CN1550513A - 具有聚烷氧基的有机硅化合物 - Google Patents
具有聚烷氧基的有机硅化合物 Download PDFInfo
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- CN1550513A CN1550513A CNA2004100421346A CN200410042134A CN1550513A CN 1550513 A CN1550513 A CN 1550513A CN A2004100421346 A CNA2004100421346 A CN A2004100421346A CN 200410042134 A CN200410042134 A CN 200410042134A CN 1550513 A CN1550513 A CN 1550513A
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Classifications
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Abstract
所公开的是通式(I)的共聚物(Q):A-B-(D-B)O-A,其中,A为-R1或-OR1基或通式(II)的一价基;E为通式(III)的基;F为通式(IV)或(V)的基;B为自选自通式(VIa)、(VIb)、(VIc)、(VId)和A的单元构成的二价基;D为通式(VIII)的二价基;条件是通式(I)的共聚物含有至少一个E基和一个F基。-R-[(NHaEbFc)(a+2b+c-1)+-R]g-(NHdEeFf)(d+2e+f-2)+[g(a+2b+c-1)+d+2e+f-2]X-(II),-R2-NR3+ 3(III),-CH2-CHR4-C(O)-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-R5(IV),-CH2-CH(OH)-CH2-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-R5(V),(SiR6 2O2/2)1(VIa),(SiR6R7O2/2)m(VIb),(-SiR6 2-)p+1(VIc),(SiO3/2)p(VId),-{[R-(NHaEbFc)]n-J-[(NHaEbFc)-R]n}-[2n(a+2b+c)-4]+[2n(a+2b+c)-4]X-(VIII)。
Description
技术领域
本发明涉及有机硅化合物,其中阳离子四基(cationic quat group)和聚醚基经氨基或铵基连至硅氧烷体,本发明还涉及其制备方法。
背景技术
由聚硅氧烷单元、聚醚基和阳离子四基组成的三元聚硅氧烷系统对于作为纺织品软化剂特别重要。然而,所述的合成为极耗时的多步骤方法,因为所用的反应物在工业上常不易获得且必须自行制备。相关的不良空时产率使得现有的合成方法不经济且不可行。
已知的上述三元聚硅氧烷系统可分为不同的4类:A)严格梳形改性的硅氧烷聚合物,其中聚醚基作为硅氧烷骨架与阳离子四基间的键结部分,或反之也然,即其中阳离子四基作为硅氧烷骨架与聚醚基间的连结体,如US 6,030,675中所述;B)具有末端阳离子四基和聚醚基的直链硅氧烷共聚物,其中聚醚基也可为进一步具有末端四基的硅氧烷嵌段的连结成员,如EP 1000959A中所述;C)聚合物,其中阳离子四基在聚合物的2个硅氧烷嵌段间构成桥联单元,其中附加的聚醚基可作为聚合物主链中的2价连结体存在,或者硅氧烷骨架或阳离子四基为梳形聚醚改性的,如WO 02/10257 A1中所述;D)聚硅氧烷,其用相互独立的聚醚基和阳离子四基在末端和/或侧端上改性,如6,313,256A中所述。
发明内容
本发明提供以下通式(I)的共聚物(Q):
A-B-(D-B)o-A (I),
其中,
A为-R1或-OR1基或以下通式(II)的一价基:
-R-[(NHaEbFc)(a+2b+c-1)+-R]g-(NHdEeFf)(d+2e+f-2)+[g(a+2b+c-1)+d+2e+f-2]X-(II),
R1为氢原子或具有1至100个碳原子的一价烃基,其可任选由原子N、O、P、B、Si、S间隔或取代,或者含有-C(O)-、-C(O)O-、-C(O)NR9-、-NR9-、-O-、-S-、=N-、≡N单元或由-NR9-、-OH、-SH基取代,
R为具有1至50个碳原子的二价烃基,其可任选由原子N、O、P、B、Si、S间隔或取代,或者含有-C(O)-、-C(O)O-、-C(O)NR9-、-NR9-、-O-、-S-、=N-单元,
R9为氢原子或具有1至18个碳原子的一价烃基,其可任选由原子N、O、P、B、Si、S间隔或由-OH、-SH基取代,
a、b及c为0至2的整数,条件为a+b+c的总和为1或2,
d、e和f为自0至3的整数,条件为d+e+f的总和为2或3,
g为自0至10的整数,
E为以下通式(III)的基:
-R2-NR3 3 + (III),
R2为具有1至10个碳原子的二价烃基,其可任选由原子N、O、P、B、Si、S间隔或取代,或含有-C(O)-、-C(O)O-、-C(O)NR9-、-NR9-、-O-、-S-、=N-、≡N单元或由-NR9-、-OH、-SH基取代,
R3为具有1至20个碳原子的一价烃基,其可任选由原子N、O、P、B、Si、S间隔或取代,或含有-C(O)-、-C(O)O-、-C(O)NR9-、-NR9-、-O-、-S-、=N-、≡N单元或由-NR9-、-OH、-SH基取代,
X-为有机或无机阴离子,
F为以下式(IV)或(V)的基:
-CH2-CHR4-C(O)-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-R5(IV),
-CH2-CH(OH)-CH2-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-R5
(V),
R4为氢原子或甲基,
R5为氢原子、具有1至10个碳原子的一价支链或直链烃基或选自以下组中的单元:CH2=CR4-C(O)-、(R1)2N-CH2-CHR4-C(O)-、R4-CH2-C(O)、HO-CH2-CH(OH)-CH2-及
G为二价基-O-或-NR9-,
h为0或1,
i、j和k各为自0至200的整数,
B为由选自式(VIa)、(VIb)、(VIc)、(VId)和A的单元构成的二价基:
(SiR6 2O2/2)l(VIa),(SiR6R7O2/2)m(VIb),
(-SiR6 2-)p+1 (VIc),(SiO3/2)p (VId),
R6为氢原子、-OR1或具有1至200个碳原子的一价烷基,其可由卤原子、羧基、环氧基、羟基或聚醚基取代,并且可任选由单元-C(O)-、-C(O)O-、-C(O)NR9-、-NR9-、-O-、-S-间隔,
R7为通式(II)的一价基,
l和m为0至5000的整数,
p为0至500的整数,
D为以下通式(VIII)的二价基,
-{[R-(NHaEbFc)]n-J-[(NHaEbFc)-R]n}-[2n(a+2b+c)-4]+[2n(a+2b+c)-4]X-(VIII),
n为1至10的整数,
J为以下通式(IX)或(X)的二价基:
-CH2-CHR4-C(O)-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-C(O)-CHR4-CH2-(IX),
-CH2-CH(OH)-CH2-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-CH2-CH(OH)-CH2-(X),
o为≥0的整数,
条件是通式(I)的共聚物含有至少一个E基和一个F基。
相对于已知结构,阳离子四基和聚醚基经共聚物(Q)的氨基或铵基连至硅氧烷体。四基不起桥的作用,而聚醚基可作为2个氨基硅氧烷体间的连结体。
共聚物(Q)易于以一锅法构建。合成大多定量地进行,并且因为良好的空时产率而比导致已知结构的全部方法更经济。此外,全部原料可以大量购得且不造成合成上的附加成本与不方便。生成的共聚物(Q)可为水溶性或自乳化的(所谓“自乳化系统”),根据选定的化学计量而定,即其不需要乳化的其它辅助剂。共聚物(Q)可用以处理纺织片材、纺织纤维及皮革,可作为油漆和涂料的添加物,作为化妆调配物的组分及作为表面活性剂。其特别具有有作为纺织品软化剂的杰出性质,其优于一般氨基二醇油。
共聚物(Q)为直链或支链的氨基聚硅氧烷,其α,ω和/或侧氨基不仅已以聚醚基改性,而且以阳离子四基改性,其氨基可作为季铵基存在。
共聚物(Q)的平均分子量Mn优选为至少500克/摩尔,更优选为至少1000克/摩尔,并且优选为至多1 000 000克/摩尔,更优选为至多500 000克/摩尔。
共聚物(Q)的粘度优选在25℃下在至少10平方毫米/秒的范围内、特别至少为15平方毫米/秒至优选为固体,
共聚物(Q)的胺数目优选为至少0.001个,特别为至少0.01个,并且优选为至多9个,更优选为至多6个。胺数目确定为中和1克共聚物所需的1-n-HCl的毫升数。
优选地,a、b和c为0或1。
优选地,a+b+c的总和为1。
优选地,d、e和f为0、1或2。
优选地,d+e+f的总和为2及a+b+c+d+e+f的总和为≤5,特别为3或4。
优选地,g为至多5。更优选地,g为0或1。
优选地,h为0。
优选地,i、j和k各为至多100及更优选为至多50。
优选地,l和m为至多1000及更优选为至多500。
优选地,p为至多100及更优选为至多20。
优选地,n为至多5。更优选地,n为1或2及特别为1。
优选地,o为至多1000及更优选为至多100。
优选地,R为具有1至10个碳原子的二价烃基,其可任选由N和O原子间隔,R更优选为选自式-CH2-、-(CH2)2、-(CH2)3-、-(CH2)2-NH-(CH2)3-的基,且更优选为选自式-(CH2)-、-(CH2)2-和(CH2)3的基。
优选地,R1为氢原子、具有1至10个碳原子的饱和或不饱和烷基及-C(O)H、-C(O)CH3、-C(O)CH2-CH3和-CH2-CH2-C(O)-O-CH2-CH3基。
特别优选氢、甲基、乙基、丙基、环己基及乙酰基。
优选地,R2为具有1至8个碳原子的未间隔二价烃基及-CH2-CH(OH)-CH2-基。
R2的优选实例为直链或支链亚烷基,如亚乙基、亚丙基、亚丁基,亚芳基如亚苯基,以及-CH2-CH(OH)-CH2-基。
优选地,R3为未间隔的一价烷基。
特别优选甲基、乙基、丙基、丁基、环己基、十二基和十八基。
优选地,R4为氢原子。
优选地,R5为氢原子、具有1至5个碳原子的饱和或不饱和烷基,或为-C(O)-CH3、CH2=CH-C(O)-、(R1)2N-CH2-CH2-C(O)-和基之一。
特别优选氢、甲基、乙基、丁基、乙酰基、丙烯酰基和
R6的实例为烷基,如甲基、乙基、正丙基、异丙基、1-正丁基、2-正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基;己基如正己基;庚基如正庚基;辛基如正辛基和异辛基,如2,2,4-三甲基戊基;壬基如正壬基;癸基如正癸基;十二基如正十二基;十八基如正十八基;环烷基如环戊基、环己基、环庚基和甲基环己基;烯基如乙烯基、烯丙基、3-丁烯基、5-己烯基、1-丙烯基和1-戊烯基;炔基如乙炔基、炔丙基和1-丙炔基;芳基如苯基、萘基、蒽基和菲基;烷芳基如邻、间、对甲苯基;二甲苯基和乙基苯基;以及芳烷基如苄基、苯基乙基和苯基壬基,或甲氧基或乙氧基。
经取代的R6基实例为卤烷基如3,3,3-三氟正丙基、2,2,2,2′,2′2′,-六氟异丙基、七氟异丙基,以及卤芳基如邻、间和对氯苯基或由羧基、环氧基、羟基或聚醚基取代的烷基。
优选地,R6为氢原子或具有1至10个碳原子的一价烷基。甲基为特别优选的。
R7基的实例为
-CH2-{N[-CH2-CH(OH)-CH2-NMe3]F}+Cl-,
-CH2-{N[-CH2-CH(OH)-CH2-NMe3]2F}3+3Cl-,
-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]F}+Cl-,
-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]2F}3+3Cl-,
-(CH2)3-NH-(CH2)2-{N[-CH2-CH(OH)-CH2-NMe3]F}+Cl-,
-(CH2)3-{N[-CH3-CH(OH)-CH2-NMe3]-(CH2)2-NHF}+Cl-,
-(CH2)3-NF-(CH2)2-{NH[-CH2-CH(OH)-CH2-NMe3]}+Cl-,
-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]-(CH2)2-NF2}+Cl-,
-(CH2)3-NF-(CH2)2-{N[-CH2-CH(OH)-CH2-NMe3]F}+Cl-,
-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3]F}2+2Cl-,
-(CH2)3-NF-(CH2)2-{N[-CH2-CH(OH)-CH2-NMe3]2}2+2Cl-,
-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]2-(CH2)2-NF2}3+3Cl-,
-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]F-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3]F}3+3Cl-,
-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3]F2}3+3Cl-,
-(CH2)3-NF-(CH2)2-{N[-CH2-CH(OH)-CH2-NMe3]2F}3+3Cl-,
-(CH2)3-NF-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3]3}4+4Cl-,
-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3]2F}4+4Cl-,
-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]2-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3]F}4+4Cl-,
-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]F-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3]2}4+4Cl-,
其中Me为甲基,并且与所述为F的实例的交换导致多个其它的类似实例。
下面将例举R7的一些说明性实例来说明共聚物(Q)的范围,(Me=甲基):-CH2-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C2H4O)5-C4H9]}+Cl-,-CH2-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C3H6O)20-(C2H4O)20-C4H9]}+Cl-,-CH2-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH2-C(O)-O-(C2H4O)5-H]}+Cl-,-CH2-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH2-C(O)-O-(C3H6O)16-CH3]}+Cl-,-CH2-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH2-C(O)-O-(C3H6O)20-(C2H4O)20-C(O)-CH=CH2]}+Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C2H4O)5-CH3]}+Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C3H6O)20-C3H5O]}+Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C2H4O)6-CH2CH(OH)CH2OH]}+Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH2-C(O)-O-(C2H4O)25-C(O)CH3]}+Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH2-C(O)-O-(C3H6O)16-CH3]}+Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH2-C(O)-O-(C3H6O)20-(C2H4O)20-C(O)-CH2CH2-NEt2]}+Cl-,-(CH2)3-NH-(CH2)2-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C2H4O)5-C4H9]}+Cl-,-(CH2)3-NH-(CH2)2-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C2H4O)22-(C3H6O)19-C4H9]}+Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]-(CH2)2-N[-CH2-CH(OH)-CH2-O-(C2H4O)11-C4H9]H}+Cl-,-(CH2)3-N[-CH2-CH(OH)-CH2-O-(C2H4O)20-C4H9]-(CH2)2-{NH[-CH2-CH(OH)-CH2-NMe3]}+Cl-,-(CH2)3-NH-(CH2)2-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH2-C(O)-O-(C3H6O)16-CH3]}+Cl-,-(CH2)3-NH-(CH2)2-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C3H6O)24-H]}+Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]-(CH2)2-N[-CH2-CH2-C(O)-O-(C2H4O)15-C(O)-CH=CH2]H}+Cl-,-(CH2)3-N[-CH2-CH(OH)-CH2-O-(C2H4O)4-C4H9]-(CH2)2-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C2H4O)22-(C3H6O)19-C4H9]}+Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C2H4O)24-CH3]}2+2Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-(C2H4O)5-C4H9]-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH2-C(O)-O-(C2H4O)15-(C3H6O)5-CH3}3+3Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3][-CH2-CH(OH)-CH2-O-(C2H4O)11-C4H9][-CH2-CH2-C(O)-O-(C2H4O)16-CH3]}3+3Cl-,-(CH2)3-{N[-CH2-CH(OH)-CH2-NMe3]-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3]2[-CH2-CH(OH)-CH2-O-(C2H4O)22-(C3H6O)19-C4H9]}4+4Cl-,-(CH2)3-{N[-CH2-CH2-C(O)-O-(C2H4O)35-CH3]-(CH2)2-N[-CH2-CH(OH)-CH2-NMe3]2[-CH2-CH(OH)-CH2-(C2H4O)4-C4H9]}4+4Cl-.
A的实例为氢、-OH基以及所述为R6和R7的基。
B的实例为
-SiMe2-O-SiMe2-,
-(SiMe2O)13-SiMe2-,
-(SiMe2O)55-SiMe2-,
-(SiMe2O)105-SiMe2-,
-(SiMe2O)200-SiMe2-,
-SiMe2O-SiMeR7O-SiMe2O-,
-(SiMe2O)70(SiMeR7O)1-SiMe2-,
-(SiMe2O)105(SiMeR7O)20-SiMe2-,
-(SiMe2O)195(SiMeR7O)15-SiMe2-,
-(SiMe2O)230(SiMeR7O)6-SiMe2-,
-(SiMe2O)108(SiMeR7O)2-SiMe2-,
-(SiMe2O)139(SiMeR7O)1-SiMe2-,
-(SiMe2O)9-SiMe3,
-(SiMe2O)59-SiMe3,
-(SiMe2O)99-SiMe3,
-(SiMe2O)13-SiMe2-OCH3,
-(SiMe2O)14-SiMe2-OC2H4,
-(SiMe2O)44-SiMe2-OC3H7,
-(SiMe2O)22-SiMe2-OC4H9,
-(SiMe2O)35-SiMe2-OC4H9.
D的实例为
-{CH2-N[-CH2-CH(OH)-CH2-NMe3]-J-N[-CH2-CH(OH)-CH2-NMe3]-CH2}-2+2Cl-,
-{CH2-NH-J-N[-CH2-CH(OH)-CH2-NMe3]-CH2}-+Cl-,
-{CH2-N[-CH2-CH(OH)-CH2-NMe3]-J-NF-CH2}-+Cl-,
-{CH2-NH-J-NF-CH2}-,
-{CH2-NF-J-NF-CH2}-,
-{(CH2)3-N[-CH2-CH(OH)-CH2-NMe3]-J-N[-CH2-CH(OH)-CH2-NMe3]-(CH2)3}-2+2Cl-,
-{(CH2)3-NH-J-N[-CH2-CH(OH)-CH2-NMe3]-(CH2)3}-+Cl-,
-{(CH2)3-N[-CH2-CH(OH)-CH2-NMe3]-J-NF-(CH2)3}-+Cl-,
-{(CH2)3-NH-J-NF-(CH2)3}-,
-{(CH2)3-NF-J-NF-(CH2)3}-,
-{CH2-N[-CH2-CH(OH)-CH2-NMe3]-J-N[-CH2-CH(OH)-CH2-NMe3]-(CH2)3}-2+2Cl-,
-{CH2-N[-CH2-CH(OH)-CH2-NMe3]-J-NH-(CH2)3}-2+2Cl-,
-{CH2-NH-J-N[-CH2-CH(OH)-CH2-NMe3]-(CH2)3}-2+2Cl-,
-{CH2-N[-CH2-CH(OH)-CH2-NMe3]-J-NF-(CH2)3}-2+2Cl-,
-{CH2-NF-J-N[-CH2-CH(OH)-CH2-NMe3]-(CH2)3}-2+2Cl-,
-{CH2-NF-J-NF-(CH2)3}-,
-{CH2-NF-J-NH-(CH2)3}-,
-{CH2-NH-J-NF-(CH2)3}-,
其中Me代表甲基,并且所述实例通过F和J的变换造成多个进-步的说明结构。
E单元的实例为
-CH2-CH(OH)-CH2-NMe3 +Cl-,-CH2-CH(OH)-CH2-NMe2C12H25 +Cl-and
-CH2-CH(OH)-CH2-NMe2C18H37 +Cl-.
F单元的实例为
-CH2-CH2-C(O)-O-(C2H4O)6-H,
-CH2-CH2-C(O)-O-(C2H4O)6-CH3,
-CH2-CH2-C(O)-O-(C2H4O)6-C(O)-CH=CH2,
-CH2-CH2-C(O)-O-(C2H4O)6-C(O)-CH2-CH2-NEt2,
-CH2-CH2-C(O)-O-(C2H4O)6-C(O)-CH2-CH2-N(CH2CH2OH)2,
-CH2-CH2-C(O)-O-(C2H4O)6-C(O)CH3,
-CH2-CH2-C(O)-O-(C2H4O)14-H,
-CH2-CH2-C(O)-O-(C2H4O)14-CH3,
-CH2-CH2-C(O)-O-(C2H4O)14-C(O)-CH=CH2,
-CH2-CH2-C(O)-O-(C2H4O)14-C(O)-CH2-CH2-NEt2,
-CH2-CH2-C(O)-O-(C2H4O)14-C(O)-CH2-CH2-N(CH2CH2OH)2,
-CH2-CH2-C(O)-O-(C2H4O)14-C(O)CH3,
-CH2-CH2-C(O)-O-(C2H4O)35-H,
-CH2-CH2-C(O)-O-(C2H4O)15-CH3,
-CH2-CH2-C(O)-O-(C2H4O)35-C(O)-CH=CH2,
-CH2-CH2-C(O)-O-(C2H4O)35-C(O)-CH2-CH2-NEt2,
-CH2-CH2-C(O)-O-(C2H4O)35-C(O)-CH2-CH2-N(CH2CH2OH)2,
-CH2-CH2-C(O)-O-(C2H4O)35-C(O)CH3,
-CH2-CH2-C(O)-O-(C3H6O)6-H,
-CH2-CH2-C(O)-O-(C3H6O)6-CH3,
-CH2-CH2-C(O)-O-(C3H6O)6-C(O)-CH=CH2,
-CH2-CH2-C(O)-O-(C3H6O)6-C(O)-CH2-CH2-NEt2,
-CH2-CH2-C(O)-O-(C3H6O)6-C(O)-CH2-CH2-N(CH2CH2OH)2,
-CH2-CH2-C(O)-O-(C3H6O)6-C(O)CH3,
-CH2-CH2-C(O)-O-(C3H6O)12-H,
-CH2-CH2-C(O)-O-(C3H6O)12-CH3,
-CH2-CH2-C(O)-O-(C3H6O)12-C(O)-CH=CH2,
-CH2-CH2-C(O)-O-(C3H6O)12-C(O)-CH2-CH2-NEt2,
-CH2-CH2-C(O)-O-(C3H6O)12-C(O)-CH2-CH2-N(CH2CH2OH)2,
-CH2-CH2-C(O)-O-(C3H6O)12-C(O)CH3,
-CH2-CH2-C(O)-O-(C3H6O)35-H,
-CH2-CH2-C(O)-O-(C3H6O)35-CH3,
-CH2-CH2-C(O)-O-(C3H6O)35-C(O)-CH=CH2,
-CH2-CH2-C(O)-O-(C3H6O)35-C(O)-CH2-CH2-NEt2,
-CH2-CH2-C(O)-O-(C3H6O)35-C(O)-CH2-CH2-N(CH2CH2OH)2,
-CH2-CH2-C(O)-O-(C3H6O)35-C(O)CH3,
-CH2-CH2-C(O)-O-(C3H6O)5-(C2H4O)5-H,
-CH2-CH2-C(O)-O-(C3H6O)5-(C2H4O)5-CH3,
-CH2-CH2-C(O)-O-(C3H6O)5-(C2H4O)5C(O)-CH=CH2,
-CH2-CH2-C(O)-O-(C3H6O)5-(C2H4O)5C(O)-CH2-CH2-NEt2,
-CH2-CH2-C(O)-O-(C3H6O)5-(C2H4O)5C(O)-CH2-CH2-N(CH2CH2OH)2,
-CH2-CH2-C(O)-O-(C3H6O)5-(C2H4O)5-C(O)CH3,
-CH2-CH2-C(O)-O-(C3H6O)10-(C2H4O)10-H,
-CH2-CH2-C(O)-O-(C3H6O)10-(C2H4O)10-CH3,
-CH2-CH2-C(O)-O-(C3H6O)10-(C2H4O)10C(O)-CH=CH2,
-CH2-CH2-C(O)-O-(C3H6O)10-(C2H4O)10C(O)-CH2-CH2-NEt2,
-CH2-CH2-C(O)-O-(C3H6O)10-(C2H4O)10C(O)-CH2-CH2-N(CH2CH2OH)2,
-CH2-CH2-C(O)-O-(C3H6O)10-(C2H4O)10-C(O)CH3,
-CH2-CH(OH)-CH2-O-(C2H4O)4-C4H9
-CH2-CH(OH)-CH2-O-(C2H4O)11-C4H9,
-CH2-CH(OH)-CH2-O-(C2H4O)20-C4H9,
-CH2-CH(OH)-CH2-O-(C2H4O)22(C3H6O)19-C4H9,
-CH2-CH(OH)-CH2-O-(C2H4O)4-C3H5O,
-CH2-CH(OH)-CH2-O-(C2H4O)11-C3H5O,
-CH2-CH(OH)-CH2-O-(C2H4O)20-C3H5O,
-CH2-CH(OH)-CH2-O-(C2H4O)22(C3H6O)19-C3H5O,
-CH2-CH(OH)-CH2-O-(C2H4O)4-CH2-CH(OH)-CH2-OH,
-CH2-CH(OH)-CH2-O-(C2H4O)11-CH2-CH(OH)-CH2-OH,
-CH2-CH(OH)-CH2-O-(C2H4O)20-CH2-CH(OH)-CH2-OH,
-CH2-CH(OH)-CH2-O-(C2H4O)22(C3H6O)19-CH2-CH(OH)-CH2-OH,
-CH2-CH(OH)-CH2-O-(C2H4O)4-CH2-CH(OH)-CH2-NEt2,
-CH2-CH(OH)-CH2-O-(C2H4O)11-CH2-CH(OH)-CH2-NEt2,
-CH2-CH(OH)-CH2-O-(C2H4O)20-CH2-CH(OH)-CH2-NEt2,
-CH2-CH(OH)-CH2-O-(C2H4O)22(C3H6O)19-CH2-CH(OH)-CH2-NEt2,
-CH2-CH(OH)-CH2-O-(C2H4O)4-CH2-CH(OH)-CH2-N(CH2CH2OH)2,
-CH2-CH(OH)-CH2-O-(C2H4O)11-CH2-CH(OH)-CH2-N(CH2CH2OH)2,
-CH2-CH(OH)-CH2-O-(C2H4O)20-CH2-CH(OH)-CH2-N(CH2CH2OH)2,
-CH2-CH(OH)-CH2-O-(C2H4O)22(C3H6O)19-CH2-CH(OH)-CH2-N(CH2CH2OH)2,
其中Me为甲基,Et为乙基。
J的实例为
-CH2-CH2-C(O)-O-(C2H4O)6-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-O-(C2H4O)14-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-O-(C2H4O)35-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-O-(C3H6O)6-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-O-(C3H6O)12-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-O-(C3H6O)35-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-O-(C3H6O)5-(C2H4O)5-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-O-(C3H6O)10-(C2H4O)10-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-O-(C3H6O)5-(C2H4O)15-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-O-(C3H6O)20-(C2H4O)20-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-NH-(C3H6O)3-C3H6-NH-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-NH-(C3H6O)6-C3H6-NH-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-NH-(C3H6O)33-C3H6-NH-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-NH-(C3H6O)68-C3H6-NH-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-NH-C3H6O-(C2H4O)2-C3H6-NH-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-NH-(C3H6O)2-(C2H4O)9-C3H6O-C3H6-NH-C(O)-CH2-CH2-,
-CH2-CH2-C(O)-NH-(C3H6O)3-(C2H4O)39-(C3H6O)2-C3H6-NH-C(O)-CH2-CH2-,
-CH2-CH(OH)-CH2-O-(C2H4O)4-CH2-CH(OH)-CH2-,
-CH2-CH(OH)-CH2-O-(C2H4O)11-CH2-CH(OH)-CH2-,
-CH2-CH(OH)-CH2-O-(C2H4O)20-CH2-CH(OH)-CH2-,
-CH2-CH(OH)-CH2-O-(C2H4O)22(C3H6O)19-CH2-CH(OH)-CH2-.
根据本发明,合适的X-阴离子的实例为氯离子、溴离子、硫酸氢根离子、乙酸根离子、硫酸根离子及有机磺酸根离子,如三氟甲磺酸根离子或对甲苯磺酸根离子。
本发明进一步提供制备上述通式(I)的共聚物(Q)的方法,其包括将选自通式(XI)、(XII)、(XIII)、(XIV)和(XV)化合物的有机硅化合物或其混合物,与选自通式(XVI)和(XVII)化合物的聚醚及选自通式(XVIII)和(XIX)化合物的有机化合物反应:H-NR1-(R-NHR1)g-R-(SiR6 2O)1-SiR6 2-R(-NHR1-R)g-NR1-H (XI),H-NR1-(R-NHR1)g-R-(SiR6 2O)1-{SiR6[-R(-NHR1-R)g-NHR1]-O}m-R(-NHR1-R)g-NR1-H (XII),R6 3SiO-(SiR6 2O)1-{SiR6[-R(-NHR1-R)g-NHR1]-O}m-SiR6 3 (XIII),MeO-SiR6 2O-(SiR6 2O)1-{SiR6[-R(-NHR1-R)g-NHR1]-O}m-SiR6 2-OMe (XIV),H-NR1-(R-NHR1)g-R-(SiR6 2O)1-SiR6 2-R5 (XV),CH2=CH-C(O)-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-R5 (XVI),
其中Me为甲基,R1、R2、R3、R5、R6、G、X、g、h、i、j、k、l和m各限定如上。
该方法可在本体、溶液或乳化液中,不仅可以逐步方式而且以一锅法进行。所用有机硅化合物为已知及可购得的。
阳离子四基在本方法中以有别于惯用现有技术的不同方通式导入。本方法采用水性试剂。水性系统本来就与疏水性硅氧烷不相容;使用水性试剂改性硅油因此通常可能有困难且产量低。本方法达成高产量。
采用的通式(XI)有机硅化合物的实例为
H2N-CH2-SiMe2O-SiMe2-CH2-NH2,
H2N-CH2-SiMe2O-(SiMe2O)6-SiMe2-CH2-NH2,
H2N-CH2-SiMe2O-(SiMe2O)11-SiMe2-CH2-NH2,
H2N-CH2-SiMe2O-(SiMe2O)98-SiMe2-CH2-NH2,
H2N-CH2-SiMe2O-(SiMe2O)150-SiMe2-CH2-NH2,
H2N-(CH2)3-SiMe2O-SiMe2-(CH2)3-NH2,
H2N-(CH2)3-SiMe2O-(SiMe2O)6-SiMe2-(CH2)3-NH2,
H2N-(CH2)3-SiMe2O-(SiMe2O)11-SiMe2-(CH2)3-NH2,
H2N-(CH2)3-SiMe2O-(SiMe2O)98-SiMe2-(CH2)3-NH2,
H2N-(CH2)3-SiMe2O-(SiMe2O)200-SiMe2-(CH2)3-NH2,
H2N-(CH2)2-NH-(CH2)3-SiMe2O-SiMe2-(CH2)3-NH-(CH2)2-NH2,
H2N-(CH2)2-NH-(CH2)3-SiMe2O-(SiMe2O)6-SiMe2-(CH2)3-NH-(CH2)2-NH2,
H2N-(CH2)2-NH-(CH2)3-SiMe2O-(SiMe2O)11-SiMe2-(CH2)3-NH-(CH2)2-NH2,
H2N-(CH2)2-NH-(CH2)3-SiMe2O-(SiMe2O)55-SiMe2-(CH2)3-NH-(CH2)2-NH2.
采用的通式(XII)有机硅化合物的实例为
H2N-(CH2)3-SiMe2O-{SiMe[(CH2)3-NH2]O}-SiMe2-(CH2)3-NH2,
H2N-(CH2)3-SiMe2O-(SiMe2O)25-{SiMe[(CH2)3-NH2]O}5-SiMe2-(CH2)3-NH2,
H2N-(CH2)3-SiMe2O-(SiMe2O)50-{SiMe[(CH2)3-NH2]O}3-SiMe2-(CH2)3-NH2,
H2N-(CH2)3-SiMe2O-(SiMe2O)70-{SiMe[(CH2)3-NH2]O}1-SiMe2-(CH2)3-NH2.
采用的通式(XIII)有机硅化合物的实例为
Me3SiO-(SiMe2O)25-{SiMe[(CH2)3-NH2]O}SiMe3,
Me3SiO-(SiMe2O)45-{SiMe[(CH2)3-NH2]O}5SiMe3,
Me3SiO-(SiMe2O)100-{SiMe[(CH2)3-NH2]O}5SiMe3,
Me3SiO-(SiMe2O)130-{SiMe[(CH2)3-NH2]O}1SiMe3,
Me3SiO-(SiMe2O)105{SiMe[(CH2)3-NH-(CH2)2-NH2]O}20-SiMe3,
Me3SiO-(SiMe2O)195(SiMe[(CH2)3-NH-(CH2)2-NH2]O)15-SiMe3,
Me3SiO-(SiMe2O)230(SiMe[(CH2)3-NH-(CH2)2-NH2]O)6-SiMe3,
Me3SiO-(SiMe2O)108(SiMe[(CH2)3-NH-(CH2)2-NH2]O)2-SiMe3,
Me3SiO-(SiMe2O)139(SiMe[(CH2)3-NH-(CH2)2-NH2]O)1-SiMe3.
采用的通式(XIV)有机硅化合物的实例为
Me3SiO-(SiMe2O)25-{SiMe[(CH2)3-NH2]O}5SiMe3,
Me3SiO-(SiMe2O)45-{SiMe[(CH2)3-NH2]O}5SiMe3,
Me3SiO-(SiMe2O)100-{SiMe[(CH2)3-NH2]O}5SiMe3,
Me3SiO-(SiMe2O)130-{SiMe[(CH2)3-NH2]O}1SiMe3,
MeOSiMe2O-(SiMe2O)40{SiMe[(CH2)3-NH-(CH2)2-NH2]O}1-SiMe2OMe,
MeOSiMe2O-(SiMe2O)70{SiMe[(CH2)3-NH-(CH2)2-NH2]O}1-SiMe2OMe,
MeOSiMe2O-(SiMe2O)200{SiMe[(CH2)3-NH-(CH2)2-NH2]O}1-SiMe2OMe.
采用的通式(XV)有机硅化合物的实例为
H2N-CH2-(SiMe2O)13-SiMe2-OCH3,
H2N-CH2-(SiMe2O)14-SiMe2-OC2H4,
H2N-CH2-(SiMe2O)44-SiMe2-OC3H7,
H2N-CH2-(SiMe2O)22-SiMe2-OC4H9,
H2N-CH2-(SiMe2O)35-SiMe2-OC4H9.
H2N-(CH2)3-(SiMe2O)9-SiMe3,
H2N-(CH2)3-(SiMe2O)59-SiMe3,
H2N-(CH2)3-(SiMe2O)99-SiMe3,
H2N-(CH2)3-(SiMe2O)13-SiMe2-OCH3,
H2N-(CH2)3-(SiMe2O)14-SiMe2-OC2H4,
H2N-(CH2)3-(SiMe2O)44-SiMe2-OC3H7,
H2N-(CH2)3-(SiMe2O)22-SiMe2-OC4H9,
H2N-(CH2)3-(SiMe2O)35-SiMe2-OC4H9.
H2N-(CH2)2-NH-(CH2)3-(SiMe2O)7-SiMe3,
H2N-(CH2)2-NH-(CH2)3-(SiMe2O)12-SiMe3.
通式(XI)、(XII)、(XIII)和(XV)的有机硅化合物为优选的,特别为通式(XI)、(XIII)和(XV)的有机硅化合物。
采用同样地可购得(例如购自Cray Valley,SiberHegner,AG,NOFCorp.)或由本领域技术人员已知的方法制备的通式(XVI)和(XVII)聚醚的实例为
CH2=CH-C(O)-O-(C2H4O)6-H,
CH2=CH-C(O)-O-(C2H4O)14-H,
CH2=CH-C(O)-O-(C2H4O)35-H,
CH2=CH-C(O)-O-(C3H6O)6-H,
CH2=CH-C(O)-O-(C3H6O)12-H,
CH2=CH-C(O)-O-(C3H6O)35-H,
CH2=CH-C(O)-O-(C2H4O)3-(C3H6O)3-H,
CH2=CH-C(O)-O-(C2H4O)5-(C3H6O)5-H,
CH2=CH-C(O)-O-(C2H4O)10-(C3H6O)10-H,
CH2=CH-C(O)-O-(C2H4O)6-CH3,
CH2=CH-C(O)-O-(C2H4O)16-CH3,
CH2=CH-C(O)-O-(C2H4O)24-CH3,
CH2=CH-C(O)-O-(C2H4O)25-CH3,
CH2=CH-C(O)-O-(C3H6O)6-CH3,
CH2=CH-C(O)-O-(C3H6O)12-CH3,
CH2=CH-C(O)-O-(C3H6O)35-CH3,
CH2=CH-C(O)-O-(C2H4O)3-(C3H6O)3-CH3,
CH2=CH-C(O)-O-(C2H4O)5-(C3H6O)5-CH3,
CH2=CH-C(O)-O-(C2H4O)10-(C3H6O)10-CH3,
CH2=CH-C(O)-O-(C2H4O)3-C(O)-CH=CH2,
CH2=CH-C(O)-O-(C2H4O)6-C(O)-CH=CH2,
CH2=CH-C(O)-O-(C2H4O)14-C(O)-CH=CH2,
CH2=CH-C(O)-O-(C2H4O)35-C(O)-CH=CH2,
CH2=CH-C(O)-O-(C3H6O)3-C(O)-CH=CH2,
CH2=CH-C(O)-O-(C3H6O)6-C(O)-CH=CH2,
CH2=CH-C(O)-O-(C3H6O)12-C(O)-CH=CH2,
CH2=CH-C(O)-O-(C3H6O)35-C(O)-CH=CH2,
CH2=CH-C(O)-O-(C2H4O)3-(C3H6O)3-C(O)-CH=CH2,
CH2=CH-C(O)-O-(C2H4O)5-(C3H6O)5-C(O)-CH=CH2,
CH2=CH-C(O)-O-(C2H4O)10-(C3H6O)10-C(O)-CH=CH2,
采用同样地可购得(例如购自Degussa AG)的通式(XVIII)和(XIX)有机化合物的实例为
优选的在本方法中每摩尔(XI)、(XII)、(XIII)、(XIV)和(XV)的有机硅化合物的氨基,使用至少0.001摩尔、特别为至少0.1摩尔、更优选为至少0.5及优选至多1.75摩尔的通式(XVI)和(XVII)的聚醚,以及优选至少0.001摩尔、特别为至少0.1摩尔、更优选为至少0.5及优选至多1.75摩尔的通式(XVIII)和(XIX)的有机化合物。
当本方法采用通式(XVI)和(XVII)的二官能聚醚化合物,并且通式(XVI)和(XVII)的聚醚化合物及通式(XVIII)和(XIX)的有机化合物部分经选定,以使过量的丙烯酸酯和环氧基出现在通式(I)的共聚物时,这些反应性端基可随后可交联或被特定交联。
具有反应性丙烯酸端基和环氧基端基的通式(I)产物可使其保存稳定数个月,借助常用的自由基抑制剂如氢醌单甲基醚或吩噻嗪防止日光引起的自由基交联。在具有丙烯酸端基和环氧基端基的产物中仍留有伯胺或仲胺,以有机酸酐或酰氯将这些氨基酰胺化,或由Michael型反应以单体丙烯酸酯化合物在实际反应进行后使氨基饱和,可稳定防止可能的后交联作用。此外,通式(I)共聚物中剩下的伯胺或仲胺基也可经质子化、烷基化或季铵化;这也适用于叔胺基。制备通式(I)共聚物的方法可采用自文献已知的化合物,其催化Michael型反应及环氧基开环反应。实例为Broensted酸如磷酸、硫酸、盐酸、冰醋酸、丙酸和甲酸或它们的水溶液,Lewis酸如高氯酸锂、四氟硼酸锌、氯化铁(II)和氯化锡(IV),以及Broensted碱例如甲氧化钠和碱金属酰胺以及氯化铵、溴化四烷基铵和碱金属碘化物。
本方法可另外采用有机溶剂、水或它们的混合物、前述通式(XVI)和(XVII)的聚醚以及其反应产物本身作为溶剂。有机溶剂的实例为甲苯、二甲苯、THF、乙酸正丁酯、异丙醇、丁醇和二甲氧基乙烷。使用的有机溶剂优选在反应后或在接着的反应后除去。
当本方法在乳液中进行时,乳化剂或表面活性剂可相应地存在。同样地,当本方法在乳化液中进行时,反应产物自身通过其表面活性可作为乳化剂或共乳化剂。
通式(I)的共聚物可用选自以下组中的有机聚硅氧烷平衡:具有末端三有机硅氧基的直链有机聚硅氧烷、具有直链末端羟基的有机聚硅氧烷、环状有机聚硅氧烷,以及二有机硅氧烷和单有机硅氧烷单元的共聚物。
作为具有末端三有机硅氧基的直链有机聚硅氧烷,其优选具有以下通式(XX):
R6 3SiO(SiR6 2O)qSiR6 3 (XX),
作为具有末端羟基的直链有机聚硅氧烷,其优选具有以下通式(XXI):
HO(SiR6 2O)rH (XXI),
作为环状有机聚硅氧烷,其优选具有以下通式(XXII):
(R6 2SiO)s (XXII),
以及作为共聚物,其优选由以下通式(XXIII)、(XXIV)和(XXV)单元组成:
R6 3SiO1/2,R6 2SiO and R6SiO3/2 (XXIII,XXIV,XXV),
其中
q和r各为0或自1至1500的整数及
s为自3至12的整数,以及R6限定如上。
任选进行的平衡而使用的通式(XX)与(XXV)的有机聚硅氧烷,及通式(I)的共聚物的定量比值仅由想要以任选进行平衡产生的聚醚和/或四基的部分及由想要硅氧烷单元的平均链长决定。
任选进行的平衡采用酸性或优选为碱性的催化剂以进一步平衡。酸性催化剂的实例优选为硫酸、磷酸、三氟甲磺酸、氯氮化磷及在反应条件下为固体的酸性催化剂,如酸活化的脱色土、酸性沸石、磺化碳和磺化苯乙烯-二乙烯基苯共聚物,优选氯氮化磷酸性催化剂。酸性催化剂优选为5至1000重量ppm(=百万分之份数)的量使用,特别为0至200重量ppm,全部基于使用有机硅化合物的总重量。
碱性催化剂的实例为氢氧化苄基三甲铵、氢氧化四甲铵、碱金属氢氧化物、碱土金属氢氧化物于甲醇溶液中、氢氧化鏻及硅烷醇化物。优选氢氧化铵,其以50至10 000重量ppm(=百万分之份数)的量使用,特别为500至2000重量ppm,全部基于使用有机硅化合物的总重量。
任选进行的平衡优选在80至150℃下及环境大气压、即900至1100百帕的压力下进行。然而,在需要时,也可采用更高或更低的压力。平衡可在与水不互容的溶剂如甲苯中进行。当使用溶剂时,相关量优选为5至20重量%,基于使用特殊有机硅化合物的总重量。催化剂可在如此平衡的混合物进行前失活。
制备通式(I)的共聚物的方法的优点为可简单地以一锅合成法完成,并且使用简单和可大量购得的原料。制备共聚物的方法具有进一步的优点,其第一为共聚物的性质简单地经选择反应物而变化,及第二在一定程度下,反应物的化学计量可与其他实际上未改变的反应参数一起使用来改变粘度,而且容易地改变疏水性、胺数目及产物端基的本质,以及硅氧烷与聚醚和/或四单元的比值。
通式(I)的共聚物(Q)以透明、低变色、耐水解及无过渡金属而著名。由于其分子中季铵基的数目而具有阳离子生成性,因此本发明的共聚物拥有对基底如纺织品或纸极优的附著力,并且其疏水性极优,其比有机硅化合物为高。
共聚物(Q)因此可作为例如乳液成分,用于水溶液中或在无溶剂下处理纺织片材如织物、编织物或非织物、纺织纤维及纱线整理和改性以及皮革和纸处理。使用适当共聚物(Q)的整理或改性可用于产生想要的性质,例如软、柔的手感、改进弹性、抗静电性、摩擦系数、表面平滑、光泽、褶痕修复、颜色持久、耐洗性、亲水性、撕裂强度、降低成丸的趋势、容易照顾及去污性质以及改进的穿着舒适性。经共聚物(Q)整理而达成的效果展现良好至极好的清洗和再调节性,根据共聚物(Q)的结构、基底的结构及清洗条件而定。纺织片材、纤维、纱线、纸和皮革以共聚物(Q)整理或改性可用以进一步改进工业加工性,例如加工和制造速度以及材料的质量。
纺织片材纤维和纱线可自矿物纤维制造,如玻璃纤维或硅酸盐纤维,天然纤维如羊毛、丝或棉,人造纤维,如聚酯或聚酰胺纤维、纤维素纤维、内聚物纤维或金属纤维。同样可使用由所提衬底组成的单纤维和人造短纤维。进一步可能的在使用由纤维混合组成的片状纤维,如棉/聚酯、纸以及天然户状纤维如皮革。
涂覆或整理可在刮涂加工、浸渍(拧压)加工、挤压加工、喷雾植绒或雾化加工、浸轧、浸染或浸渍-脱水加工中进行。同样地,各种滚筒涂覆如凹版滚筒、润湿滚筒或经多滚筒系统的施用以及印刷,例如圆网印刷是可能的。整理或涂覆进一步可用泡沫施加并随后砑光,使用轧光机,包括热熔性砑光机。
共聚物(Q)进一步可作为涂料和油漆的添加剂。添加共聚物(Q)至例如放射或加成固化油漆导致表面粗糙性降低,并因此降低油漆的滑动阻力。共聚物(Q)可进一步作为化妆制品的组分,例如作为洗发液的调节剂及作为建筑物保护剂。此外,共聚物(Q)构成表面活性剂并可作为清洁剂、表面活性剂、乳化剂、消泡剂及泡沫稳定剂。
上述通式的全部符号彼此独立地各具有其意义。在全部通式中的硅原子为四价。
具体实施方式
在随后的实施例中,全部份数和百分率都基于重量,除非另有说明。再者,除非另有说明,随后的实施例在环境大气压力下、即在约1000百帕下,及在室温下、即约20℃下或在无另加热和冷却下当反应物一起加入时生成的温度下进行。实施例中报告的全部粘度所涉及的温度为25℃。
AZ为胺数目,胺数目为中和1克物质所需的1N HCl毫升数。
实施例1
250克末端氨丙基官能的硅油(AZ=0.18)在50℃下与4.85克2,3-环氧丙基三甲基氯化铵(QUAB151,Degussa AG)在4克异丙醇的70%水溶液一起搅拌12小时。其后,加入含25.69克α-丙烯酸官能和ω-甲氧基官能低聚乙二醇(Mn=约1142)的250克异丙醇,并在回流条件下搅拌2小时。在减压下除去溶剂,留下279克无色牛脂状固体(AZ=0.16)。
实施例2
250克末端氨丙基官能的硅油(AZ=0.26)在50℃与14.02克2,3-环氧丙基三甲基氯化铵(QUAB151,Degussa AG)在10克异丙醇的70%水溶液一起搅拌12小时。加入含143克α-去水甘油基官能和ω-丁氧基官能的聚乙二醇-聚丙二醇共聚物(Mn=约2200;约22个EO单元和19个PO单元)的250克异丙醇,并在回流条件下再搅拌6小时。在减压下除去溶剂,留下302.5克无色固体(AZ=0.21)。
实施例3
250克末端氨丙基官能的硅油(AZ=0.56)在50℃下与15.1克2,3-环氧丙基三甲基氯化铵(QUAB151,DegussaAG)在10.6克异丙醇的70%水溶液一起搅拌12小时。其后,加入含67克α-去水廿油基官能的和ω-丁氧基官能的聚乙二醇(Mn=约319)的250克异丙醇,并在回流条件下再搅拌6小时。在减压下除去溶剂,留下327.5克白色腊状固体(AZ=0.42)。
实施例4
250克α-氨丙基和ω-异丁氧基官能的硅油(AZ=0.5)在50℃下与27克2,3-环氧丙基三甲基氯化铵(QUAB151,Degussa AG)在19克异丙醇中的70%水溶液一起搅拌12小时。其后,加入含142.75克α-丙烯酸官能的和ω-甲氧基官能的低聚乙二醇(Mn=约1142)的250克异丙醇,并在回流条件下搅拌4小时。在减压下除去溶剂,留下412克淡黄色固体(AZ=0.30)。
实施例5
250克具有三甲基硅烷基端基的氨乙基氨丙基官能的硅油(AZ=0.25)在50℃下与13.48克2,3-环氧丙基三甲基氯化铵(QUAB151,DegussaAG)在9.5克异丙醇的70%水溶液一起搅拌12小时。其后,加入含25.2克α-丙烯酸官能的和ω-甲氧基官能的低聚乙二醇(Mn=约807)的250克异丙醇,并在回流条件下搅拌3小时。在减压下除去溶剂,留下284.5克淡黄色固体(AZ=0.22)。
实施例6
250克具有三甲基硅烷基端基的氨乙基氨丙基官能的硅油(AZ=0.60)在70℃下与64.13克2,3-环氧丙基二甲基十二基氯化铵(QUAB342,Degussa AG)和4.35克KOH在100克乙醇中的水溶液一起搅拌12小时。其后,加入含75.8克α-去水甘油基和ω-丁氧基官能的聚乙二醇(Mn=约1010)和150克异丙醇,并在回流条件下再搅拌8小时。在减压下除去溶剂,留下351克白色蜡状固体(AZ=0.43)。
实施例7
250克末端氨丙基官能的硅油(AZ=0.18)在50℃下与9.7克2,3-环氧丙基三甲基氯化铵(QUAB151,Degussa AG)在7克异丙醇中的70%水溶液一起搅拌12小时。其后,加入含12.45克α,ω-二丙烯酸官能的低聚乙二醇(Mn=约830)及34.2克α-丙烯酸官能和ω-甲氧基官能的低聚乙二醇(Mn=约1142)的250克异丙醇,并在回流条件下搅拌4小时。在减压下除去溶剂,留下303克淡黄色牛脂状固体(AZ=0.15)。
实施例8
250克末端氨丙基官能的硅油(AZ=0.18)在50℃下与9.7克2,3-环氧丙基三甲基氯化铵(QUAB151,Degussa AG)在7克异丙醇的70%水溶液一起搅拌12小时。其后,加入含38克α,ω-二丙烯酸官能的低聚乙二醇(Mn=约1126)的250克异丙醇,并在回流条件下搅拌2小时。在减压下除去溶剂,留下295克淡黄色牛脂状固体(AZ=0.15)。
性能实施例
填料加工:
使用单位重量200克/平方米的脱色、未整理的PES/CO 65/35斜纹织品。使用的参考物为具有标准硅氧烷软化剂乳液(氨基官能的聚二甲基硅氧烷的微乳液)的整理剂以及以水浸轧后干燥的纺织品。
纺织品以个别溶液饱和,在二碗轧液机的拉幅架上轧掉70%湿轧液率及在Mathis实验室拉幅机上在150℃下干燥2分钟。纺织品然后在23℃和相对湿度50%下调湿至少12小时。
性能实施例结果的测定方法:
A)柔软手感的测定(手感评估)
因为纺织品的柔软手感大大依赖测试者的主观手感,所以仅界面条件可标准化而评估本身则不能。不过为确认再现性,成品样品经评估并以其柔软手感顺序评分。为此目的,10个测试者对n个样品给予1至n分,n分为最软的样品及1分为最不软的样品。报告的结果因此为各样品评分的平均值。
B)小水滴吸收时间的测定
整理后,成品样品在23℃及50%相对湿度下调节8小时,然后去离子水的小滴由6厘米高度置于拉紧的纺织品表面上,测定小水滴被纺织品吸收所需时间,3分钟为允许的最长时间。进行5次测定并且结果经平均。
表1列出要出浸轧加工完成的纺织品结果的一些性能实施例。
表1:
实施例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
实施例1的乳液 | 20g/l | |||||||||
实施例2的乳液 | 20g/l | |||||||||
实施例3的乳液 | 20g/l | |||||||||
实施例4的乳液 | 20g/l | |||||||||
实施例5的乳液 | 20g/l | |||||||||
实施例6的乳液 | 20g/l | |||||||||
实施例7的乳液 | 20g/l | |||||||||
实施例8的乳液 | 20g/l | |||||||||
标准Si微乳液 | 20g/l | |||||||||
冰醋酸 | 0.5g/l | 0.5g/l | 0.5g/l | 0.5g/l | 0.5g/l | 0.5g/l | 0.5g/l | 0.5g/l | 0.5g/l | 0.5g/l |
小水滴吸收时间(秒) | 16 | <1 | <1 | <1 | 130 | 54 | 8 | 13 | >180 | 108 |
手感 | 7.1 | 2.1 | 3.6 | 1.9 | 6.3 | 3.8 | 7.9 | 8.7 | 3.6 | 0 |
Claims (6)
1.一种以下通式(I)的共聚物(Q):
A-B-(D-B)o-A (I),
其中,
A为-R1或-OR1基或以下通式(II)的一价基:
-R-[(NHaEbFc)(a+2b+c-1)+-R]g-(NHdEeFf)(d+2e+f-2)+[g(a+2b+c-1)+d+2e+f-2]X-
(II),
R1为氢原子或具有1-100个碳原子的一价烃基,该一价烃基可任选由原子N、O、P、B、Si、S间隔或取代,或含有-C(O)-、-C(O)O-、-C(O)NR9-、-NR9-、-O-、-S-、=N-、≡N单元或由-NR9-、-OH、-SH基取代,
R为具有1-50个碳原子的二价烃基,其可任选由原子N、O、P、B、Si、S间隔或取代,或者含有-C(O)-、-C(O)O-、-C(O)NR9-、-NR9-、-O-、-S-、=N-单元,
R9为氢原子或具有1至18个碳原子的一价烃基,该一价烃基可任选由原子N、O、P、B、Si、S间隔或由-OH、-SH基取代,
a、b及c为0-2的整数,条件为a+b+c的总和为1或2,
d、e和f为0-3的整数,条件为d+e+f的总和为2或3,
g为0-10的整数,
E为以下通式(III)的基:
-R2-NR3+ 3 (III),
R2为具有1-10个碳原子的二价烃基,该二价烃基可任选由原子N、O、P、B、Si、S间隔或取代,或含有-C(O)-、-C(O)O-、-C(O)NR9-、-NR9-、-O-、-S-、=N-、≡N单元或由-NR9-、-OH、-SH基取代,
R3为具有1-20个碳原子的一价烃基,该一价烃基可任选由原子N、O、P、B、Si、S间隔或取代,或含有-C(O)-、-C(O)O-、-C(O)NR9-、-NR9-、-O-、-S-、=N-、≡N单元或由-NR9-、-OH、-SH基取代,
X-为有机或无机阴离子,
F为以下通式(IV)或(V)的基:
-CH2-CHR4-C(O)-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-R5(IV),
-CH2-CH(OH)-CH2-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-R5
(V),
R4为氢原子或甲基,
R5为氢原子、具有1-10个碳原子的一价支链或直链烃基或选自以下组中的单元:CH2=CR4-C(O)-、(R1)2N-CH2-CHR4-C(O)-、R4-CH2-C(O)、HO-CH2-CH(OH)-CH2-及
G为二价基-O-或NR9-,
h为0或1,
i、j和k各为0-200的整数,
B为由选自以下通式(VIa)、(VIb)、(VIc)、(VId)和A的单元构成的二价基:
(SiR6 2O2/2)1 (VIa), (SiR6R7O2/2)m (VIb),
(-SiR6 2-)p+1 (VIc), (SiO3/2)p (VId),
R6为氢原子、-OR1或具有1-200个碳原子的一价烷基,该一价烷基可由卤原子、羧基、环氧基、羟基或聚醚基取代,并且可任选由单元-C(O)-、-C(O)O-、-C(O)NR9-、-NR9-、-O-、-S-间隔,
R7为通式(II)的一价基,
l和m为0-5000的整数,
p为0-500的整数,
D为以下通式(VIII)的二价基:
-([R-(NHaEbFc)]n-J-[(NHaEbFc)-R]n}-(2n(a+2b+c)-4}+[2n(a+2b+c)-4]X-
(VIII),
n为1至10的整数,
J为以下通式(HX)或(X)的二价基:
-CH2-CHR4-C(O)-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-C(O)-CHR4-CH2-
(IX),
-CH2-CH(OH)-CH2-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-CH2-CH(OH)-CH2-
(X),
o为≥0的整数,
条件是通式(I)的共聚物含有至少一个E基和一个F基。
2.权利要求1的共聚物(Q),其平均分子量Mn为500克/摩尔至1000000克/摩尔。
3.权利要求1或2的共聚物(Q),其中R为-(CH2)-、-(CH2)2-或-(CH2)3-基。
4.权利要求1-3之一的共聚物(Q),其中R1为氢、甲基、乙基、丙基、环己基或乙酰基。
5.权利要求1-4之一的共聚物(Q),其中R2为直链或支链亚烷基。
6.一种制备权利要求1的通式(I)的共聚物(Q)的方法,其包括使选自通式(XI)、(XII)、(XIII)、(XIV)和(XV)化合物的有机硅化合物或其混合物,与选自通式(XVI)和(XVII)化合物的聚醚及选自通式(XVIII)和(XIX)化合物的有机化合物反应:
H-NR1-(R-NHR1)g-R-(SiR6 2O)1-SiR6 2-R(-NHR1-R)g-NR1-H (XI),
H-NR1-(R-NHR1)g-R-(SiR6 2O)1-{SiR6[-R(-NHR1-R)g-NHR1]-O}m-R(-NHR1-R)g-NR1-H
(XII),
R6 3SiO-(SiR6 2O)1-{SiR6[-R(-NHR1-R)g-NHR1]-O}m-SiR6 3 (XIII),
MeO-SiR6 2O-(SiR6 2O)1-{SiR6[-R(-NHR1-R)g-NHR1]-O}m-SiR6 2-OMe
(XIV),
H-NR1-(R-NHR1)g-R-(SiR6 2O)1-SiR6 2-R8 (XV),
CH2=CH-C(O)-G-(R2-G)h-[CH2CH2O]i-[C3H6O]j-[(CH2)4O]k-(R2-G)h-R5 (XVI),
其中Me为甲基,R1、R2、R3、R5、R6、G、X、g、h、i、j、k、l和m分别如权利要求1所限定。
Applications Claiming Priority (2)
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DE10320631.0 | 2003-05-08 | ||
DE10320631A DE10320631A1 (de) | 2003-05-08 | 2003-05-08 | Polyalkoxyreste aufweisende Organosiliciumverbindungen |
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CN1246364C CN1246364C (zh) | 2006-03-22 |
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US (1) | US7153922B2 (zh) |
EP (1) | EP1477513B1 (zh) |
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DE (2) | DE10320631A1 (zh) |
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-
2003
- 2003-05-08 DE DE10320631A patent/DE10320631A1/de not_active Withdrawn
-
2004
- 2004-04-15 DE DE502004000014T patent/DE502004000014D1/de not_active Expired - Lifetime
- 2004-04-15 EP EP04009000A patent/EP1477513B1/de not_active Expired - Lifetime
- 2004-04-23 US US10/831,042 patent/US7153922B2/en not_active Expired - Fee Related
- 2004-05-07 JP JP2004139154A patent/JP2004331977A/ja active Pending
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CN102952272B (zh) * | 2011-08-12 | 2017-03-01 | 赢创德固赛有限公司 | 制备具有含氮基团的聚硅氧烷的方法 |
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Also Published As
Publication number | Publication date |
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CN1246364C (zh) | 2006-03-22 |
US20040225099A1 (en) | 2004-11-11 |
EP1477513B1 (de) | 2005-06-15 |
EP1477513A1 (de) | 2004-11-17 |
US7153922B2 (en) | 2006-12-26 |
DE10320631A1 (de) | 2004-12-09 |
JP2004331977A (ja) | 2004-11-25 |
DE502004000014D1 (de) | 2005-07-21 |
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