CN113366044A - 基于有机硅的固化性组合物和其应用 - Google Patents
基于有机硅的固化性组合物和其应用 Download PDFInfo
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- CN113366044A CN113366044A CN201980090586.6A CN201980090586A CN113366044A CN 113366044 A CN113366044 A CN 113366044A CN 201980090586 A CN201980090586 A CN 201980090586A CN 113366044 A CN113366044 A CN 113366044A
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Abstract
本技术提供基于有机硅的固化性组合物,其包括杂化有机硅聚合物、催化剂、和填料。本技术提供包括如下的固化性有机硅组合物:聚合物A,其包括包含烷氧基自由基、羟基自由基、异氰酸酯自由基、伯胺、或羧基自由基的有机分子或硅氧烷分子;任选地,聚合物B,其包括有机分子、硅氧烷分子、或杂化‑硅氧烷分子;催化剂;和填料。
Description
本申请要求2018年12月26日提交的印度临时申请201821049328的优先权和权益,将其公开内容完全引入本文作为参考。
技术领域
本技术涉及基于有机硅的固化性组合物。具体地,本技术涉及包括杂化(hybrid)有机硅聚合物、催化剂、和填料的基于有机硅的固化性组合物。所述组合物在固化时提供有机硅复合物(复合材料,composite)。
背景技术
有机硅因其固有性质例如高的热稳定性、柔性和/或耐化学性而闻名。硅氧烷基于它们的性质例如以上提及的那些而被用于电子或电气应用。虽然在其中导电性可为重要的应用中使用硅氧烷可为期望的,但是开发导电性硅氧烷材料是挑战性的。
在有机硅中可通过将填料添加到有机硅基质中而实现电性质,并且期望的传导性可通过提高组合物中的填料加载量而实现。然而,在高的加载量下,经过一段时间填料颗粒可从组合物分离出来。因此,具有高加载量的填料在硅氧烷基质中的分散是主要挑战。组合物中较高的填料加载量还可不利地影响组合物的固化动力学和加工性。其它常见挑战包括,但不限于,可变的接触电阻和体积电阻率。
为了解决这些技术问题,努力开发具有期望的机械和化学性质的固化性有机硅组合物。
发明内容
提供固化性有机硅组合物,其能够提供期望的粘附以及其它机械和化学性质以及良好的传导性。在一些实施方式中,本技术提供固化性组合物,其包括聚合物A、催化剂、和一种或多种填料,其中聚合物A包括硅氧烷、或杂化硅氧烷分子。
在一些实施方式中,所述固化性组合物进一步包括聚合物B。在一个或多个实施方式中,聚合物B可充当交联剂。在一个或多个实施方式中,聚合物B可包括硅氧烷、杂化硅氧烷、硅烷或其组合。在这些实施方式中,所述固化性组合物包括聚合物A、聚合物B、催化剂、和一种或多种填料,其中聚合物A包括硅氧烷、或杂化硅氧烷分子。在这些实施方式中,聚合物A包括烷氧基自由基(基团,radical)、羟基自由基、异氰酸酯自由基、伯胺、或羧基(羧型,carboxylic)自由基。
在一些实施方式中,提供固化性有机硅组合物。所述组合物包括(i)式1的聚合物A;(ii)填料;(iii)催化剂,和任选地(iv)式2的聚合物B;其中所述固化性有机硅组合物为缩合固化体系;和所述固化性组合物的经固化的形式为传导性材料。聚合物A可由式1表示:
(R)a(VV)b(R)a″......................式1
其中a、a"和b可为零或更大,条件是a+a"+b总是大于0,
R可由式(1a)表示,其可为线型或支化的:
(CH2)c(CH2O)d(CHOH)e(S)f(X)a....................式(1a)
S可独立地选自羟基自由基、异氰酸酯自由基、伯胺、或羧基自由基并且X独立地选自式(1b)
其中R1、R1′、和R1"独立地选自烷基自由基,烷氧基自由基,羟基自由基,氢自由基,或者选自具有C1-C20碳原子的未取代烃、或氟化烃,
c、d、e、f、g为整数并且可为0或更大,条件是c+d+e+f+g>0,
式1中的W可由式(1c)表示
(Y)h(Z)i........................................式(1c)
其中h、i可为零或更大,条件是h+i>0,
式(1c)中的Y可由式(1d)表示:
(M1)x″(D1)j(D2)k(D*)l(T1)m(Q1)n(M2)y″.............式(1d)
其中j、k、l、m、n、x″、和y″可为零或更大,条件是(j+k+1+m+n+x″+y″)>0。
其中M1由式(1e)表示:
R2R3R4Sil1/2.......................式(1e)
D1由式(1f)表示:
R5R6Sil2/2...........................式(1f)
D2由式(1g)表示:
R7R8SiI2/2................................式(1g)
D*由式(1h)表示:
D3由式(1i)表示:
R9R10SiI2/2....................式(1i)
D4由式(1j)表示:
R11R12Sil2/2...................式(1j)
D5由式(1k)表示:
R13R14SiI2/2.......................式(1k)
D6由式(11)表示:
R15R16SiI2/2...................式(11)
T1由式(1m)表示:
R17Sil3/2.....................式(1m)
Q1由式(1n)表示:
Sil4/2.................式(1n)
M2由式(1o)表示:
R18R19R20Sil1/2.....................式(1o)
R2-R20可独立地选自R,或者具有C1-C20碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,或羧酸根自由基或环氧自由基,
其中o、p可为零或更大,条件是o+p>0,
I可选自O或CH2基团,其遵从如下限制:分子含有偶数个O1/2和偶数个(CH2)1/2,
式(1c)中的Z可由式(1p)表示:
其中E可独立地选自氨基甲酸酯,脲,酸酐,酰胺,酰亚胺,氢自由基,或者具有1-20个碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,q可为0或更大,r>0。
J可独立地选自式(1q)或(1q′):
其中M可独立地选自碳原子或杂原子,
G为选自氧的杂原子,
其中t、s可为零或更大,条件是t+s>0,
L1可独立地选自氨基甲酸酯、脲、酸酐、或酰胺,
L2、L3、L4可独立地选自邻苯二甲酰亚胺、氟化烃、取代或未取代的烃、取代或未取代的芳族烃,
u、v、w、x可为0或更大,并且K可独立地选自碳、杂原子、烃、或羰基自由基,条件是y>o。
聚合物B可由式(2a)表示:
其中M′可独立地选自碳原子或杂原子,
G′为选自氧的杂原子,
s′可为0或更大,t′>0,
L1′可独立地选自异氰酸酯、伯胺、或者由式(2b)表示的R’:
(M3)y”(D7)c’(D8)d’(D**)e’(T2)f’(Q2)g’(M4)z’...........式(2b)
其中M3由式(2c)表示:
R25R26R27Sil′1/2.........................式(2c)
D7由式(2d)表示
R28R29Sil′2/2...........................................式(2d)
D8由式(2e)表示:
R30R31Sil′2/2.........................................式(2e)
D**由式(2f)表示:
D9由式(2g)表示:
R32R3xSil′2/2......................................式(2g)
D10由式(2h)表示:
R34R35Sil′2/2..................................式(2h)
D11由式(2i)表示:
R36R37Sil′2/2..................................式(2i)
D12由式(2j)表示:
R38R39Sil′2/2...................................式(2j)
T2由式(2k)表示:
R40Sil′3/2........................................式(2k)
Q2由式(21)表示:
Sil′4/2........................式(2l)
M4由式(2m)表示:
R41R42R43Sil′1/2............................式(2m)
其中R25-R43可独立地选自氢自由基,具有C1-C20碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,烷氧基自由基,或羟基自由基,
I′为O或CH2基团,其遵从如下限制:分子含有偶数个O1/2和偶数个(CH2)1/2
c′、d′、e′、f′、g′、y″和z′可为零或更大,条件是(c′+d′+e′+f+g′+y″+z′)>0,
当e′>0时h′、i′>0。
式(2a)的L1′还可由式(2n)表示:
(R′)a′(W′)b′(R′)a″″....................................式(2n)
其中R′由以上式(2b)表示,
W′可独立地选自例如如下的官能性:1-20个碳原子的取代或未取代的烃自由基、氟化烃、或全氟醚,
a′、a″′可为0或更大,条件是a″+a″′>0,并且b′可为0或更大。
聚合物B还可由式(2a′)表示:
其中E′可独立地选自R′,异氰酸酯,胺,氢,具有C1-C20碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,或其组合,
其中q′、r′可为零或更大,条件是q′+r′>0,
J′可独立地选自式(2b′):
L2′、L3′、L4′可独立地选自邻苯二甲酰亚胺自由基,氟化烃,取代或未取代的烃,取代或未取代的脂族或芳族烃,脲键,烷氧基或氨基甲酸酯键,
u′、v′、w′、x可为0或更大,条件是(u′+v′+w′+x′)>0,
K可独立地选自碳、硅、杂原子、烃自由基、或羰基自由基,条件是y’>0。
这些和其它实施方式和方面参照以下详细描述而进一步理解。
具体实施方式
在以下说明书和所附权利要求中,将涉及多个术语,其应被定义为具有以下含义。
单数形式“一(个)”、“一(种)”和“该(所述)”包括复数指代物,除非上下文清楚地另有规定。“任选的”或“任选地”意味着随后描述的事件或者情况可发生或者可不发生,并且该描述包括其中事件发生的情况和其中其不发生的情况。
如本文中在整个说明书和权利要求中使用的近似语言可用于修饰可获准变化的任何数量表示法而不导致其所涉及的基本功能的变化。因此,通过术语例如“约”修饰的值不应局限于所详述的精确值。在一些情况下,近似语言可对应于用于测量该值的仪器的精度。
如本文中使用的,术语“芳族”和“芳族自由基”是可互换地使用的并且指的是包括至少一个芳族基团的具有至少1价的原子组(系列,array)。所述包括至少一个芳族基团的具有至少1价的原子组可包括杂原子例如氮、硫、硒、硅和氧,或者可仅由碳和氢组成。如本文中使用的,术语“芳族”包括但不限于苯基、吡啶基、呋喃基、噻吩基、萘基、亚苯基、和联苯自由基。如指出的,芳族自由基含有至少一个芳族基团。芳族基团一定是具有4n+2个“离域”电子的环状结构,其中“n”为等于1或更大的整数,如通过苯基基团(n=1)、噻吩基基团(n=1)、呋喃基基团(n=1)、萘基基团(n=2)、薁基基团(n=2)、蒽基基团(n=3)等所说明的。芳族自由基也可包括非芳族成分。例如,苄基基团为包括苯基环(芳族基团)和亚甲基基团(非芳族成分)的芳族自由基。类似地,四氢萘基自由基为包括与非芳族成分—(CH2)4—稠合的芳族基团(C6H3)的芳族自由基。为了方便起见,术语“芳族自由基”或“芳族”在本文中定义为涵盖宽范围的官能团例如烷基基团、烯基基团、炔基基团、卤代烷基基团、卤代芳族基团、共轭二烯基基团、醇基团、醚基团、醛基团、酮基团、羧酸基团、酰基基团(例如羧酸衍生物例如酯和酰胺)、胺基团、硝基基团等。例如,4-甲基苯基自由基为包括甲基基团的C7芳族自由基,该甲基基团为作为烷基基团的官能团。类似地,2-硝基苯基基团为包括硝基基团的C6芳族自由基,该硝基基团为官能团。芳族自由基包括卤化的芳族自由基例如4-三氟甲基苯基、六氟异丙叉双(4-苯-1-基氧基)(即,—OPhC(CF3)2PhO—)、4-氯甲基苯-1-基、3-三氟乙烯基-2-噻吩基、3-三氯甲基苯-1-基(即,3-CCl3Ph-)、4-(3-溴丙-1-基)苯-1-基(即,4-BrCH2CH2CH2Ph-)等。芳族自由基的进一步实例包括4-烯丙基氧基苯基-1-氧基、4-氨基苯-1-基(即,4-H2NPh-)、3-氨基羰基苯-1-基(即,NH2COPh-)、4-苯甲酰基苯-1-基、二氰基甲叉双(4-苯-1-基氧基)(即,—OPhC(CN)2PhO—)、3-甲基苯-1-基、亚甲基双(4-苯-1-基氧基)(即,—OPhCH2PhO—)、2-乙基苯-1-基、苯乙烯基、3-甲酰基-2-噻吩基、2-己基-5-呋喃基、六亚甲基-1,6-双(4-苯-1-基氧基)(即,—OPh(CH2)6PhO—)、4-羟甲基苯-1-基(即,4-HOCH2Ph-)、4-巯甲基苯-1-基(即,4-HSCH2Ph-)、4-甲硫基苯-1-基(即,4-CH3SPh-)、3-甲氧基苯-1-基、2-甲氧基羰基苯-1-基氧基(例如,甲基水杨基)、2-硝基甲基苯-1-基(即,2-NO2CH2Ph)、3-三甲基甲硅烷基苯-1-基、4-叔丁基二甲基甲硅烷基苯-1-基、4-乙烯基苯-1-基、乙烯叉双(苯基)等。术语“C3-C10芳族自由基”包括含有至少三个,但是不超过10个碳原子的芳族自由基。芳族自由基1-咪唑基(C3H2N2—)表示C3芳族自由基。苄基自由基(C7H7—)表示C7芳族自由基。在一个或多个实施方式中,芳族基团可包括C6-C30芳族基团、C10-C30芳族基团、C15-C30芳族基团、C20-C30芳族基团。在一些具体实施方式中,芳族基团可包括C3-C10芳族基团、C5-C10芳族基团、或C8-C10芳族基团。
如本文中使用的,术语“脂环族基团”和“脂环族自由基”可为可互换地使用的并且指的是具有至少1价的自由基,和其中所述自由基包括是环状的但不是芳族的原子组。如本文中定义的,“脂环族自由基”不含有芳族基团。“脂环族自由基”可包括一个或多个非环状成分。例如,环己基甲基基团(C6H11CH2—)为包括环己基环(是环状的但不是芳族的原子组)和亚甲基基团(非环状成分)的脂环族自由基。脂环族自由基可包括杂原子例如氮、硫、硒、硅和氧,或者可仅由碳和氢组成。为了方便起见,术语“脂环族自由基”在本文中定义为涵盖宽范围的官能团例如烷基基团、烯基基团、炔基基团、卤代烷基基团、共轭二烯基基团、醇基团、醚基团、醛基团、酮基团、羧酸基团、酰基基团(例如羧酸衍生物例如酯和酰胺)、胺基团、硝基基团等。例如,4-甲基环戊-1-基自由基为包括甲基基团的C6脂环族自由基,该甲基基团为作为烷基基团的官能团。类似地,2-硝基环丁-1-基自由基为包括硝基基团的C4脂环族自由基,该硝基基团为官能团。脂环族自由基可包括一个或多个卤素原子(其可相同或不同)。卤素原子包括,例如;氟、氯、溴、和碘。包括一个或多个卤素原子的脂环族自由基包括2-三氟甲基环己-1-基、4-溴二氟甲基环辛-1-基、2-氯二氟甲基环己-1-基、六氟异丙叉-2,2-双(环己-4-基)(即,—C6H10C(CF3)2C6H10—)、2-氯甲基环己-1-基、3-二氟亚甲基环己-1-基、4-三氯甲基环己-1-基氧基、4-溴二氯甲基环己-1-基硫基、2-溴乙基环戊-1-基、2-溴丙基环己-1-基氧基(例如,CH3CHBrCH2C6H10O—)等。脂环族自由基的进一步实例包括4-烯丙基氧基环己-1-基、4-氨基环己-1-基(即,H2C6H10—)、4-氨基羰基环戊-1-基(即,NH2COC5H8—)、4-乙酰氧基环己-1-基、2,2-二氰基异丙叉双(环己-4-基氧基)(即,—OC6H10C(CN)2C6H10O—)、3-甲基环己-1-基、亚甲基双(环己-4-基氧基)(即,—OC6H10CH2C6H10O—)、1-乙基环丁-1-基、环丙基乙烯基、3-甲酰基-2-四氢呋喃基、2-己基-5-四氢呋喃基、六亚甲基-1,6-双(环己-4-基氧基)(即,—OC6H10(CH2)6C6H10O—)、4-羟甲基环己-1-基(即,4-HOCH2C6H10—)、4-巯甲基环己-1-基(即,4-HSCH2C6H10—)、4-甲硫基环己-1-基(即,4-CH3SC6H10—)、4-甲氧基环己-1-基、2-甲氧基羰基环己-1-基氧基(2-CH3OCOC6H10O—)、4-硝基甲基环己-1-基(即,NO2CH2C6H10—)、3-三甲基甲硅烷基环己-1-基、2-叔丁基二甲基甲硅烷基环戊-1-基、4-三甲氧基甲硅烷基乙基环己-1-基(例如,(CH3O)3SiCH2CH2C6H10—)、4-乙烯基环己烯-1-基、乙烯叉双(环己基)等。术语“C3-C10脂环族自由基”包括含有至少三个但是不超过10个碳原子的脂环族自由基。脂环族自由基2-四氢呋喃基(C4H7O—)表示C4脂环族自由基。环己基甲基自由基(C6H11CH2—)表示C7脂环族自由基。在一些实施方式中,脂环族基团可包括C3-C20环状基团、C5-C15环状基团、C6-C10环状基团、或C8-C10环状基团。
如本文中使用的,术语“脂族基团”和“脂族自由基”是可互换地使用的并且指的是由不是环状的线型或支化的原子组构成的具有至少1价的有机自由基。脂族自由基定义为包括至少一个碳原子。包括脂族自由基的原子组可包括杂原子例如氮、硫、硅、硒和氧或者可仅由碳和氢组成。为了方便起见,术语“脂族自由基”在本文中定义为涵盖作为“不是环状的线型或支化的原子组”的一部分的宽范围的官能团例如烷基基团、烯基基团、烯基基团、卤代烷基基团、共轭二烯基基团、醇基团、醚基团、醛基团、酮基团、羧酸基团、酰基基团(例如羧酸衍生物例如酯和酰胺)、胺基团、硝基基团等。例如,4-甲基戊-1-基自由基为包括甲基基团的C6脂族自由基,该甲基基团为作为烷基基团的官能团。类似地,4-硝基丁-1-基基团为包括硝基基团的C4脂族自由基,该硝基基团为官能团。脂族自由基可为包括一个或多个卤素原子(其可相同或不同)的卤代烷基基团。卤素原子包括,例如;氟、氯、溴、和碘。包括一个或多个卤素原子的脂族自由基包括烷基卤三氟甲基、溴二氟甲基、氯二氟甲基、六氟异丙叉、氯甲基、二氟乙烯叉、三氯甲基、溴二氯甲基、溴乙基、2-溴三亚甲基(例如,—CH2CHBrCH2—)等。脂族自由基的进一步实例包括烯丙基、氨基羰基(即,—CONH2)、羰基、2,2-二氰基异丙叉(即,—CH2C(CN)2CH2—)、甲基(即,—CH3)、亚甲基(即,—CH2—)、乙基、亚乙基、甲酰基(即,—CHO)、己基、六亚甲基、羟甲基(即,—CH2OH)、巯甲基(即,—CH2SH)、甲硫基(即,—SCH3)、甲硫基甲基(即,—CH2SCH3)、甲氧基、甲氧基羰基(即,CH3OCO—)、硝基甲基(即,-CH2NO2)、硫羰基、三甲基甲硅烷基(即,(CH3)3Si-)、叔丁基二甲基甲硅烷基、3-三甲氧基甲硅烷基丙基(即,(CH3O)3SiCH2CH2CH2-)、乙烯基、乙烯叉等。作为进一步实例,C1-C10脂族自由基含有至少一个但是不超过10个碳原子。甲基基团(即,CH3—)是C1脂族自由基的实例。癸基基团(即,CH3(CH2)9-)是C10脂族自由基的实例。在一个或多个实施方式中,脂族基团或脂族自由基可包括,但不限于,具有1-20个碳原子、2-15个碳原子、3-10个碳原子、或者4-8个碳原子的直链或支链烃。
本技术提供基于有机硅的固化性组合物以及这样的组合物在各种各样的应用中的用途。所述固化性有机硅组合物提供期望的粘附以及其它机械和化学性质以及良好的导电性。所述组合物中如本文中描述的聚合物A、和一种或多种填料、和任选地聚合物B的选择提供具有多方面性质的杂化复合材料。进一步地,本组合物容许在有机硅基质中使用相对高的填料加载量而并不影响所述组合物的固化和加工条件。非有机硅有机单元的存在可用于为所述杂化有机硅复合物的总体性质提供另外的益处。
在一些实施方式中,本技术提供固化性组合物,其包括聚合物A、催化剂、和一种或多种填料,其中聚合物A包括杂化硅氧烷分子。所述组合物可通过缩合固化而固化。该固化不需要单独的交联剂。在一些实施方式中,所述固化性组合物进一步包括聚合物B。
本技术的一个或多个实施方式提供固化性组合物,其包括聚合物A、一种或多种填料、和任选地聚合物B。聚合物A包括包含烷氧基自由基、羟基自由基、异氰酸酯自由基、伯胺、或羧基自由基的有机分子或硅氧烷分子。聚合物B包括有机分子、硅氧烷分子、或杂化-硅氧烷分子。在这些实施方式的一些中,聚合物B可充当有机交联剂、硅氧烷交联剂、或杂化交联剂。在所述杂化交联剂中,存在有机单元和硅氧烷单元两者。这些实施方式的固化性组合物可在固化时形成杂化有机硅复合物。
在一些实施方式中,聚合物A可由式1表示:
(R)a(W)b(R)a″.......................式1
其中a和a"可为零或更大并且b不能为零,条件是a+a″+b总是大于0,R可由式(1a)表示:
(CH2)c(CH2O)d(CHOH)e(S)f(X)g...................式(1a)
如式(1a)中所示的R可表示线型或支化的结构,
S可独立地选自羟基自由基、异氰酸酯自由基、伯胺、或羧基自由基,
X独立地选自式(1b):
R1、R1′、和R1″独立地选自烷基自由基,烷氧基自由基,羟基自由基,氢自由基,或者选自具有C1-C20碳原子的取代或未取代的烃、或氟化烃,c、d、e、f、g为整数并且可为0或更大,条件是c+d+e+f+g>0,
式1中的W可由式(1c)表示
(Y)h(Z)i.........................式(1c)
其中h、i可为零或更大,条件是h+i>0,
式(1c)中的Y可由式(1d)表示:
(M1)x″(D1)j(D2)k(D*)l(T1)m(Q1)n(M2)y″...............式(1d)
其中j、k、l、m、n、x″、和y″可为零或更大,条件是(j+k+l+m+n+x″+y″)>0。
M1由式(1e)表示:
R2R3R4Sil1/2............................式(1e)
D1由式(1f)表示:
R5R6Sil2/2..........................式(1f)
D2由式(1g)表示:
R7R8Sil2/2..........................式(1g)
D*由式(1h)表示:
D3由式(1i)表示:
R9R10Sil2/2...........................式(1i)
D4由式(1j)表示:
R11R12Sil2/2....................式(1j)
D5由式(1k)表示:
R13R14SiI2/2....................式(1k)
D6由式(11)表示:
R15R16SiI2/2......................式(11)
T1由式(1m)表示:
R17Sil3/2.....................式(1m)
Q1由式(1n)表示:
Sil4/2.....................式(1n)
M2由式(1o)表示:
R18R19R20Sil1/2.....................式(lo)
R2-R20可独立地选自R,具有C1-C20碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,或者羧酸根自由基或环氧自由基,
其中o、p可为零或更大,条件是o+p>0,
I可为O或CH2基团,其遵从如下限制:分子含有偶数个O1/2和偶数个(CH2)1/2,
式(1c)中的Z可由式(1p)表示:
其中E可独立地选自氨基甲酸酯,脲,酸酐,酰胺,酰亚胺,氢自由基,或者具有1-20个碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,
q可为0或更大,r>0。
J可独立地选自式(1q)或(1q′):
其中M可独立地选自碳原子或杂原子,
G为选自氧的杂原子,其中t、s可为零或更大,条件是t+s>0,L1可独立地选自氨基甲酸酯、脲、酸酐、或酰胺,L2、L3、L4可独立地选自邻苯二甲酰亚胺、氟化烃、取代或未取代的烃、取代或未取代的芳族烃,u、v、w、x可为0或更大,K可独立地选自碳、杂原子、烃、或羰基自由基,条件是y>0。
在多个实施方式中,a、a”和b各自为1,并且R中的c、d、e独立地可为0、1-10、10-20、5-20、10-30。f、g独立地为1。进一步地,W中的h和i独立地为1。Y中的x”、y”、m、n独立地为0-10。Y中的j、k和l独立地为0-100。D*中的o、p独立地为0-10。Z中的q、r独立地为1。J中的t、s独立地为0、1-10、10-20并且M为碳/或氮。J中的u、v、w、x独立地为0、1-10、或10-20并且y为1-10。
在一个或多个实施方式中,聚合物A可由以下结构表示:
在一些实施方式中,聚合物B可由式(2a)表示:
其中M′可独立地选自碳原子或杂原子,
G′为选自氧的杂原子,
s′可为0或更大,
t′>0,
L1′可独立地选自异氰酸酯或伯胺或者由式(2b)或(2n)表示的R’,其中式(2b)为下式的化合物:
(M3)y″(D7)c′(D8)d′(D**)e′(T2)f(Q2)g′(M4)z′..........................式(2b)
其中M3由式(2c)表示:
R25R26R27Sil′1/2....................式(2c)
D7由式(2d)表示
R28R29Sil′2/2.....................................式(2d)
D8由式(2e)表示:
R30R31Sil′2/2...................................式(2e)
D**由式(2f)表示:
D9由式(2g)表示:
R32R33Sil′2/2.................................式(2g)
D10由式(2h)表示:
R34R35Sil′2/2...................................式(2h)
D11由式(2i)表示:
R36R37Sil′2/2...................................式(2i)
D12由式(2j)表示:
R38R39Sil′2/2...........................式(2j)
T2由式(2k)表示:
R40Sil′3/2...........................式(2k)
Q2由式(2l)表示:
Sil′4/2......................式(2l)
M4由式(2m)表示:
R41R42R43Sil′1/2............................式(2m)
其中R25-R43可独立地选自氢自由基,具有C1-C20碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,烷氧基自由基,或羟基自由基,
I′为O或CH2基团,其遵从如下限制:分子含有偶数个O1/2和偶数个(CH2)1/2,
c′、d′、e′、f′、g′、y″和z′可为零或更大,条件是(c′+d′+e′+f′+g′+y″+z′)>0,当e′>0时h′、i′>0。
式(2a)的L1′还可由式(2n)表示:
(R′)a′(W′)b′(R′)a″′...........................................式(2n)
其中R′由以上式(2b)表示,
W′可独立地选自例如如下的官能性:1-20个碳原子的取代或未取代的烃自由基、氟化烃、或全氟醚,a′、a″′和b′可为0或更大,条件是a′+a″′+b′>0。
在一些实施方式中,聚合物B可由式(2a′)表示:
其中E′可独立地选自R′,异氰酸酯,胺,氢,具有C1-C20碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,或其组合,
其中q’、r’可为零或更大,条件是q′+r′>0,
J′可独立地选自式(2b′):
其中L2′、L3′、L4′可独立地选自邻苯二甲酰亚胺自由基、氟化烃、取代或未取代的烃、取代或未取代的脂族或芳族烃、脲键、烷氧基或氨基甲酸酯键,
u'、v′、w′、x′可为0或更大,条件是(u'+v′+w′+x′)>0,
K可独立地选自碳、硅、杂原子、烃自由基、或羰基自由基,条件是y’>0。
在多个实施方式中,M’可独立地为碳或氮。s’为1并且t’独立地为1-5、5-10、或10-20。R’中的c′、d′、e′独立地为0-100并且R’中的f′、g′、y”、z’独立地为0、或1-10。在D**中,h’和i’可独立地为0或1-10。进一步地,在L1’中a’和a”为1并且b’为1-15。当r’为零时q’为1。J’中的u'、v′、w′、x′独立地为0、1-10、或10-20并且y’为1。
在一个或多个实施方式中,聚合物B可由以下结构表示:
将各种重量比率的聚合物A、聚合物B、或者聚合物A和聚合物B两者添加至所述组合物以实现对于所述杂化复合物而言期望的性质。在一个或多个实施方式中,所述固化性组合物包括在约5%-60%的范围内的聚合物A。在一些实施方式中,所述固化性组合物包括在约10%-50%的范围内的聚合物A。在一些实施方式中,所述固化性组合物包括在约20%-50%的范围内的聚合物A。在一些实施方式中,所述固化性组合物包括在约30%-50%的范围内的聚合物A。在一些实施方式中,所述固化性组合物包括在约30%-40%的范围内的聚合物A。在一些实施方式中,所述固化性组合物包括在约25%-40%的范围内的聚合物A。在一些实施方式中,所述固化性组合物包括30%的聚合物A。在这些实施方式的一些中,所述组合物仅包括30%的聚合物A。
在一个或多个实施方式中,所述固化性组合物进一步包括聚合物B,其中聚合物B在约1%-80%的范围内。在一些实施方式中,所述固化性组合物包括在约2%-75%的范围内的聚合物B。在一些实施方式中,所述固化性组合物包括在约10%-75%的范围内的聚合物B。在一些实施方式中,所述固化性组合物包括在约15%-80%的范围内的聚合物B。在一些实施方式中,所述固化性组合物包括在约20%-75%的范围内的聚合物B。在一些实施方式中,所述固化性组合物包括在约30%-80%的范围内的聚合物B。在一些实施方式中,所述固化性组合物包括在约10%-30%的范围内的聚合物B。
如所指出的,所述组合物包括一种或多种填料,其中所述填料包括,但不限于,矾土(氧化铝,alumina),硅,氧化镁,二氧化铈,二氧化铪,氧化镧,氧化钕,氧化钐,氧化镨,氧化钍,二氧化铀,氧化钇,氧化锌,氧化锆,氮氧化硅铝,硼硅酸盐玻璃,钛酸钡,碳化硅,硅石,碳化硼,碳化钛,碳化锆,氮化硼,氮化硅,氮化铝,氮化钛,氮化锆,硼化锆,二硼化钛,十二硼化铝,含钡轻火石玻璃(重晶石,baryte),硫酸钡,石棉,重晶石,硅藻土,长石,石膏,纤维棒石(hormite),高岭土,云母,霞石正长岩,珍珠岩,叶蜡石,蒙皂石,滑石,蛭石,沸石,方解石,碳酸钙,硅灰石,偏硅酸钙,粘土,硅酸铝,滑石,硅酸镁铝,水合矾土,水合氧化铝,硅石,二氧化硅,二氧化钛,玻璃纤维,玻璃片(鳞片,flake),粘土,片状剥离(exfoliated)粘土,或者其它高纵横比纤维、棒或片,碳酸钙,氧化锌,氧化镁,二氧化钛,碳酸钙,滑石,云母,硅灰石,矾土,氮化铝,石墨,石墨烯,金属包覆的石墨,金属包覆的石墨烯,铝粉末,铜粉末,青铜粉末,黄铜粉末,碳、石墨、碳化硅、氮化硅、矾土、氮化铝的纤维或晶须,银,氧化锌,碳纳米管,氮化硼纳米片,氧化锌纳米管,黑磷,银包覆的铝,银包覆的玻璃,镀银的铝,镀镍的银,镀镍的铝,不同结构的碳黑,蒙乃尔合金(Monel)网和丝,以及其两种或更多种的组合。
在一个或多个实施方式中,所述填料包括石墨、镍包覆的石墨、银、铜或其组合。在一个或多个实施方式中,所述填料包括石墨、镍包覆的石墨、或其组合。在一个实施方式中,所述填料为镍包覆的石墨。
在一些实施方式中,所述组合物进一步包括第二(副,secondary)填料。第二填料可为基于非金属的填料。在一个或多个实施方式中,使用聚吡咯作为第二填料。在一些实施方式中,所述组合物包括0.1-50%的第二填料。在一些实施方式中,所述组合物包括0.1-30%的第二填料。在一个实施方式中,所述组合物包括20%的第二填料。
将各种重量比率的填料添加至所述组合物以实现对于所述杂化复合物而言期望的性质。在一个或多个实施方式中,所述固化性组合物包括在约5%-80%的范围内的填料。在一些实施方式中,所述固化性组合物包括在约20%-80%的范围内的填料。在一些实施方式中,所述固化性组合物包括在约20%-60%的范围内的填料。在一些实施方式中,所述固化性组合物包括在约30%-80%的范围内的填料。在一些实施方式中,所述固化性组合物包括在约30%-60%的范围内的填料。在一些实施方式中,所述固化性组合物包括在约50%-80%的范围内的填料。在一些实施方式中,所述固化性组合物包括在约60%-80%的范围内的填料。
如所指出的,所述固化性组合物包括催化剂,其中该至少一种催化剂为缩合和/或交联用催化剂。在一些实施方式中,所述组合物可包括选自金属缩合催化剂和非金属缩合催化剂的催化剂。所述金属缩合催化剂可为选自如下的至少一种:锡、钛、锆、铅、铁、钴、锑、锰、铋和锌化合物。在一个或多个实施方式中,所述组合物包括锡催化剂。
在一些实施方式中,所述组合物仅包括聚合物A、催化剂和填料。在这样的实施方式中,所述催化剂选自Sn催化剂。在Sn催化剂的存在下,聚合物A在不使用任何交联剂的情况下被固化为经固化的组合物。在这样的实施方式中,聚合物A可为甲硅烷基化有机聚合物、或者甲硅烷基化聚氨基甲酸酯有机聚合物(甲硅烷基化聚氨基甲酸酯树脂或SPUR)。
在异氰酸酯封端的PU预聚物的制备中通常使用催化剂。有利地,采用缩合催化剂,因为这些还将催化本发明的固化性组合物的SPU-树脂组分的固化(水解之后交联)。合适的缩合催化剂包括二羧酸二烷基锡例如二月桂酸二丁基锡和乙酸二丁基锡、叔胺、羧酸的亚锡盐例如辛酸亚锡和乙酸亚锡等。在本发明的一个实施方式中,在制造PUR预聚物时使用二月桂酸二丁基锡催化剂。其它有用的催化剂包括含锆的和含铋的络合物例如由KingIndustries,Inc.供应的KAT XC6212、K-KAT XC-A209和K-KAT 348,铝螯合物例如可得自DuPont company的类型、和可得自Kenrich Petrochemical,Inc.的KR类型,和其它有机金属催化剂例如含有金属如Zn、Co、Ni、Fe等的那些。
在一些实施方式中,所述组合物包括0.0001重量%-0.1重量%的催化剂。在一些其它实施方式中,所述组合物包括0.0005-0.001重量%的催化剂。在一些其它实施方式中,所述组合物包括0.001重量%-0.1重量%的催化剂。在一些其它实施方式中,所述组合物包括0.005重量%-0.1重量%的催化剂。
在一些实施方式中,所述固化性组合物进一步包括选自如下的粘附促进剂:三烷氧基环氧硅烷、三烷氧基伯氨基硅烷、含有伯和仲胺的三烷氧基硅烷的组合、基于三(三烷氧基)异氰脲酸酯的硅烷、烷基硫代羧化三烷氧基硅烷。
在一些实施方式中,所述固化性组合物进一步包括反应性稀释剂。所述反应性稀释剂可包括,但不限于,取代的缩水甘油基醚。所述反应性稀释剂可包括一种或多种溶剂。合适的溶剂可包括,但不限于,液体烃或者有机硅流体。所述烃溶剂可包括己烷或庚烷,有机硅流体可包括聚二有机基硅氧烷。
在一些实施方式中,所述固化性组合物进一步包括流变改性剂、或流动添加剂。所述流变改性剂可包括,但不限于,四氢芳樟醇、热塑性树脂和聚乙烯醇缩醛。所述流动添加剂可包括,但不限于有机硅流体、或丙烯酸酯化(丙烯酸(酯)改性的,acrylated)的共聚物。
在一个或多个实施方式中,所述配方(制剂,formulation)通过将杂化硅氧烷(聚合物A)和填料在催化剂存在下均化而制备。将所述杂化硅氧烷聚合物(聚合物A)、过渡金属催化剂、以及任选地交联剂(聚合物B)与颗粒状填料在高速混合器中以2000rpm混合30-60秒。将混合物在室温下固化。通过使用固化组合物而制备了一系列实例(如以下实施例中所示的)。在一个或多个实施方式中,所述固化性组合物的固化为缩合固化。
在一些实施方式中,经固化的材料的应用以及其最终用途是在如下中:涂料、胶粘剂、密封剂、电极、墨、导热性材料、导电性材料、传感器、致动器、加热垫、抗菌包装材料、传导性(导电)塑料、电磁屏蔽材料。
该书面描述使用实例来公开本发明,包括最佳模式,并且还使得任何本领域技术人员能够实践本发明,包括制造和使用任何装置或系统和进行任何所引入的方法。本发明的可专利性范围由权利要求限定,并且可包括本领域技术人员想到的其它实例。如果这样的其它实例具有与权利要求的字面语言没有区别的结构要素,或者如果它们包括与权利要求的字面语言没有实质区别的等同结构要素,则它们意图在权利要求的范围内。
实施例
聚合物A的实施例1氨基甲酸酯官能的烷氧基硅氧烷(结构I)的合成
将50g的A-link 35*(Momentive Performance Material)在氮气气氛下加入三颈圆底烧瓶中。向其加入Sn催化剂(0.01-0.05%)至反应混合物。在室温下滴加6.27g的乙二醇。将反应混合物从室温温和地加热至80℃达12小时。在通过监测FTIR光谱而完成反应之后,将反应混合物用活性炭处理以使催化性Sn失活。将反应混合物使用硅藻土(Celite)床过滤。将产物通过真空蒸馏而进一步纯化以获得大约70%纯的产物。分离产物(结构I)并且在室温下保存。
聚合物A的实施例2:烷氧基官能的环状硅氧烷(结构II)的合成
将8.6g的乙烯基三甲氧基硅烷在氮气气氛下加入三颈圆底烧瓶中。将反应物在75度下加热,之后将Karstedt催化剂(5-10ppm)添加至反应混合物。将15g的七甲基环四硅氧烷滴加至反应混合物并且观察到反应混合物中的放热最高至90度。将反应混合物在75度下搅拌2小时。在通过监测1HNMR光谱而完成反应之后,将反应混合物用活性炭处理以使催化性Pt失活。将反应混合物使用硅藻土床过滤。将产物通过真空蒸馏而进一步纯化以获得大约80%纯的产物。分离产物(结构II)并且在室温下保存。
聚合物B的实施例1:具有氟取代的苯基环的氨基甲酸酯官能的烷氧基硅烷(结构III)的合成
将76g的A-link 35*(Momentive Performance Material)在氮气气氛下加入三颈圆底烧瓶中。向其加入Sn催化剂(0.01-0.05%)至反应混合物。在室温下滴加67g的4-(三氟甲基)苄醇。将反应混合物从室温温和地加热至70℃达12小时。在通过监测FTIR光谱而完成反应之后,将反应混合物用活性炭处理以使催化性Sn失活。将反应混合物使用硅藻土床过滤。将产物通过真空蒸馏而进一步纯化以获得大约65%纯的产物。分离产物(结构III)并且在室温下保存。
聚合物B的实施例2:氟醚官能的烷氧基硅氧烷(结构IV)的合成
将20g的Fluorolink-E10H和20ml的作为溶剂的1,3-双(三氟甲基)苯在氮气吹扫下加入三颈圆底烧瓶中。向其加入Sn催化剂(0.01-0.05%)至反应混合物。然后,将5.1g的A-link 35*(Momentive Performance Material)添加到反应混合物中。将反应混合物在70℃下加热10小时。在通过监测FTIR光谱而完成反应之后,将反应混合物用活性炭处理以使催化性Sn失活。将反应混合物使用硅藻土床过滤。将产物通过真空蒸馏而进一步纯化以获得大约70%纯的产物。分离产物(结构IV)并且在室温下保存。
所用材料的概述
SPUR+*1050、MTMS、三甲氧基环氧硅烷A187、三甲氧基氨基硅烷A1110购自Momentive Performance Materials。双羟基封端的硅烷醇(D400)购自Gelest,Inc。杂化硅烷为如在实施例1和2中所述那样合成的。表1提供配方中使用的不同材料的描述和来源。
表1:材料的描述和来源
**标记-在本文中用于描述配方。*Momentive的商业材料各种配方的制备
使用聚合物A和任选地聚合物B在一种或多种填料的存在下制备杂化有机硅复合物。将各种重量比率的填料添加至聚合物A和任选地聚合物B的混合物。在将聚合物A、填料、和任选地聚合物B混合之后,将混合物在室温下固化。各种配方的细节在以下描述于表2中。对于不同配方,选择不同类型的具有不同官能性的固化性有机硅、和不同类型的填料。各种配方呈现于表2中。为了制造所述配方,已经使用了金属催化剂(基于Sn和Ti的催化剂)。
表2:代表性实施例和它们的组成
物理机械性质测试方法
EMI屏蔽测量:根据IEEE299标准进行不同形式的样品的EMI屏蔽测量,而电导率测量:根据ASTM D257标准,使用四探针仪器进行不同形式的样品的电阻率测量。将所获得的电阻率值转换成电导率。热导率:按照ASTM E1530标准进行样品的热导率测量。使用ASTMD3163标准测量所开发配方的搭接剪切。对于其使用Instron仪器。硬度测量:根据ASTMD2240标准测量所开发复合物的硬度。
表3:所开发配方的性质
还在6GHz-12GHz的范围内检查所开发配方的EMI屏蔽能力。样品的厚度在0.5mm至1.5mm之间。所选择样品的EMI屏蔽效力示于表4中。所选择样品的热导率值示于表5中
表4:EMI屏蔽效力
配方编号 | 屏蔽效力(dB) |
F3 | 65 |
F7 | 100 |
F8 | 85 |
表5:热导率
配方编号 | 热导率(w/mK) |
F2 | 1.74 |
F3 | 1.25 |
F5 | 1.1 |
F6 | 1.13 |
对比例1
为了将基于杂化有机硅的配方与基于纯有机硅的对比物进行比较,制造对照样品(相比于配方F7)并且测试。
表6:对比例1
以上已经描述了本技术的多种实施方式并且其他人在阅读和理解本说明书时可想到改动和变更。所附权利要求意图包括所有的改动和变更,只要它们进入权利要求或者其等同物的范围内。
Claims (24)
1.固化性有机硅组合物,其包括:
(i)式1的聚合物A;
(ii)填料;
(iii)催化剂,和任选地
(iv)式2的聚合物B;
其中所述固化性有机硅组合物为缩合固化体系;和固化性组合物的经固化的形式为传导性材料,
(R)a(W)b(R)a″...........................式1;
其中a和a″为零或更大,条件是a+a″>0并且b不能为零,
其中R由式(1a)表示:
(CH2)c(CH2O)d(CHOH)e(S)f(×)g............式(1a)
S独立地选自羟基自由基、异氰酸酯自由基、伯胺、或羧基自由基并且X独立地选自式(1b)
其中R1、R1′、和R1″独立地选自烷基自由基,烷氧基自由基,羟基自由基,氢自由基,或者选自具有C1-C20碳原子的未取代烃、或氟化烃,
c、d、e、f、g为整数并且为0或更大,条件是c+d+e+f+g>0,
式1中的W由式(1c)表示
(Y)h(Z)i...............................式(1c)
其中h、i为零或更大,条件是h+i>0,
式(1c)中的Y由式(1d)表示:
(M1)x″(D1)j(D2)k(D*)l(T1)m(Q1)n(M2)y″..............式(1d)
其中j、k、l、m、n、x”、和y”为零或更大,条件是(j+k+l+m+n+x”+y”)>0;
其中M1由式(1e)表示:
R2R3R4Sil1/2.......................式(1e)
D1由式(1f)表示:
R5R6Sil2/2......................式(1f)
D2由式(1g)表示:
R7R8Sil2/2................................式(1g)
D*由式(1h)表示:
D3由式(1i)表示:
R9R10Sil2/2......................式(1i)
D4由式(1j)表示:
R11R12Sil2/2......................式(1j)
D5由式(1k)表示:
R13R14Sil2/2.....................式(1k)
D6由式(11)表示:
R15R16Sil2/2.....................式(11)
T1由式(1m)表示:
R17Sil3/2.....................式(1m)
Q1由式(1n)表示:
Sil4/2....................式(1n)
M2由式(1o)表示:
R18R19R20Sil1/2.....................式(1o)
R2-R20独立地选自R,或者具有1-20个碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,或羧酸根自由基或环氧自由基,
其中o、p为零或更大,条件是o+p>0,
I为O或CH2基团,其遵从如下限制:分子含有偶数个O1/2和偶数个(CH2)1/2,
式(1c)中的Z由式(1p)表示:
其中E独立地选自氨基甲酸酯,脲,酸酐,酰胺,酰亚胺,氢自由基,或者具有1-20个碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,q可为0或更大,r>0,
J独立地选自式(1q)或(1q′):
其中M独立地选自碳原子或杂原子,
G为选自氧的杂原子,
其中t、s为零或更大,条件是t+s>0,
L1独立地选自氨基甲酸酯、脲、酸酐、或酰胺,
L2、L3、L4独立地选自烷氧基、邻苯二甲酰亚胺、氟化烃、取代或未取代的烃、取代或未取代的芳族烃,u、v、w、x可为0或更大,
K独立地选自碳、硅、杂原子、烃、或羰基自由基,条件是y>o;
聚合物B可由式(2a)表示:
其中M′独立地选自碳原子或杂原子,
G′为选自氧的杂原子,
s′可为0或更大,
t'>0,
L1′独立地选自异氰酸酯、伯胺、或者由式(2b)表示的R’:
(M3)y”(D7)c'(D8)d'(D**)e'(T2)f'(Q2)g'(M4)z'........式(2b)
其中M3由式(2c)表示:
R25R26R27Sil′1/2....................式(2c)
D7由式(2d)表示
R28R29Sil′2/2.....................................式(2d)
D8由式(2e)表示:
R30R31Sil′2/2....................................式(2e)
D**由式(2f)表示:
D9由式(2g)表示:
R32R33Sil′2/2..................................式(2g)
D10由式(2h)表示:
R34R35Sil′2/2..................................式(2h)
D11由式(2i)表示:
R36R37Sil′2/2..................................式(2i)
D12由式(2j)表示:
R38R39Sil′2/2........................................式(2j)
T2由式(2k)表示:
R40Sil′3/2.................................式(2k)
Q2由式(21)表示:
Sil′4/2......................式(2l)
M4由式(2m)表示:
R41R42R43Sil′1/2................................式(2m)
其中R25-R43独立地选自氢自由基,具有C1-C20碳原子的单价环状或非环状、脂族或芳族的取代或未取代烃、或氟化烃,烷氧基自由基,或羟基自由基,
I′为O或CH2基团,其遵从如下限制:分子含有偶数个O1/2和偶数个(CH2)1/2
c′、d、e′、f′、g′、y″′和z′为零或更大,条件是(c′+d+e′+f′+g′+y″′+z′)>0,
当e′>0时h′、i′>0;
式(2a)的L1′由式(2n)表示:
(R')a'(W')b'(R')a””.......................................式(2n)
其中R′由上式(2b)表示,
W′独立地选自例如如下的官能性:1-20个碳原子的取代或未取代的烃自由基、氟化烃、或全氟醚;
a'、a”'为0或更大,条件是a'+a”'>0,并且b'可为0或更大。
2.如权利要求1所述的固化性有机硅组合物,其中聚合物A包括硅烷醇、杂化硅烷醇、甲硅烷基化有机聚合物或杂化硅氧烷。
3.如权利要求1所述的固化性有机硅组合物,其中式(1a)选自线型链、支化链、或环状结构。
5.如权利要求4所述的固化性有机硅组合物,其中使用如由式2a或2a′表示的聚合物B作为交联剂、或扩链剂。
6.如权利要求4所述的固化性有机硅组合物,其中如由式2a或2a′表示的聚合物B选自线型聚合物、支化聚合物、或环状聚合物。
7.如权利要求1所述的固化性有机硅组合物,其中如由式2a表示的聚合物B为环状聚合物。
8.如权利要求7所述的固化性有机硅组合物,其中M'选自杂原子。
9.如权利要求7所述的固化性有机硅组合物,其中式2n的W'选自1-20个碳原子的取代或未取代的烃自由基、氟化烃、或全氟醚。
10.如权利要求1-9所述的固化性有机硅组合物,其中聚合物A以约5%-60%的范围存在。
11.如权利要求1-9所述的固化性有机硅组合物,其中聚合物B以约1%-80%的范围存在。
12.如权利要求1-11所述的固化性有机硅组合物,其中所述填料选自矾土,氧化镁,二氧化铈,二氧化铪,硅,氧化镧,氧化钕,氧化钐,氧化镨,氧化钍,二氧化铀,氧化钇,氧化锌,氧化锆,氮氧化硅铝,硼硅酸盐玻璃,钛酸钡,碳化硅,硅石,碳化硼,碳化钛,碳化锆,氮化硼,氮化硅,氮化铝,氮化钛,氮化锆,硼化锆,二硼化钛,十二硼化铝,含钡轻火石玻璃,硫酸钡,石棉,重晶石,硅藻土,长石,石膏,纤维棒石,高岭土,云母,霞石正长岩,珍珠岩,叶蜡石,蒙皂石,滑石,蛭石,沸石,方解石,碳酸钙,硅灰石,偏硅酸钙,粘土,硅酸铝,滑石,硅酸镁铝,水合矾土,水合氧化铝,硅石,二氧化硅,二氧化钛,玻璃纤维,玻璃片,粘土,片状剥离粘土,或者其它高纵横比纤维、棒、或片,碳酸钙,氧化锌,氧化镁,二氧化钛,碳酸钙,滑石,云母,硅灰石,矾土,氮化铝,石墨,石墨烯,金属包覆的石墨,金属包覆的石墨烯,铝粉末,铜粉末,青铜粉末,黄铜粉末,碳、石墨、碳化硅、氮化硅、矾土、氮化铝的纤维或晶须,银,氧化锌,碳纳米管,氮化硼纳米片,氧化锌纳米管,黑磷,银包覆的铝,银包覆的玻璃,镀银的铝,镀镍的银,镀镍的铝,不同结构的碳黑,蒙乃尔合金网和丝,或者其两种或更多种的组合。
13.如权利要求1-12所述的固化性有机硅组合物,其中所述填料以约5%-80%的范围存在。
14.如权利要求1-13所述的固化性有机硅组合物,其进一步包括选自如下的催化剂:锡、钛、锆、铅、铁、钴、锑、锰、铋和锌化合物。
15.如权利要求14所述的固化性有机硅组合物,其中所述催化剂以约0.0001重量%-约0.1重量%的范围存在。
16.如权利要求1-15所述的固化性有机硅组合物,其进一步包括选自如下的粘附促进剂:三烷氧基环氧硅烷、三烷氧基伯氨基硅烷、含有伯和仲胺的三烷氧基硅烷的组合、基于三(三烷氧基)异氰脲酸酯的硅烷、烷基硫代羧化三烷氧基硅烷、以及其两种或更多种的组合。
17.如权利要求1-16所述的固化性有机硅组合物,其进一步包括选自如下的反应性稀释剂:取代的缩水甘油基醚、液体烃、有机硅流体、及其组合。
18.如权利要求1-17所述的固化性有机硅组合物,其进一步包括选自如下的流变改性剂:烷烃、硅烷、有机硅、丙烯酸类共聚物、二醇、多元醇、醚、酯、聚酯、醇、酰胺、聚酰胺、胺、多元胺、亚胺、聚亚胺、氨基甲酸酯、聚氨基甲酸酯、酮、聚酮、糖、多糖、纤维素、含氟化合物、热塑性或热固性树脂、聚乙烯基、合成或天然油、天然存在的添加剂、瓜尔胶、苍耳烷、海藻酸盐或酯、乳酸盐或酯、丙交酯、酸酐、树胶、硅酸盐或酯、硼酸盐或酯、氧化物、硫化物、硫酸盐或酯及其组合。
19.如权利要求1-18任一项所述的固化性组合物的经固化的材料。
20.如权利要求19所述的经固化的材料,其中所述经固化的材料为导热性的、导电性的、或其组合。
21.如权利要求19所述的经固化的材料,其中所述经固化的材料具有在50至170dB之间的电磁干扰(EMI)屏蔽效率。
22.如权利要求19所述的经固化的材料,其中所述经固化的材料用于如下中:涂料、胶粘剂、密封剂、电极、墨、导热性材料、导电性材料、传感器、致动器、加热垫、抗菌包装材料、传导性塑料、或EMI屏蔽材料。
23.固化性有机硅组合物,其包括:
(i)包括甲硅烷基化有机聚合物、甲硅烷基化聚氨基甲酸酯有机聚合物、或烷氧基有机硅的聚合物A;
(ii)填料,和
(iii)催化剂;和任选地
(iv)聚合物B;
其中聚合物A和聚合物B为有机硅聚合物,并且所述固化性有机硅组合物为缩合固化体系。
24.制造有机硅组合物的方法,其包括:
(i)将包括一个或多个烷氧基官能团的聚合物A、一种或多种填料、催化剂和任选的包括一个或多个烷氧基官能团的聚合物B一起混合以形成混合物,所述催化剂是相对于聚合物A和聚合物B、以及填料的总重量添加的;
(ii)然后将所述混合物均化以形成混合物;和
(iii)然后将经均化的混合物通过缩合固化而固化,
其中聚合物A和聚合物B为有机硅聚合物。
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