CN1063291A - 网状聚硅氮烷及其制造方法 - Google Patents

网状聚硅氮烷及其制造方法 Download PDF

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CN1063291A
CN1063291A CN91112776A CN91112776A CN1063291A CN 1063291 A CN1063291 A CN 1063291A CN 91112776 A CN91112776 A CN 91112776A CN 91112776 A CN91112776 A CN 91112776A CN 1063291 A CN1063291 A CN 1063291A
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chemical formula
polysilazanes
reticular
hydrogen atom
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P·蓬斯
M·-B·韦格尔
C·科隆比耶
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/589—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained from Si-containing polymer precursors or organosilicon monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/62—Nitrogen atoms

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Abstract

网状聚硅氮烷及其制造方法。
本发明涉及陶瓷领域，更确切地说，本发明涉及 网状产物母体领域。
这些产物母体是一些用铝的衍生物得到的网状 硅氮烷。
这些网状产物在热解之后的陶瓷产率很高。

Description

本发明涉及陶瓷的产物母体领域，更确切地说，本发明涉及用有机金属交联剂得到的网状聚硅氮烷。
在美国专利4730026中，人们提出了一些具有下述循环单元的聚合物：
Figure 911127763_IMG2
在单元之间是由至少一个化学式为-MR'n-的桥连接的，所说的一个或多个桥连接于循环单元的氮原子上，符号M代表选自于元素周期表中的ⅢA、ⅡB、ⅣB和ⅡA族的一种金属，在制备网状聚合物中所使用的聚合物属于有机硅氮烷类，作为实例，该专利列举了聚（1，1-二甲基硅氮烷）、（1，2-二甲基硅氮烷）（1-甲基硅氮烷）共聚物，或者一种由环甲基硅氮烷衍生的聚合硅氮烷。一般地说，这些不同的聚合物的制备都是从卤代硅烷和氨或胺开始的。根据同一份专利，在金属反应物的化学式中，符号R'代表一个氢原子、一个具有1-6个碳原子的烷基或单一和双一芳基、或烷基氨基、烷苯基和烷芳基之一个基团。
本发明的目的在于一些网状聚硅氮烷，其特征在于它们是由许多如下述化学式的单元构成的，
Figure 911127763_IMG3
在所述单元的氮原子之间是由至少一个＝AlX桥连接的，硅原子或氮原子可使用的价可以载带一个氢原子、一个具有1-6个碳原子的烷基、一个乙烯基或烯丙基、一个环己基、一个碳原子最多为18个的芳基、烷芳基或芳烷基、符号X代表一个基团-NHZ，其中Z代表一个氢原子或一种金属和非金属，其中特别是硅，X也可以代表Si≡。
在本说明书中，“可使用的价”这种表达意思是未被用来构成聚硅氮烷与上述桥的线性或环状连接的硅原子和氮原子的价。
本发明的目的还在于一种上面定义的网状聚硅氮烷的制备方法，所说方法在于一种含有许多化学式Ⅰ单元的化合物与一种化学式为H2NAlR1R2（Ⅱ）的氨基有机铝（amino organoaluminane）进行反应，其化学式中，R1代表一个含有1-12个碳原子的烷基或一个苯基、烷（C1-C4）苯基或苯烷基（C1-C4），R2代表H或由R1所表示的基团之一，反应是在能形成桥＝AlX的条件下进行的。
本发明还涉及到如上所述的反应混合物。
根据一种变更的方案或补充方案，当化学式Ⅰ单元的硅载带一个氢原子时，其反应可能因SiH与＝NH反应而导致另外的交联，同时释放出H2和/或NH3和/或与R1和R2相对应的一种或多种烃。
在由硅原子或氮原子可使用价（上述定义的）载带的原子或基团中，可更具体地列举出氢、甲基、乙烯基或苯基，人们较喜欢选用具有化学式Ⅰ单元的产品，在其式中的氮原子带有一个氢原子，而硅原子带有一个甲基或乙烯基和/或一个氢原子。由反应物的混合物，人们实际上可以得到化学式Ⅰ的单元，该化学式中各单元的硅原子和氮原子取代基是不相同的。
含有化学式Ⅰ单元的非网状聚硅氮烷是已知的，且不构成本发明的内容。至于其制备，例如可以参考已公开的欧洲专利申请EP209472。
一般地说，可在室温下进行生成＝AlX桥的反应。更一般地，可在-40-200℃进行操作。
在溶剂介质中进行上述反应较有利。
作为说明可使用的溶剂，特别列举卤代物如二氯甲烷;二烷醚，如***;环醚，如四氢呋喃、四氢呋喃、1、4-二噁烷;脂族烃，如戊烷或己烷;芳烃，如苯、甲苯、二甲苯。
在制备本发明的网状聚合物时，所使用的反应物（含有许多化学式Ⅰ单元的化合物和化学式Ⅱ的铝衍生物）的量，是Si/Al摩尔比为1-100，最好是3-40。这些含有化学式Ⅰ聚硅氮烷和有机铝的组合物同样是本发明的一个内容。
本发明的网状产品具有各种物理状态，从粘稠的液体到固体。通常在850-1200℃进行热解，得到的陶瓷产率（热解剩余率）比只含化学式Ⅰ单元的化合物所得到的要明显地多。另一方面，人们可以认为，除加入到聚硅氮烷链中的交联剂的作用外（形成桥＝AlX），氨基有机铝（Ⅱ）在由SiH/NH桥交联时或例如在上述欧洲专利申请EP209472中描述的其他交联反应中起到催化作用。
下述实施例说明本发明。
实施例
所使用的聚硅氮烷具有下列化学式
Figure 911127763_IMG4
它是在欧洲专利申请EP209472实施例1中所描述的条件下由氨与甲基二氯硅烷进行反应而制备的。
在美国专利US-A-4696968（实施例1）所描述的条件下，用三乙基铝和氨（摩尔比1/1）制备出氨基二乙基铝。
把一种氨基二乙基铝（NH2Al（C2H5）2）正己烷溶液加入到1克聚硅氮烷二氯甲烷溶液中（摩尔比Si/Al＝18）。这一操作是在室温下进行，并使反应持续16小时。
除去正己烷和二氯甲烷之后，得到一种可溶于正己烷的粘稠液体。
在氩气中于1000℃热解之后，剩余率（陶瓷化产率）为80%，而只用聚硅氮烷的仅为40%，用三乙基铝则为55%（摩尔比Si/Al＝21）。
热解之后所得到的粘稠液体和陶瓷的百分组成如下：
C  H  N  Al  Si  O
粘稠液体  23.8  7.5  18.4  2.4  43.8  3.4
陶瓷  12.48  0.24  27.6  2.9  52.9  2.7

Claims (7)

1、网状聚硅氮烷，其特征在于它们是由许多如下述化学式单元构成的
在所说单元的氮原子之间是由至少一个化学式为=AlX的桥连接的，硅原子或氮原子可使用价可以带有一个氢原子、一个具有1-6个碳原子的烷基、一个乙烯基或烯丙基、一个环已基、一个碳原子数最多为18个的芳基、烷芳基或芳烷基，符号X代表一个基团-NHZ，其中Z代表一个氢原子或一种金属和非金属，其中特别是硅，X也可以代表Si≡。
2、根据权利要求1所述的聚硅氮烷，其特征在于在至少一部分化学式Ⅰ单元中，氮原子带有一个氢原子，硅原子带有一个氢原子和/或一个甲基或乙烯基。
3、制备权利要求1和2之任何一个权利要求所述的聚硅氮烷的方法，其特征在于将一种具有许多化学式Ⅰ单元的化合物与一种化学式为H2NAlR1R2（Ⅱ）的氨基有机铝进行反应，其中R1代表一个含有1-12个碳原子的烷基或一个苯基、烷（C1-C4）苯基或苯烷（C1-C4）基，R2代表H或由R1所表示的基团之一，反应是在能使桥＝AlX形成的条件下进行的。
4、根据权利要求3所述的方法，其特征在于Si/Al摩尔比为1-100，最好是3-40。
5、根据权利要求3所述的方法，其特征在于氨基有机铝是氨基二乙基铝（NH2Al（C2H5）2）。
6、网状聚硅氮烷组合物，它是由含有许多化学式Ⅰ单元和化学式Ⅱ铝的、其Si/Al摩尔比为1-100的聚硅氮烷混合物构成的。
7、如由权利要求1和2之任何一个权利要求的网状聚硅氮烷经热解而生成的陶瓷材料。
CN91112776A 1990-12-19 1991-12-19 网状聚硅氮烷及其制造方法 Pending CN1063291A (zh)

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CN101353426B (zh) * 2008-09-09 2011-04-27 西北工业大学 一种液态乙烯基聚硅氮烷树脂及其制备方法

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US5229468A (en) * 1992-02-13 1993-07-20 Hercules Incorporated Polymer precursor for silicon carbide/aluminum nitride ceramics
DE4241287A1 (de) * 1992-12-08 1994-06-09 Bayer Ag Siliciumaluminiumnitridkeramik und Vorläuferverbindungen, Verfahren zu ihrer Herstellung sowie deren Verwendung
US9856400B2 (en) 2012-04-27 2018-01-02 Burning Bush Group, Llc High performance silicon based coating compositions
WO2013170124A1 (en) 2012-05-10 2013-11-14 Burning Bush Group High performance silicon based thermal coating compositions
EP2869977B1 (en) 2012-07-03 2020-04-22 Burning Bush Group, LLC High performance silicon based coating compositions
US9006355B1 (en) 2013-10-04 2015-04-14 Burning Bush Group, Llc High performance silicon-based compositions
CN104830230A (zh) * 2015-05-13 2015-08-12 江西科技师范大学 一种抗空间环境损伤的防护涂层及其制备方法和应用
CN108676167B (zh) * 2018-04-03 2020-06-16 中国科学院化学研究所 一种聚硅氮烷的制备装置与方法

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US4886860A (en) * 1988-03-23 1989-12-12 Toa Nenryo Kogyo Kabushiki Kaisha Polymetalosilazane and process for preparing same
US4946809A (en) * 1989-05-26 1990-08-07 Ultraystems Defense And Space, Inc. Precursor for A1NBN ceramic and method of use

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* Cited by examiner, † Cited by third party
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CN101353426B (zh) * 2008-09-09 2011-04-27 西北工业大学 一种液态乙烯基聚硅氮烷树脂及其制备方法

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NO914998L (no) 1992-06-22
KR920012192A (ko) 1992-07-25
AU8984891A (en) 1992-06-25
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JPH04335033A (ja) 1992-11-24
IE914416A1 (en) 1992-07-01
NO914998D0 (no) 1991-12-18

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