CN104508032A - 具有低压缩形变的可加成交联的聚硅氧烷组合物 - Google Patents
具有低压缩形变的可加成交联的聚硅氧烷组合物 Download PDFInfo
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- CN104508032A CN104508032A CN201380039809.9A CN201380039809A CN104508032A CN 104508032 A CN104508032 A CN 104508032A CN 201380039809 A CN201380039809 A CN 201380039809A CN 104508032 A CN104508032 A CN 104508032A
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- Prior art keywords
- silicon
- amino
- group
- addition
- triazole
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- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 125000006017 1-propenyl group Chemical group 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
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- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- HOTMSLZVBZIVIV-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCCCCCCCCCCCCCC)O.[Si] Chemical group C(CCCCCCCCCCCCCCCCCCCCCCCCCCCCC)O.[Si] HOTMSLZVBZIVIV-UHFFFAOYSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IBDXYWZBNMTHJV-UHFFFAOYSA-N hexyl-dimethoxy-(oxiran-2-ylmethoxymethoxy)silane Chemical compound C(C1CO1)OCO[Si](OC)(OC)CCCCCC IBDXYWZBNMTHJV-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000012763 reinforcing filler Substances 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
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- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
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Abstract
本发明涉及一种可加成交联的聚硅氧烷混合物(S),其包含(A)每分子至少含有两个烯基的聚有机硅氧烷,且其在25℃下的粘度为0.2至1000Pa.s,(B)Si-H官能交联剂,(C)氢化硅烷化催化剂,和(D)基于硅氧烷混合物(S),10至200重量ppm的键接于二氧化硅的3-氨基-1,2,4-三唑-5-硫醇;经二价有机键键接至二氧化硅的3-氨基-1,2,4-三唑-5-硫醇(D),以及其制备方法。
Description
技术领域
本发明涉及一种可加成交联的聚硅氧烷混合物(S),其包含键接至二氧化硅的3-氨基-1,2,4-三唑-5-硫醇作为添加剂。
背景技术
EP 0834 534 A1描述了包含有机硫化合物作为低压缩形变添加剂的组合物,这些组合物是可交联的,以产生弹性体。所述有机硫化合物可以被应用于非有机填料。
EP 0442 143 A1描述了一种制备氧化的或硅化填料的方法,其用3-硫-氰酰丙基三乙氧基硅烷或双(3-三甲氧基硅基丙基)四硫化物进行表面改性。
最佳的压缩形变减小是通过3-巯基-1,2,4-三唑来获得的。US 5104 919描述了通过加成交联可固化的、包含三唑化合物的聚硅氧烷组合物,在所述三唑化合物中有3-巯基-1,2,4-三唑。所述三唑化合物的加入是为了提高组合物在有机溶剂中以溶液形式的分散性。因此橡胶会变得微黄和黯哑。
发明内容
本发明提供一种可加成交联的聚硅氧烷混合物(S),其包含:
(A)聚有机硅烷,其每分子包含至少两个烯基,在25℃下的粘度为0.2至1000Pa.s,
(B)SiH官能交联剂,
(C)氢化硅烷化催化剂,和
(D)基于氧化硅烷混合物(S),10-200重量ppm的键接至二氧化硅的3-氨基-1,2,4-三唑-5-硫醇。
3-巯基-1,2,4-三唑至二氧化硅的化学连接可以得到低压缩变形的硫化产品,且不会带来黯哑和黄色染色。
另外令人惊喜地发现,该可加成交联的聚硅氧烷混合物(S)的起始温度比包含未键接之3-巯基-1,2,4-三唑的聚硅氧烷混合物更低,且该硫化作用进行得更令人满意,特别是更快速。
所述聚有机硅氧烷(A)组分包含烯基,优选具有通式(1)
R1 xR2 ySiO(4-x-y)/2 (1),
其中
R1是任选被卤素或氰基取代的、含脂肪族碳碳多键的、且任选经二价有机基团键接于硅的单价C1-C10烃基,
R2是任选被卤素或氰基取代的、由SiC键接的、不含脂肪族碳碳多键的单价C1-C10烃基,
x是非负数,以致每个分子中存在至少两个基团R1,和
y为非负数,以致(x+y)在1.8至2.5的范围内。
使烯基R1易于与SiH官能交联剂(B)发生加成反应。通常使用具有2至6个碳原子的烯基,例如乙烯基、烯丙基、甲代烯丙基、1-丙烯基、5-己烯基、乙炔基、丁二烯基、己二烯基、环戊烯基、环戊二烯基、环己烯基,优选为乙烯基和烯丙基。
烯基R1经二价有机基团键接于聚合物链的硅上,所述二价有机基团是由例如氧化烯烃组成的,例如下列通式(2)
-(O)m[(CH2)nO]o- (2)
其中
m为0或1,特别是0的值,
n为1至4,特别是1或2的值,且
o为1至20,特别是1至5的值。
通式(2)的氧化烯烃键接于硅原子的左侧。
基团R1可以沿着聚合物链的任意位置键接,特别是在末端的硅原子处。
未经取代的基团R2的实例有烷基,例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、叔戊基;己基,例如正己基;庚基,例如正庚基;辛基,例如正辛基和异辛基,例如2,2,4-三甲基戊基;壬基,例如正壬基;癸基,例如正癸基;烯基,例如乙烯基、烯丙基、正-5-己烯基、4-乙烯基环己基和3-降冰片烯基;环烷基,例如环戊基、环己基、4-乙基环己基、环庚基、降冰片基和甲基环己基;芳基,例如苯基、联苯基、萘基;烷芳基,如邻-、间-、和对-甲苯基和乙苯基;芳苯基,例如苯甲基、α-和β-苯乙基。
以基团R2形式被取代的烃基的实例有卤代烃,例如氯甲基、3-氯甲基、3-溴甲基、3,3,3-三氟丙基和5,5,5,4,4,3,3-七氟戊基、以及还有氯苯基、二氯苯基和三氯苯基。
优选R2具有1至6个碳原子,特别优选的是甲基和苯基。
组分(A)还可以是多种包含烯基的聚有机基硅氧烷的混合物,这些聚有机基硅氧烷例如在烯基含量、烯基性质或结构上不同。
包含烯基的聚有机硅氧烷(A)的结构可以是直链、环状或分支的。形成分支聚有机硅氧烷的三官能和/或四官能团单体的含量通常很小,优选至多20mol%,特别为至多0.1%。
特别优选为使用包含乙烯基的聚二甲基硅氧烷,其分子和通式(3)相对应
(ViMe2SiO1/2)2(ViMeSiO)p(Me2SiO)q (3),
其中非负整数p和q遵照下列关系:
p≥0,50<(p+q)<20000,优选200<(p+q)<1000,且0<(p+1)/(p+q)<0.2。特别地,p=0。
所述聚有机硅氧烷(A)在25℃下的粘度优选为0.5至500Pa.s,特别为1至200Pa.s,非常特别优选为1至100Pa.s。
有机硅化合物(B)组分每分子包含至少两个SiH官能团,优选具有通式(4)
HaR3 bSiO(4-a-b)/2 (4),
其中,
R3任选为被卤素和氰基取代的、不含脂肪族碳碳多键的、与SiC键接的单价C1-C18烃基,和
a和b是非负整数,
且附带条件为0.5<(a+b)<3.0,且0<a<2,且每个分子至少包含两个键接硅的氢原子。
R3的实例如同R2所述基团。优选的R3具有1至6个碳原子,特别优选为甲基和苯基。
优选使用每个分子包含3个或更多的SiH键的有机硅化合物(B)。如果使用每分子仅含2个SiH键的有机硅化合物(B),则建议使用每分子至少含有3个烯基的聚有机硅氧烷(A)。
仅基于直接键接于硅原子的氢原子,有机硅化合物(B)的氢含量优选为0.002至1.7重量%范围内的氢,优选为0.1至1.7重量%范围的氢。
优选的有机硅化合物(B)每分子包括至少3个且最多600个硅原子。优选使用每分子包含4至200个硅原子的有机硅化合物(B)。
有机硅化合物(B)的结构可以是直链、分支、环状或网状。
特别优选的有机硅化合物(B)是通式(5)的直链聚有机硅氧烷
(HR4 2SiO1/2)c(R4 3SiO1/2)d(HR4SiO2/2)e(R4 2SiO2/2)f (5)
其中,
R4定义同R3,且
非负整数c、d、e、f遵照下列关系:
(c+d)=2,(c+e)>2,5<(e+f)<200,且1<e/(e+f)<0.1。
在可交联硅氧烷组合物中包含的SiH官能的有机硅化合物(B)的量优选为SiH基团与烯基的摩尔比为0.5-5,特别为1.0-3.0。
可以用在对加成交联的聚硅氧烷混合物的交联过程中对氢化硅烷化反应实施催化的任何已知催化剂作为氢化硅烷化催化剂(C)。
特别地,使用选自铂、铑、钯、钌和铱的金属以及其化合物作为氢化硅烷化催化剂(C)。优选使用铂和铂化合物。特别优选的是可溶于聚有机硅氧烷的铂化合物。例如可以使用式(PtCl2·烯烃)2和H(PtCl3·烯烃)的烯烃合铂络合物作为可溶的铂化合物,在此优选使用具有2至8个碳原子的烯烃,例如乙烯、丙烯、丁烯的异构体和辛烯的异构体,或具有5至7个碳原子的环烯烃,例如环戊烯、环己烯和环庚烯。其它可溶的铂催化剂有式(PtCl2C3H6)2的环丙烷合铂络合物,六氯铂酸分别与醇、与醚、与醛的反应产物以及其混合物,或六氯铂酸与甲基乙烯基环四硅氧烷在存在碳酸氢钠的情况下在乙醇溶液中的反应产物。特别优选为铂与乙烯基硅氧烷(如sym-二乙烯基四甲基二硅氧烷)的络合物。欧洲专利EP 1077226 A1和EP0994159A1中所述的铂化合物同样也是适合的,且这里将其所公开的内容并入本申请作为参考。
可以以任何需要的形式使用氢化硅烷化催化剂(C),例如也可以包含氢化硅烷化催化剂的微胶囊,或以聚有机硅氧烷颗粒的形式加以使用,例如EP 1006147 A1中所述,这里将其公开的内容并入本申请作为参考。
选择氢化硅烷化催化剂(C)的含量,优选使可加成交联的硅氧烷混合物(S)的Pt含量为0.1至200重量ppm,特别是0.5至40重量ppm。
组分(D)优选为经二价有机基团在3-氨基基团处与二氧化硅键接的3-氨基-1,2,4-三唑-5-硫醇。
所述经二价有机基团键接至二氧化硅的3-氨基-1,2,4-三唑-5-硫醇同样在本发明中被提供。
优选通过3-氨基-1,2,4-三唑-5-硫醇在经二价有机基团键接至二氧化硅的环氧基团上的加成反应制备组分(D)。在左侧键接至二氧化硅的硅原子上并在右侧携带环氧基团的此处所提供的二价有机基团优选具有通式(6)所示结构
-(CH2)g[O(CH2)h]i(CH2)k- (6)
其中
g为1至10,特别为1至4的值,
h为1至4,特别为2或3的值,
i为0、1、2或3,特别为1的值,和
k为1至10,特别为1至5的值。
键接至二氧化硅的硅原子上并携带环氧基团的二价有机基团,优选是通过二氧化硅与具有经二价有机基团连接的环氧基团的环氧烷氧基硅烷反应而制备的。
合适的实例为环氧丙氧基丙基三甲氧基硅烷、环氧丙氧基丙基二甲氧基甲基硅烷、环氧丙氧基己基三甲氧基硅烷和环氧丙氧基己基二甲氧基甲基硅烷。
组分(D)中二氧化硅优选被蒸汽沉积二氧化硅或沉积二氧化硅,优选具有BET比表面积至少为50m2/g,特别是100至400m2/g。
环氧烷氧基硅烷与二氧化硅反应的反应时间优选为1小时至3天,特别优选为6小时至2天,特别为12至36小时。其反应温度优选为20℃至100℃,特别为40℃至80℃。其反应压力优选为0.1至10bar,特别为0.5至2bar。
每克二氧化硅所用的环氧烷氧基硅烷的量优选为0.01至0.9g,特别优选为0.05至0.5g,特别为0.1至0.3g。
优选地,携带经二价有机基团连接的环氧基团的二氧化硅随后与3-氨基-1,2,4-三唑-5-硫醇反应,得到组分(D)。
携带经二价有机基团连接的环氧基团的二氧化硅与3-氨基-1,2,4-三唑-5-硫醇之间反应的反应时间优选为1小时至3天,特别为6小时至2天,特别是12至36小时。优选的反应温度为20℃至100℃,特别为40℃至80℃。优选的反应压力为0.1至10bar,特别为0.5至2bar。
相对于每摩尔在二氧化硅上的环氧基团,3-氨基-1,2,4-三唑-5-硫醇的用量优选为0.8至1.5mol,特别优选为0.9至1.1mol。
在3-氨基-1,2,4-三唑-5-硫醇与经二价有机基团键接至二氧化硅的环氧基团之间的加成反应之后,优选用有机硅烷、有机硅氮烷或有机硅氧烷对所得组分(D)中二氧化硅表面剩余的自由硅烷醇基团进行后疏水化处理。特别优选的是用六甲基二硅氮烷进行后疏水化。所述疏水化会引起压缩变形额外减小。
各种情况下都基于硅烷混合物(S),键接至二氧化硅上的3-氨基-1,2,4-三唑-5-硫醇(D)的量优选为20至120重量ppm,特别为30至90重量ppm。
所述硅烷混合物(S)可不仅仅包括链接至3-氨基-1,2,4-三唑-5-硫醇(D)的二氧化硅,而且还包括至少一种其他的填料(E)。
BET表面积至多为50m2/g的非增强型填料(E)的实例有石英、硅藻土、硅酸钙、硅酸锆、沸石类、金属氧化物粉末(例如氧化铝、氧化钛、氧化铁和氧化锌,以及这些物质的混合氧化物)硫酸钡、碳酸钙、石膏、氮化硅、碳化硅、碳化硼、玻璃粉以及塑料粉末。增强填料,即BET表面积至少为50m2/g、特别为100至400m2/g的填料例如是蒸汽沉积二氧化硅、沉积二氧化硅、氢氧化铝、炭黑,例如炉黑和乙炔黑,以及具有更大BET比表面积的硅铝混合氧化物。
所述填料(E)可以被疏水化,例如通过用有机硅烷、有机硅氮烷、或有机硅氧烷处理,或通过羟基基团的醚化得到烷氧基。可以使用一种填料(E),且也可以使用至少两种填料(E)的混合物。
所述聚硅烷混合物(S)优选包含至少3重量%,特别优选至少5重量%,特别至少10重量%,且至多40重量%的填料含量(E)。
如果希望,所述硅烷混合物(S)还可以包含0重量%至70重量%,优选0.0001重量%至40重量%的可能的添加剂作为其他的组分(F)。这些添加剂例如可以为不同于聚有机硅氧烷(A)和(B)的树脂类聚有机硅氧烷、分散剂、溶剂、助粘剂、颜料、染料、增塑剂、有机聚合物、热稳定剂和抑制剂。其中提及的添加剂如颜料和染料。其他组分可以是具有触变作用的组分,例如二氧化硅细粒或其他可商购的触变性添加剂。优选包含最高0.5重量%,特别优选最多0.3重量%,特别为<0.1重量%的过氧化氢作为用于更好交联的其他组分(F)。
还可以包含用于调节组合物的加工时间、起始温度和交联速率的其他添加剂。这些抑制剂和稳定剂在交联组合物领域中是公知的。
本发明另外涉及用于制备可加成交联的聚硅氧烷混合物(S)的方法,由聚硅氧烷混合物(S)制备交联聚硅氧烷弹性体的方法,以及由此获得的聚硅氧烷弹性体成型体。
所述聚硅氧烷混合物(S)的制造或者配混优选通过将组分(A)和(D)以及任选填料(E)的混合而实现。在添加交联剂(B)和氢化硅烷化催化剂(C)之后,优选通过加热进行交联,优选在30至250℃下,更优选在至少50℃下,特别是至少100℃下,更优选在150至210℃下。
上式中所有符号的定义均彼此独立。所有式子中的硅原子均为四价。全部聚硅氧烷混合物(S)的组分为100重量%。
具体实施方式
除非另有说明,下列实施例中所有的数量以及百分数均基于重量,所有压力为0.10MPa(abs.),且所有温度为20℃。
本发明实施例1:
与EP 0926210B2文中实施例7所述类似,将100g BET表面积为300m2/g的蒸汽沉积二氧化硅(其可以T30从Wacker Chemie AG处商购)和18.0g(0.076mol)的环氧丙氧基丙基三甲氧基硅烷(可以GF 80从Wacker Chemie AG处商购)反应。元素分析显示每克的硅烷化二氧化硅产品含有0.75mmol的环氧官能团。随后将3.5L甲醇中6.097g(52.5mmol)的3-氨基-1,2,4-三唑-5-硫醇作为初始进料,并将上述制备的70g(相对应的52.5mmol环氧官能团)硅烷化二氧化硅分批加入。一旦添加结束,将混合物在回流下进一步加热24个小时。随后通过旋转蒸发器脱去溶剂。这产生66.85g(理论上的88%)的白色粉末。元素分析显示,3-氨基-1,2,4-三唑-5-硫醇的键接程度相对于硫含量是定量的,而相对于氮含量是90%。1H核磁共振波普显示3-氨基-1,2,4-三唑-5-硫醇通过3-氨基基团以92%的选择性、开环键接至环氧基团。
本发明实施例2:
制备压缩变形母体:将15g粘度为20000mPa s乙烯基封端的、直链型聚二甲基硅氧烷(乙烯基聚合物2000)作为实验室捏合机的初始进料。将9.7g上述包含3-氨基-1,2,4-三唑-5-硫醇的二氧化硅随后分批加入,同时不断地捏合。所述混合物随后再被捏合1个小时。随后将另外51.7g的乙烯基聚合物2000分批加入,并将混合物另外捏合一个小时。产量为60.0g(理论值的80%)。
本发明实施例3:
通过与来自Wacker Chemie AG的3005/40相类似的方法制备包含组分(A)、(B)、(C)和(E)的交联聚硅氧烷弹性体,其具有0.7重量%的在更早阶段描述的压缩变形母体混合物作为组分(D)(键接有二氧化硅的活性组分3-氨基-1,2,4-三唑-5-硫醇的相应含量为70ppm)。所述弹性体是无色透明的。根据DIN ISO 815,在175℃的温度下7天后的压缩变形为44%。
本发明实施例4:
对根据本发明实施例1中所制备的已键接3-氨基-1,2,4-三唑-5-硫醇的二氧化硅的表面上所存在的剩余硅烷醇进行后疏水化:在具有回流冷凝器的250ml三颈烧瓶中,在氮气下将140ml的六甲基二硅氧烷(可以AK 065oil从Wacker Chemie AG处商购)用作初始进料。然后将下列添加于此:首先是2.77g的六甲基二硅氮烷,随后在grounding下添加16g在本发明实施例1中所述的3-氨基-1,2,4-三唑-5-硫醇官能化二氧化硅。所述混合物随后在30分钟期间被加热至80℃,并在该温度下另外搅拌2个小时。将所述混合物在搅拌下冷却至室温,随后在旋转蒸发器上于65℃下蒸干,并逐渐减压,将最终压力<1.0mbar持续20分钟。粉碎结块的粉末,并在120℃下,在通入温和的氮气流的干燥箱中将其进一步干燥2个小时。产量为:13.5g(理论上的92%)。
本发明实施例5:
制备压缩变形母体:将15g粘度为20000mPa s的、乙烯基封端的、直链型聚二甲基硅氧烷(乙烯基聚合物2000)作为实验室捏合机的初始进料。随后伴随不断捏合,分批加入6.9g本发明实施例4中的包含3-氨基-1,2,4-三唑-5-硫醇并用六甲基二硅氮烷进行后疏水化的二氧化硅。随后将混合物再捏合一个小时。随后分批加入另外38.1g的乙烯基聚合物20000,并将混合物另外捏合一个小时。产量为45.3g(理论上的76%)。
本发明实施例6:
通过与来自Wacker Chemie AG的3005/40相类似的方法制备包含组分(A)、(B)、(C)和(E)的交联聚硅氧烷弹性体,其包含0.7重量%的上述后疏水化压缩变形母体混合物(键接有二氧化硅的活性组分3-氨基-1,2,4-三唑-5-硫醇的相应含量为70ppm)。所述弹性体是无色透明的。根据DIN ISO 815,在175℃的温度下7天后的压缩变形为36%。
对比例1:
根据本发明实施例3和6制备的交联聚硅氧烷弹性体,但是不含任何压缩变形母体。所述弹性体是无色透明的。根据DIN ISO815,在175℃的温度下7天后的压缩变形为87%。
对比例2:
根据本发明实施例3和6制备的交联聚硅氧烷弹性体,但是含有下列压缩变形母体。
将6.9g BET表面积为300m2/g的蒸汽沉积二氧化硅(可以T30从Wacker Chemie AG处商购)与1g 3-氨基-1,2,4-三唑-5-硫醇在5g水中的溶液混合,并通过蒸发将水去除。
将15g粘度为20000m Pa.s的、乙烯基封端的直链型聚二甲基硅氧烷(乙烯基聚合物2000)作为实验室捏合机的初始进料。随后伴随不断捏合,分批加入上述包含3-氨基-1,2,4-三唑-5-硫醇的二氧化硅。随后将混合物再捏合一个小时。随后分批加入另外51.7g的乙烯基聚合物20000,并将混合物另外捏合一个小时。产量为58.5g(理论上的78%)。
该弹性体着色轻微发黄,并轻微黯哑。
根据DIN ISO815,在175℃的温度下7天后的压缩变形为46%。
本发明实施例1中T30与Geniosil GF的反应:
在本发明实施例1中,3-氨基-1,2,4-三唑-5-硫醇在键接有二氧化硅的Geniosil GF的环氧基团上的开环加成反应。
在本发明实施例4中,二氧化硅表面上的剩余硅烷醇基团的后疏水化。
Claims (9)
1.一种可加成交联的聚硅氧烷混合物(S),其包括:
(A)每分子包含至少两个烯基的聚有机硅氧烷,其在25℃下的粘度为0.2至1000Pa.s,
(B)Si-H官能交联剂,
(C)氢化硅烷化催化剂,和
(D)基于聚硅氧烷混合物(S),10至200重量ppm的键接至二氧化硅的3-氨基-1,2,4-三唑-5-硫醇。
2.根据权利要求1所述的可加成交联的聚硅氧烷混合物(S),其中所用的聚有机硅氧烷(A)为包含乙烯基团的聚二甲基硅氧烷,其中他们的分子与通式(3)相对应
(ViMe2SiO1/2)2(ViMeSiO)p(Me2SiO)q (3),
其中
Vi为乙烯基,且Me为甲基,且非负整数p和q遵照下列关系:
p≥0,50<(p+q)<20000,优选200<(p+q)<1000,且0<(p+1)/(p+q)<0.2。
3.根据权利要求1或2所述的可加成交联的硅氧烷混合物(S),其中所用的SiH官能交联剂(B)为每个分子包含至少两个SiH官能团的有机硅化合物(B),且其组成具有以下平均通式(4)
HaR3 bSiO(4-a-b)/2 (4),
其中
R3为任选被卤素和氰基取代的、不含脂肪族碳碳多键的、与SiC键接的单价C1-C18烃基,和
a和b是非负整数,
且附带条件为0.5<(a+b)<3.0,且0<a<2,且每个分子至少包含两个键接硅的氢原子。
4.根据前述任意一项权利要求所述的可加成交联的聚硅氧烷混合物(S),其中所述的氢化硅烷化催化剂(C)选自铂、铑、钯、钌和铱的金属以及其化合物。
5.根据前述任意一项权利要求所述的可加成交联的聚硅氧烷混合物(S),其中所述的组分(D)为经二价有机基团在3-氨基基团处与二氧化硅键接的3-氨基-1,2,4-三唑-5-硫醇。
6.一种经二价有机基团键接至二氧化硅的3-氨基-1,2,4-三唑-5-硫醇(D)。
7.一种制备经二价有机基团键接至二氧化硅的3-氨基-1,2,4-三唑-5-硫醇的方法,其中第一步是使具有经二价有机基团连接的环氧基团的环氧烷氧基硅烷与二氧化硅反应,并在第二步中,使携带经二价有机基团连接的环氧基团的二氧化硅与3-氨基-1,2,4-三唑-5-硫醇反应,得到组分(D)。
8.根据权利要求7所述的方法,在所述第二步之后,用有机硅烷、有机硅氮烷或有机硅氧烷对组分(D)中二氧化硅表面剩余的自由硅烷醇基进行后疏水化。
9.根据权利要求1至5中任意一项所述的可加成交联的聚硅氧烷混合物(S),其包含至少一种其他的填料(E)。
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CN107922622A (zh) * | 2015-07-09 | 2018-04-17 | 莫门蒂夫性能材料股份有限公司 | 使用硫化合物和铂催化剂的硅氧烷交联法 |
CN107922622B (zh) * | 2015-07-09 | 2021-03-16 | 莫门蒂夫性能材料股份有限公司 | 使用硫化合物和铂催化剂的硅氧烷交联法 |
CN105419341A (zh) * | 2015-12-15 | 2016-03-23 | 江苏天辰新材料股份有限公司 | 一种低压缩永久变形硅橡胶及其制备方法和使用方法 |
CN105419341B (zh) * | 2015-12-15 | 2018-04-10 | 江苏天辰新材料股份有限公司 | 一种低压缩永久变形硅橡胶及其制备方法和使用方法 |
CN109592690A (zh) * | 2018-12-18 | 2019-04-09 | 山东东岳有机硅材料股份有限公司 | 一种利用气相二氧化硅制备疏水性二氧化硅的方法 |
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EP2877527B1 (de) | 2018-04-18 |
WO2014016122A1 (de) | 2014-01-30 |
EP2877527A1 (de) | 2015-06-03 |
JP5908658B2 (ja) | 2016-04-26 |
US9200146B2 (en) | 2015-12-01 |
CN104508032B (zh) | 2016-11-16 |
KR20150036275A (ko) | 2015-04-07 |
US20150203664A1 (en) | 2015-07-23 |
KR101751763B1 (ko) | 2017-07-11 |
JP2015522699A (ja) | 2015-08-06 |
DE102012213260A1 (de) | 2014-01-30 |
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