f-g-h-i)/(((k+m+o)p)q)确定,为4.59~0.25,优选为4.5~0.25,更优选为4.5~0.25,最优选为4.0~0.25,以及介于其间的所有子区间,并且特别包括3.5~0.25;3.0~0.25;2.5~0.25及2.0~0.25;其中化合物:
M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i
可以通过以下反应获得:
MaMH bDcDH dTeTH f+αCH2=CHR1→M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i
其中α+1≤b+d+f,且g≤b,h≤d,i≤f,同时1.5≤b+d+f≤100;2≤a+b≤12;0≤c+d≤1000;0≤e+f≤10,且R1是一价基团,其选自卤素、氢、C1~C60一价烃基、C1~C60一价聚酯基团、C1~C60一价腈基、C1~C60一价烷基卤化物基团和C1~C60一价聚醚基团,及其混合物;其中
M=R2R3R4SiO1/2
MH=HR5R6SiO1/2
Mvi=RViR5R6SiO1/2
D=R7R8SiO2/2
DH=HR9SiO2/2
DVi=RViR10SiO2/2
T=R11SiO3/2
TH=HSiO3/2
TVi=RViSiO3/2
Q=SiO4/2
M′=(CH2CHR1)R5R6SiO1/2
D′=(CH2CHR1)R9SiO2/2;和
T′=(CH2CHR1)SiO3/2
其中各R2、R3、R4、R5、R6、R7、R8、R9、R10和R11独立地选自C1~C60一价烃基,并且各RVi独立地选自C2~C60一价烯烃基团;应注意本发明的组合物要求b+d+f-g-h-i>0。在美国专利5,817,729、美国专利5,399,614和美国专利2,676,182中描述了制备MQ树脂如((MjMVi kDlDVi mTnTVi o)pQ)q的方法,在此特别引入作为参考。短语C1~C60是指碳数范围为1~60,且包括脂族和芳族基团,例如苯乙烯基,该范围也包括以下特定的子区间:15~60,30~60,45~60,1~15,1~30,1~45,10~30,10~40,10~50,以及介于其间的所有子区间。
由于在将被反应的各组分分子上用于反应的氢化硅烷化位置的多样性,以及将这种随机化学反应简化至分析说明的困难,本发明的星形支化的硅氧烷化合物描述为以下两种化合物的反应产物:M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i和(MjMVi kDlDVi mTnTVi o)pQ)q
可通过净反应(neat reaction)或反应物被溶剂稀释的反应来制备本发明的组合物。由于这些物质中取代基的长链性质,净反应,即不存在任何不参与反应的溶剂(non-participating solvent)时进行的反应,将倾向于产生与此处分子描述一致的产物,但具有更杂乱的(entangled)宏观结构(macro-structure)。如果希望这些化合物的宏观结构不太杂乱,应在合适的溶剂介质,如环状硅氧烷、惰性烃溶剂等中进行这些制备反应。
已知多种类型的贵金属催化剂用于这种氢化硅烷化反应,并且这些催化剂可用于本发明的反应中。当要求光学透明度时,优选的催化剂是可溶于反应混合物中的催化剂。至于贵金属,申请人定义Ru、Rh、Pd、Os、Ir和Pt为贵金属,在定义中还包括Ni,这是因为它公知的氢化活性。催化剂优选为铂化合物,且该铂化合物可以选自如美国专利3,159,601中描述的通式为(PtCl2Olefin)和H(PtCl3Olefin)的那些,在此引入该专利作为参考。在上面两式中示出的烯烃(olefin)可以为几乎所有类型的烯烃,但优选具有2~8个碳原子的亚烯烃(alkenylene)、5~7个碳原子的环亚烯烃(cycloalkenylene)或苯乙烯。在上式中可利用的具体烯烃有乙烯、丙烯、丁烯的各种异构体、辛烯、环戊烯、环己烯、环庚烯等。
在本发明的组合物中可使用的另外的含铂材料为美国专利3,159,662中描述的氯化铂的环丙烷络合物,在此引入该专利作为参考。
此外,如美国专利3,220,972中描述的,含铂材料可以为由氯铂酸和每克铂高达2摩尔选自醇、醚、醛和上述物质的混合物中的物质形成的络合物,在此引入该专利作为参考。
在Karstedt的美国专利3,715,334、3,775,452和3,814,730中描述了用于液体注塑组合物的优选催化剂。关于本领域的其它背景技术可以在由Academic Press出版(New York,1979),F.G.A.Stone和R.West编辑,J.L.Spier的“Homogeneous Catalysis of Hydrosilation by Transition Metals,Advances in Organometallic Chemistry,第17卷,pp.407-447中找到。本领域的技术人员可以容易地确定铂催化剂的有效量。通常,用于氢化硅烷化的有效量为每百万份总有机聚硅氧烷组合物大约0.1~50份,以及介于其间的所有子区间。
实施例
作为实施例,在氮气层(blanket)下将19.9克(0.083摩尔)C16-18α-烯烃与1000克(0.21摩尔)甲硅烷基氢化物封端的聚二甲基硅氧烷混合,并加入10ppm Pt作为Karstedt催化剂。在95℃加热反应并搅拌大约4小时,以使烯烃加成至硅氧烷聚合物。残留SiH的定量化学分析表明在将烯烃连接至硅氧烷中已经消耗了所需的氢量。任选可在进一步反应之前将产物分离出来。
将5.2克(0.05摩尔)((MVi)2Q)4树脂加入第一步反应的产物中。加入另外的10ppm Pt作为Karstedt催化剂,并且反应搅拌和加热至95℃约4小时。定量化学分析表明乙烯基和氢化物官能团已经反应到需要的程度。分离产物并作为防雾添加剂进行测试,结果报告在下面的表1和2中。
表1示出了基于上述路径合成防雾添加剂的结构的实施例。SiH/SiVinyl是用于反应的甲硅烷基氢化物的摩尔数与用于反应的甲硅烷基乙烯基的摩尔数的比率。在示出的化合物中,SiH/SiVinyl比率为0.2~2.75,但更大的可使用的范围为0.22~4.5。
表2示出了本发明的防雾表现。使用导向涂布机(pilot coater)在2000ft/min的线速度下在2.5mil SC Rhi-Liner 12的纸上运行期间进行测量。用含~2%防雾添加剂的标准硅氧烷脱膜纸制剂涂布该纸,国标为每令0.6~0.9磅。使用DustTrack Aerosol Monitor测量雾量。将进气口(intake eport)安置在最高观测的起雾区域,从而得到最高期望值。在所有的操作条件下,该位置既不反映正常的环境测试,也不能保证特定的值。测量为起雾材料(mg)/空气(立方米),较低的值更理想,因为它们表示起雾较少。
测量结果表明,本发明得到的防雾材料相比于不含防雾添加剂的对照配制物在2000ft/min下降低了产生的雾量。十分意料不到的,雾量通常下降到原来的十分之一以下,常常下降到原来的约百分之一。
表1:防雾添加剂的合成
  实施例     烯烃     克 甲硅烷基氢化物     克    ppmPt    SiH/SiVinyl   克((Mvi)2Q)4
  2021222324252627     C16-18C30+C16-18C16-18C16-18C16-18C16-18C16-18     19.948.719.937.210.211.911.94.0 MHD125MHMHD125MHMHD125MHMHD125MHMHD125MHMHD125MHMHD125MHMHD125MH     1000100010001500500600600200    10101010510105    2.502.502.502.001.201.752.002.50   5.25.25.28.15.24.43.91.0
表2:防雾测量
AMA# Mg/m3 at 2000ft/min
121B346347370122C384383379A 对照2021222324252627 102.0034.6010.001.601.731.641.133.800.43
上述实施例仅仅是说明本发明,仅用来说明本发明的一些特征。所附的权利要求意指要求本发明如所设想的一样宽,并且此处给出的实施例是说明从所有可行的实施方案的多种形式中选择的实施方案。因此,申请人的目的是:所附的权利要求不应受限于用来说明本发明特征的实施例的选择。正如在权利要求中所用的,开放式措词“包含”和它的语法变化形式逻辑上也对着(subtend)并包含变化的和不同范围的措词,例如,但不限于“基本上包括”和“由......组成”。必要时,提供了范围,那些范围包括它们之间的所有子区间。可以认识到:对本领域的普通技术人员而言,这些范围内的变化将显示它们自身,并且在没有对公知作出贡献时,那些变化用可能地认为被所附的权利要求覆盖。还可以预料到科技的进步使得等同物和替换物成为可能,这些等同物和替换物因语言的不精确目前未被注意过,并且这些变化也应认为可以被所附的权利要求覆盖。附上在此所引用的所有美国专利,由此具体引入作为参考。

Claims (30)

1.一种在涂布柔性支持物期间减少起雾的组合物,其包括以下物质的氢化硅烷化反应产物:
a)MaMH bDcDH dTeTH f;和
b)α量的CH2=CHR1
其中α+1≤b+d+f,同时1.5≤b+d+f≤100;2≤a+b≤12;0≤c+d≤1000;0≤e+f≤10,且R1是一价基团,其选自卤素、氢、C1~C60一价烃基、C1~C60一价聚酯基团、C1~C60一价腈基、C1~C60一价烷基卤化物基团和C1~C60一价聚醚基团,及其混合物;其中
M=R2R3R4SiO1/2
MH=HR5R6SiO1/2
D=R7R8SiO2/2
DH=HR9SiO2/2
T=R11SiO3/2
TH=HSiO3/2
并且所述反应产物具有通式:
M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i,其中
M′=(CH2CHR1)R5R6SiO1/2
D′=(CH2CHR1)R9SiO2/2;和
T′=(CH2CHR1)SiO3/2
其中各R2、R3、R4、R5、R6、R7、R8、R9和R11独立地选自C1~C60一价烃基,其中下标a、b、c、d、e、f、g、h和i为0或正数,受限于b+d+f-g-h-i>0。
2.一种组合物,包含以下物质的氢化硅烷化反应产物:
a)权利要求1的反应产物组合物和
b)((MjMVi kDlDVi mTnTVi o)pQp)q,其中
下标j、k、l、m、n、o和p为0或正数,受限于k+m+o>0,k+m+o<b+d+f-g-h-i,p为0.4~4.0,q不为0且为正数,受限于:
(b+d+f-g-h-i)/(((k+m+o)p)q)为4.59~0.25,其中
Mvi=RViR5R6SiO1/2
DVi=RViR10SiO2/2
TVi=RViSiO3/2
Q=SiO4/2;其中
R10独立地选自C1~C60一价烃基团,且各RVi独立地选自C2~C60一价烯烃基团。
3.权利要求2的组合物,其中R1选自C1~C60一价烃基、C1~C60一价聚酯基团、C1~C60一价腈基、C1~C60一价烷基卤化物基团和C1~C60一价聚醚基团。
4.权利要求2的组合物,其中R1选自C15~C60一价烃基、C15~C60一价聚酯基团、C15~C60一价腈基、C15~C60一价烷基卤化物基团和C15~C60一价聚醚基团。
5.权利要求2的组合物,其中R1选自C30~C60一价烃基、C30~C60一价聚酯基团、C30~C60一价腈基、C30~C60一价烷基卤化物基团和C30~C60一价聚醚基团。
6.权利要求3的组合物,其中各R2、R3、R4、R5、R6、R7、R8、R9、R10和R11是甲基。
7.权利要求4的组合物,其中各R2、R3、R4、R5、R6、R7、R8、R9、R10和R11是甲基。
8.权利要求5的组合物,其中各R2、R3、R4、R5、R6、R7、R8、R9、R10和R11是甲基。
9.权利要求2的组合物,其中R1是苯乙烯基。
10.权利要求9的组合物,其中各R2、R3、R4、R5、R6、R7、R8、R9、R10和R11是甲基。
11.一种组合物,其包括以下物质的氢化硅烷化反应产物:
a)MaMH bDcDH dTeTH f,和
b)α量的CH2=CHR1
其中α+1≤b+d+f,且g≤b,h≤d,i≤f,同时1.5≤b+d+f≤100;2≤a+b≤12;0≤c+d≤1000;0≤e+f≤10,且R1是一价基团,其选自卤素、氢、C1~C60一价烃基、C1~C60一价聚酯基团、C1~C60一价腈基、C1~C60一价烷基卤化物基团和C1~C60一价聚醚基团;其中
M=R2R3R4SiO1/2
MH=HR5R6SiO1/2
D=R7R8SiO2/2
DH=HR9SiO2/2
T=R11SiO3/2
TH=HSiO3/2
并且所述反应产物具有通式:
M′gMaMH b-gDcD′hDH d-hTeT′iTH f-i,其中
M′=(CH2CHR1)R5R6SiO1/2
D′=(CH2CHR1)R9SiO2/2;和
T′=(CH2CHR1)SiO3/2
其中各R2、R3、R4、R5、R6、R7、R8、R9和R11独立地选自C1~C60一价烃基,其中下标a、b、c、d、e、f、g、h和i为0或正数,受限于g>0;b-g>0;h>0和d-h>0。
12.一种组合物,包含以下物质的氢化硅烷化反应产物:
a)权利要求11的反应产物组合物和
b)(MjMVi kDlDVi mTnTVi o)pQp)q,其中
下标j、k、l、m、n、o和p为0或正数,受限于k+m+o>0,k+m+o<b+d+f-g-h-i,p为0.4~4.0,q不为0且为正数,受限于:
(b+d+f-g-h-i)/(((k+m+o)p)q)为4.59~0.25,其中
Mvi=RViR5R6SiO1/2
DVi=RViR10SiO2/2
TVi=RViSiO3/2
Q=SiO4/2;其中
R10独立地选自C1~C60一价烃基团,且各RVi独立地选自C2~C60一价烯烃基团。
13.权利要求12的组合物,其中R1选自C1~C60一价烃基、C1~C60一价聚酯基团、C1~C60一价腈基、C1~C60一价烷基卤化物基团和C1~C60一价聚醚基团。
14.权利要求12的组合物,其中R1选自C15~C60一价烃基、C15~C60一价聚酯基团、C15~C60一价腈基、C15~C60一价烷基卤化物基团和C15~C60一价聚醚基团。
15.权利要求12的组合物,其中R1选自C30~C60一价烃基、C30~C60一价聚酯基团、C30~C60一价腈基、C30~C60一价烷基卤化物基团和C30~C60一价聚醚基团。
16.权利要求13的组合物,其中各R2、R3、R4、R5、R6、R7、R8、R9、R10和R11是甲基。
17.权利要求14的组合物,其中各R2、R3、R4、R5、R6、R7、R8、R9、R10和R11是甲基。
18.权利要求15的组合物,其中各R2、R3、R4、R5、R6、R7、R8、R9、R10和R11是甲基。
19.权利要求12的组合物,其中R1是苯乙烯基。
20.权利要求19的组合物,其中各R2、R3、R4、R5、R6、R7、R8、R9、R10和R11是甲基。
21.一种在柔性基底涂布中减少起雾的方法,所述方法包括制备用于涂布所述基底的涂布组合物和向其中加入权利要求11的组合物。
22.一种在柔性基底涂布中减少起雾的方法,所述方法包括制备用于涂布所述基底的涂布组合物和向其中加入权利要求12的组合物。
23.一种在柔性基底涂布中减少起雾的方法,所述方法包括制备用于涂布所述基底的涂布组合物和向其中加入权利要求13的组合物。
24.一种在柔性基底涂布中减少起雾的方法,所述方法包括制备用于涂布所述基底的涂布组合物和向其中加入权利要求14的组合物。
25.一种在柔性基底涂布中减少起雾的方法,所述方法包括制备用于涂布所述基底的涂布组合物和向其中加入权利要求15的组合物。
26.一种在柔性基底涂布中减少起雾的方法,所述方法包括制备用于涂布所述基底的涂布组合物和向其中加入权利要求16的组合物。
27.一种在柔性基底涂布中减少起雾的方法,所述方法包括制备用于涂布所述基底的涂布组合物和向其中加入权利要求17的组合物。
28.一种在柔性基底涂布中减少起雾的方法,所述方法包括制备用于涂布所述基底的涂布组合物和向其中加入权利要求18的组合物。
29.一种在柔性基底涂布中减少起雾的方法,所述方法包括制备用于涂布所述基底的涂布组合物和向其中加入权利要求19的组合物。
30.一种在柔性基底涂布中减少起雾的方法,所述方法包括制备用于涂布所述基底的涂布组合物和向其中加入权利要求20的组合物。
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