JPS62199623A - Production of polymer having cyclic polymethyl silazane structure - Google Patents
Production of polymer having cyclic polymethyl silazane structureInfo
- Publication number
- JPS62199623A JPS62199623A JP4146786A JP4146786A JPS62199623A JP S62199623 A JPS62199623 A JP S62199623A JP 4146786 A JP4146786 A JP 4146786A JP 4146786 A JP4146786 A JP 4146786A JP S62199623 A JPS62199623 A JP S62199623A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- cyclic
- reaction
- acceptor
- chlorosilane compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 24
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 18
- -1 chlorosilane compound Chemical class 0.000 claims abstract description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 claims abstract description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000008030 elimination Effects 0.000 abstract 3
- 238000003379 elimination reaction Methods 0.000 abstract 3
- 239000013638 trimer Substances 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001709 polysilazane Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QKDIBALFMZCURP-UHFFFAOYSA-N 1-methyl-1$l^{3}-silinane Chemical group C[Si]1CCCCC1 QKDIBALFMZCURP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
／２ Ｘス叩ハ雷ｔ６羽か雷呂■
［発明の技術分野］
本発明はセラミックス製造用の前駆体として有用な環状
ポリメチルシラザン構造を有する重合体の製造方法に関
する。[Detailed Description of the Invention] /2 Regarding.
［発明の技術的背景とその問題点］
互いに摺動もしくは接触して動作せしめる各種の機械部
品、電子部品の表面には高度の耐摩耗性が要求される。[Technical Background of the Invention and its Problems] A high degree of wear resistance is required on the surfaces of various mechanical parts and electronic parts that operate by sliding or contacting each other.
また、近年、省エネルギーの観点から、各種機器の高効
率化が求められる中で、それに用いられる材料の軽量化
は重要な課題である。Furthermore, in recent years, there has been a demand for higher efficiency in various types of equipment from the perspective of energy conservation, and reducing the weight of the materials used therein has become an important issue.
各種のセラミックス、例えば窒化ケイ素、炭化ケイ素等
の非酸化物系セラミックスは、一般に軽量で化学安定性
に富み耐熱性にも優れているので、従来汎用されてきた
金属材料に代わって各種部品材料として脚光を浴びてい
る。Various types of ceramics, such as non-oxide ceramics such as silicon nitride and silicon carbide, are generally lightweight, have high chemical stability, and have excellent heat resistance, so they are being used as materials for various parts in place of conventional metal materials. is in the spotlight.
このような窒化ケイ素等のセラミックスは、例えばその
原料粉体を成形型に充填したのち窒素気流中で加熱・焼
結せしめることにより製造される。しかしながらこのよ
うな原料粉体は一般に難焼結性であるため、通常は、原
料粉体中に焼結助剤を添加したのち焼結を行うか、また
は高温高圧下で焼結を行う方法が適用されている。Ceramics such as silicon nitride are manufactured by, for example, filling raw material powder into a mold and then heating and sintering it in a nitrogen stream. However, such raw material powders are generally difficult to sinter, so sintering is usually performed after adding a sintering aid to the raw material powders, or sintering is performed under high temperature and high pressure. Applied.
したがって、このような従来の方法では所望の形状の特
に複雑な形状の焼結体を得ることが困難である。このよ
うな問題を解消するためシラザン系ポリマーを製造原料
として用いる方法が考えられている。たとえば、特開昭
５７−１１７５３２号公報および特開昭５８−６３７２
５号公報では、塩素含有ジシランとジシランを接触反応
させる方法が開示されている。また、特開昭５７−１３
９１２４号公報では、オルガノクロロシランとジシラザ
ンを接触反応させる方法が開示されている。しかしなが
らこれらの従来方法では得られるポリシラザンの分子量
をコントロールすることが困難である。このため、最終
的に一定した品質のセラミックスを得ることができない
。また、得られたポリシラザンは有機溶媒に不溶のガラ
ス状の固体であることから、ポリメチルシラザンを有機
溶媒に溶解させ、この溶解液を所望の形状の成形型に充
填する通常の成形方法では、成形が困難であり、所望の
形状の、特に複雑な形状の焼結体を得ることが困難であ
る。Therefore, with such conventional methods, it is difficult to obtain a sintered body having a desired shape, particularly a complex shape. In order to solve these problems, methods using silazane-based polymers as raw materials have been considered. For example, JP-A-57-117532 and JP-A-58-6372.
No. 5 discloses a method of causing a catalytic reaction between a chlorine-containing disilane and a disilane. Also, JP-A-57-13
No. 9124 discloses a method of causing a contact reaction between organochlorosilane and disilazane. However, with these conventional methods, it is difficult to control the molecular weight of the polysilazane obtained. For this reason, it is not possible to finally obtain ceramics of constant quality. Furthermore, since the obtained polysilazane is a glass-like solid that is insoluble in organic solvents, the usual molding method involves dissolving polymethylsilazane in an organic solvent and filling a mold with the desired shape. Molding is difficult, and it is difficult to obtain a sintered body having a desired shape, particularly a complicated shape.
［発明の目的］
本発明は上記の問題点を解消し、所望の形状のセラミッ
クスを比較的板やかな条件で、より容易に製造すること
ができる、セラミックス製造用の前駆体として有用な環
状ポリメチルシラザン構造を有する重合体の提供を目的
とする。[Object of the Invention] The present invention solves the above-mentioned problems, and provides a cyclic polyester useful as a precursor for producing ceramics, which allows ceramics of a desired shape to be produced more easily under relatively gentle conditions. The purpose of the present invention is to provide a polymer having a methylsilazane structure.
［発明の構成］
すなわち本発明の環状ポリメチルシラザン構造を有する
重合体の製造方法は、
（Ａ）ヘキサメチルシクロトリシラザン；および（Ｂ）
式 （、ＣＨｓ ）ａＳ ｉ ＣｆＬ４−ａ （ただ
し、式中ａは０．１または２である）で示されるクロロ
シラン化合物；を塩化水素受容体の存在下で加熱・重合
せしめたのち、前記塩化水素受容体を除いた残部にアン
モニアを反応させることを特徴とする。[Structure of the Invention] That is, the method for producing a polymer having a cyclic polymethylsilazane structure of the present invention comprises: (A) hexamethylcyclotrisilazane; and (B)
A chlorosilane compound represented by the formula (,CHs)aS i CfL4-a (wherein a is 0.1 or 2) is heated and polymerized in the presence of a hydrogen chloride acceptor, and then the hydrogen chloride It is characterized by reacting the remaining part, excluding the receptor, with ammonia.
本発明の製造方法において出発原料となるヘキサメチル
シクロトリシラザン（以下、「三量体」という）は、例
えばジョン・シー・バラ−、ジェイアール他、インオー
ガニック シンセシス ｊ６１ （１９５３） ［Ｊ
ＯＨＮ Ｃ，ＢＡＬＡＲ，Ｊｒ、 ｅｔ ａｔ。Hexamethylcyclotrisilazane (hereinafter referred to as "trimer"), which is a starting material in the production method of the present invention, is described, for example, by John C. Barra, JR et al., Inorganic Synthesis J61 (1953) [J
OHN C, BALAR, Jr. et at.
Ｉｎｏｒｇａｎｉｃ ５ｙｎｔｈｅｓｉｓ ５ ６１
（１９５３） ］に記載のブレシーおよびハーバ−（
Ｂｒｅｗｅｒ ａｎｄＨａｒｂｅｒ）改良法を適用して
製造することができる。Inorganic 5 synthesis 5 61
(1953) ] Brecy and Haber (
It can be produced by applying a modified method (Brewer and Harbor).
このようにして得られる三量体を式（１）で示されるク
ロロシラン化合物と反応させ、環状ポリメチルシラザン
構造を有する重合体を製造する。The trimer thus obtained is reacted with a chlorosilane compound represented by formula (1) to produce a polymer having a cyclic polymethylsilazane structure.
この式（Ｉ）で示されるクロロシラン化合物は、具体的
にはジメチルジクロロシラン、メチルトリクロロシラン
またはテトラクロロシランである。The chlorosilane compound represented by formula (I) is specifically dimethyldichlorosilane, methyltrichlorosilane or tetrachlorosilane.
このクロロシラン化合物は、三量体の窒素原子に結合し
た水素原子と脱塩化水素反応を行うことにより、架橋剤
として作用するものであることから、上記の化合物の中
でもより官能基が多い、メチルトリクロロシラン、テト
ラクロロシラン、特にテトラクロロシランが好ましい。This chlorosilane compound acts as a crosslinking agent by performing a dehydrochlorination reaction with the hydrogen atom bonded to the nitrogen atom of the trimer. Chlorosilane, tetrachlorosilane, especially tetrachlorosilane are preferred.
本発明の製造方法においては、三量体とクロロシラン化
合物の反応を塩化水素受容体の存在下で行うものであれ
ば、その個々の操作手順は特に制限されない、以下、本
発明の製造方法についてその一例を掲げ説明する。In the production method of the present invention, the individual operating procedures are not particularly limited as long as the reaction between the trimer and the chlorosilane compound is carried out in the presence of a hydrogen chloride acceptor. An example will be given and explained.
まず、三量体と塩化水素受容体（以下、「受容体」とい
う）を反応容器中に投入する。ここで用いる受容体は、
三量体とクロロシラン化合物との反応により発生する塩
化水素を吸収するためのものである。この受容体として
は、一般に用いられている第３級アミン、例えば、ピリ
ジン、１．８−ジアザビシクロ（５、４、０）−ウンデ
セン−７（ＤＢＵ）、ピリジンまたはＮ、Ｎ−ジメチル
アセトアミド（ＤＭＡＣ）等を挙げることができる。こ
れらの受容体の中でも、生成物である環状ポリメチルシ
ラザン構造を有する重合体の熱重量減少率が小さいこと
からＤＭＡＣが好ましい、この受容体は三量体とクロロ
シラン化合物との反応により発生する塩化水素を完全に
吸収できる量、すなわち理論量か、または過剰量を加え
る。また、受容体は溶媒を兼ねて用いてもよいし、ベン
ゼン、トルエンのような他の有機溶媒を併用してもよい
。First, a trimer and a hydrogen chloride acceptor (hereinafter referred to as "receptor") are charged into a reaction vessel. The receptor used here is
This is to absorb hydrogen chloride generated by the reaction between the trimer and the chlorosilane compound. This acceptor may include commonly used tertiary amines such as pyridine, 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU), pyridine or N,N-dimethylacetamide (DMAC). ) etc. Among these receptors, DMAC is preferred because the thermal weight loss rate of the product, a polymer with a cyclic polymethylsilazane structure, is small. Add an amount that can completely absorb hydrogen, ie, the stoichiometric amount, or an excess amount. Further, the receptor may also be used as a solvent, or other organic solvents such as benzene and toluene may be used in combination.
次いで、反応系内を乾燥雰囲気にする。これは系内の空
気を不活性ガス、例えば窒素ガスに置換することにより
行う。その後、系内を加熱・還流しながら、クロロシラ
ン化合物を添加する。この場合の加熱温度は用いる受容
体により異なる。例えば上述した各受容体のうち、ピリ
ジンを用いた場合は沸点温度まで、その他の受容体の場
合は約ｓｏ’ｃ程度まで加熱する。添加は、例えば滴下
法等により少量ずつ添加することが良好な反応を行うた
めに好ましい、添加量は、目的とする環状ポリメチルシ
ラザン構造を有する重合体の分子量に応じて、三量体の
添加量に関連して適宜決定することができる０例えば、
三量体１モルに対して、テトラクロロシランを０．７５
モル用いると、分子量約９００の環状ポリメチルシラザ
ン構造を有する重合体ないし、それらがさらに架橋重合
した重合体を製造することができる。またこの場合に受
容体例えばピリジンは３モル以上必要である。Next, a dry atmosphere is created in the reaction system. This is done by replacing the air in the system with an inert gas, such as nitrogen gas. Thereafter, a chlorosilane compound is added while heating and refluxing the system. The heating temperature in this case varies depending on the receptor used. For example, among the above-mentioned receptors, when pyridine is used, it is heated to the boiling point temperature, and when other receptors are used, it is heated to about so'c. It is preferable to add the trimer little by little by, for example, a dropwise addition method in order to perform a good reaction. 0, which can be determined accordingly in relation to the amount, e.g.
0.75% tetrachlorosilane per 1 mole of trimer
When using molar amounts, it is possible to produce a polymer having a cyclic polymethylsilazane structure having a molecular weight of about 900, or a polymer obtained by further crosslinking polymerization thereof. In this case, the amount of receptor such as pyridine is required to be 3 moles or more.
クロロシラン化合物を添加したのち、さらに系内を６０
〜１２０℃、好ましくは８０〜１１５℃で６〜１２時間
加熱・攪拌還流し、反応を完結させる。その後受容体を
除去したのち、液状の生成物ヲベンゼン、トルエン、キ
シレン、シクロヘキサン等の有機溶媒に溶解させる０次
いでこの溶液をアンモニアで処理する。このアンモニア
処理は、生成物の分子末端に結合する５ｔ−Ｃ１基を５
ｉ−ＮＨ２基に変換し、その後の塩化水素の発生を防止
するものである。この処理はたとえば前記溶液中にアン
モニアガスを吹き込むことによって行う９次いで、濾過
を行い前記反応で副生じた塩化アンモニウムを分離する
。その後、溶媒を除去したのち、加熱下で減圧蒸留する
ことにより、未反応の三量体等を除去し、環状ポリメチ
ルシラザン構造を有する重合体を得ることができる。After adding the chlorosilane compound, the system was further heated to 60%
The reaction is completed by heating, stirring and refluxing at ~120°C, preferably 80-115°C for 6-12 hours. Thereafter, after removing the receptor, the liquid product is dissolved in an organic solvent such as benzene, toluene, xylene, or cyclohexane.Then, this solution is treated with ammonia. This ammonia treatment removes the 5t-C1 group attached to the molecular end of the product.
It converts into i-NH2 group and prevents the subsequent generation of hydrogen chloride. This treatment is carried out, for example, by blowing ammonia gas into the solution.9 Next, filtration is performed to separate ammonium chloride produced as a by-product in the reaction. Thereafter, after removing the solvent, unreacted trimer and the like can be removed by distilling under reduced pressure under heating to obtain a polymer having a cyclic polymethylsilazane structure.
［発明の実施例］ 以下、実施例を掲げ本発明をさらに詳述する。[Embodiments of the invention] Hereinafter, the present invention will be explained in further detail with reference to Examples.
実施例１〜５
三量体は、前述したブレワーおよびハーバ−改良法を適
用し、ジメチルジクロロシランのアンモノリシスにより
合成したものを用いた。受容体およびクロロシラン化合
物はそれぞれ表に示すものを用いた。また、実施例１，
２では理論量の１．５倍の受容体とベンゼンの混合物を
、実施例３〜５では受容体をそれぞれクロロシラン化合
物１００容量部に対して４００容量部加え、クロロシラ
ン化合物は三量体に対して表に示すモル比で添加し、反
応を行った。Examples 1 to 5 Trimers were synthesized by ammonolysis of dimethyldichlorosilane by applying the above-mentioned Brewer and Haber improved method. The receptors and chlorosilane compounds shown in the table were used. In addition, Example 1,
In Example 2, a mixture of 1.5 times the theoretical amount of receptor and benzene was added, and in Examples 3 to 5, 400 parts by volume of each receptor was added to 100 parts by volume of the chlorosilane compound. They were added at the molar ratio shown in the table and the reaction was carried out.
まず冷却管、温度計および滴下漏斗を備えた三ツ−フラ
スコに受容体を投入し、続いて三量体を投入した。次い
で、フラスコの空気を完全に窒素ガスに置換した。その
後、実施例１および２では約８０℃、実施例３〜５では
約１１５℃まで加熱し、還流しながら、滴下漏斗から所
定量のクロロシラン化合物を２時間かけて滴下した。次
いで、さらにそのままの温度で８時間加熱中還流し、反
応を完結させた０反応終了後受容体を除去し、反応生成
物を含む残液を５００−のベンゼンに溶解させた０次い
で、この溶液中にアンモニアガスを７０ｆＬ／時間で１
．５時間吹き込んだ、その後吸引濾過し、副生じた塩化
アンモニウムを除去した０次いでさらに４０〜ｂ
圧蒸留を行ってベンゼンを除去し、環状ポリメチルシラ
ザン構造を有する重合体を得た。The receptor was first charged to a three-two flask equipped with a condenser, thermometer and addition funnel, followed by the trimer. Then, the air in the flask was completely replaced with nitrogen gas. Thereafter, the mixture was heated to about 80° C. in Examples 1 and 2, and to about 115° C. in Examples 3 to 5, and a predetermined amount of the chlorosilane compound was added dropwise from the dropping funnel over 2 hours while refluxing. Next, the reaction was further heated under reflux at the same temperature for 8 hours to complete the reaction. After the reaction was completed, the receptor was removed, and the residual solution containing the reaction product was dissolved in 500% benzene. ammonia gas at 70fL/hour
．． Bubbling was carried out for 5 hours, and then suction filtration was performed to remove by-produced ammonium chloride.Then, further distillation was performed under a pressure of 40~B to remove benzene, thereby obtaining a polymer having a cyclic polymethylsilazane structure.
得られた環状ポリメチルシラザン構造を有する重合体の
分子量、性状、収率および熱重量減少率を表に示す、な
お、熱重量減少率は、窒素ガス雰囲気下、５°Ｃ／分の
割合で８００℃まで加熱したのち測定した。The molecular weight, properties, yield, and thermogravimetric reduction rate of the obtained polymer having a cyclic polymethylsilazane structure are shown in the table.The thermogravimetric reduction rate was measured at a rate of 5°C/min under a nitrogen gas atmosphere. Measurements were taken after heating to 800°C.
実施例６
受容体としてピリジンを用い、クロロシラン化合物とし
てジメチルジクロロシランを三量体１モルに対して１．
５モルを用いて実施例１と同様にして環状ポリメチルシ
ラザン構造を有する重合体を得た。Example 6 Pyridine was used as the acceptor, and dimethyldichlorosilane was used as the chlorosilane compound at 1.0% per mole of trimer.
A polymer having a cyclic polymethylsilazane structure was obtained in the same manner as in Example 1 using 5 mol.
この生成物は無色透明液体であり、分子量は６００であ
った。また収率は４２％、熱重量減少率は９２％であっ
た。この生成物の赤外線吸収スペクトルは図の（ｂ）に
示すように、１，０３０ＣＩｌ″ｌの５ｉ−Ｎ（三量体
の環の外）の吸収を生じ、Ｎ−Ｈの吸収が減少している
。また、この生成物の構造式は下記のとおりであると推
定される。ただし、式中Ｍｅ２は２つのメチル基がケイ
素原子に結合していることを表す、以下同様である。This product was a colorless transparent liquid with a molecular weight of 600. Further, the yield was 42%, and the thermogravimetric reduction rate was 92%. As shown in figure (b), the infrared absorption spectrum of this product shows that 1,030 CIl''l of 5i-N (outside the trimer ring) is absorbed, and the N-H absorption is decreased. In addition, the structural formula of this product is estimated to be as shown below.However, in the formula, Me2 represents two methyl groups bonded to a silicon atom, and the same applies hereinafter.
実施例７
受容体としてピリジンを用い、クロロシラン化合物とし
てテトラクロロシランを三量体１モルに対して０．７５
モ、ル用いて、実施例１と同様にして環状ポリメチルシ
ラザン構造を有する重合体を得た。Example 7 Pyridine was used as the acceptor, and tetrachlorosilane was used as the chlorosilane compound at a concentration of 0.75 per mole of trimer.
A polymer having a cyclic polymethylsilazane structure was obtained in the same manner as in Example 1 using the following methods.
この生成物は淡黄色の粘稠液体であり、分子量は８４０
であった。また、収率は３６％、熱重量減少率は９０％
であった。この生成物の赤外線吸収スペクトルを図の（
Ｃ）に示した。またこの生成物の構造式は下記のとおり
であると推定される。The product is a pale yellow viscous liquid with a molecular weight of 840
Met. In addition, the yield is 36% and the thermogravimetric reduction rate is 90%.
Met. The infrared absorption spectrum of this product is shown in the figure (
Shown in C). Moreover, the structural formula of this product is estimated to be as follows.
実施例８
受容体としてＤＭＡＣを用い、クロロシラン化合物とし
てテトラクロロシランを三量体１モルに対して０．７５
モルを用いて実施例１と同様にして環状ポリメチルシラ
ザン構造を有する重合体を得た。Example 8 DMAC was used as a receptor, and tetrachlorosilane was used as a chlorosilane compound at a concentration of 0.75% per mole of trimer.
A polymer having a cyclic polymethylsilazane structure was obtained in the same manner as in Example 1 using molar.
この生成物はゼラチン状であった。収率は７３％、熱重
量減少率は４１％であった。この生成物の赤外線吸収ス
ペクトルを図の（ｄ）に示した。The product was gelatinous. The yield was 73%, and the thermogravimetric reduction was 41%. The infrared absorption spectrum of this product is shown in (d) of the figure.
また、この生成物の構造式は、下記のとおりであると推
定される。Moreover, the structural formula of this product is estimated to be as follows.
参考例１
実施例５で得られた環状ポリメチルシラザン構造を有す
る重合体を用いてセラミックスを製造した。Reference Example 1 Ceramics were manufactured using the polymer having a cyclic polymethylsilazane structure obtained in Example 5.
メチルシクロポリシラザンを所望の成形型に充填したの
ち、窒素ガス雰囲気中で５°Ｃ／分の割合で１，０００
℃まで加熱・昇温せしめる。その後、さらにこの温度で
２時間保持せしめることにより、焼成した。After filling a desired mold with methylcyclopolysilazane, it was heated at a rate of 5°C/min at 1,000°C in a nitrogen gas atmosphere.
Heat and raise the temperature to ℃. Thereafter, the mixture was further held at this temperature for 2 hours to perform firing.
このセラミックスの表面は、ＳＥＭ観楽により均一な平
滑面を有していた。また、ビッカース硬度は１ 、２５
０ｋｇ／ｃｍ２であった。このことからこのセラミック
スは空孔の少ない緻密な構造を有していることがわかっ
た。The surface of this ceramic was found to have a uniform smooth surface by SEM observation. Also, Vickers hardness is 1, 25
It was 0 kg/cm2. This indicates that this ceramic has a dense structure with few pores.
参考例２
実施例７で得られた環状ポリメチルシラザン構造を有す
る重合体を用いて、参考例１と同様にしてセラミックス
を製造した。ただし、昇温速度は５℃／分であり、１，
４００℃まで加熱した。また、昇温後の保持時間は２時
間であった。Reference Example 2 Using the polymer having a cyclic polymethylsilazane structure obtained in Example 7, a ceramic was produced in the same manner as in Reference Example 1. However, the temperature increase rate is 5°C/min, and 1,
It was heated to 400°C. Further, the holding time after the temperature rise was 2 hours.
このセラミックスの表面は、ＳＥＭ観察により均一な平
滑面を有していた。また、ビッカース硬度はｌ 、 ９
３０ｋｇ／ｃｍ２であった。このことからこのセラミッ
クスは空孔の少ない緻密な構造を有していることがわか
った。The surface of this ceramic was found to have a uniform smooth surface by SEM observation. Also, the Vickers hardness is l, 9
It was 30 kg/cm2. This indicates that this ceramic has a dense structure with few pores.
［発明の効果］
以上説明したとおり本発明の製造方法によれば、生成物
である環状ポリメチルシラザン構造を有する重合体の分
子量を自由にコントロールすることができ、これにより
焼成後のセラミックスの品質を一定化することができる
。また、得られた環状ポリメチルシラザン構造を有する
重合体は有機溶媒に可溶であることから成形が容易であ
り、したがって所望の形状の、特に複雑な形状のセラミ
ックスを得ることができる。さらに、この環状ポリメチ
ルシラザン構造を有する重合体は緩やかな条件（常圧、
焼成温度８００℃以上）で焼成することにより、高硬度
で、かつ緻密な構造を有するセラミックスを得ることが
でき、したがって種々の分野への適用が可能となるもの
である。[Effects of the Invention] As explained above, according to the production method of the present invention, it is possible to freely control the molecular weight of the product, a polymer having a cyclic polymethylsilazane structure, which improves the quality of ceramics after firing. can be made constant. Furthermore, the resulting polymer having a cyclic polymethylsilazane structure is soluble in organic solvents and is therefore easily molded, making it possible to obtain ceramics having a desired shape, particularly a complex shape. Furthermore, the polymer with this cyclic polymethylsilazane structure can be produced under mild conditions (normal pressure,
By firing at a firing temperature of 800°C or higher), ceramics with high hardness and a dense structure can be obtained, and therefore can be applied to various fields.
４、図面のな説明
図の（ａ）は三量体の赤外線吸収スペクトルを、（ｂ）
〜（ｄ）はそれぞれ実施例６〜８で得られた環状ポリシ
ラザン構造を有する重合体の赤外線吸収スペクトルを示
す。4. In the explanatory diagram (a) of the drawing, (b) shows the infrared absorption spectrum of the trimer.
- (d) show infrared absorption spectra of the polymers having a cyclic polysilazane structure obtained in Examples 6 to 8, respectively.
＋３００ １０００ ８００ （Ｃ＋’ｎ”
）手続補正書（方式）
昭和８１年８月５日+300 1000 800 (C+'n"
) Procedural amendment (formality) August 5, 1981
Claims (3)
し、式中ａは０、１または２である）で示されるクロロ
シラン化合物；を塩化水素受容体の存在下で加熱・重合
せしめたのち、前記塩化水素受容体を除いた残部にアン
モニアを反応させることを特徴とする環状ポリメチルシ
ラザン構造を有する重合体の製造方法。(1) (A) hexamethylcyclotrisilazane; and (B) a chlorosilane compound represented by the formula (CH_3)_aSiCl_4_-_a (wherein a is 0, 1 or 2); 1. A method for producing a polymer having a cyclic polymethylsilazane structure, which comprises heating and polymerizing the polymer in the presence of the hydrogen chloride acceptor, and then reacting the remaining portion after removing the hydrogen chloride acceptor with ammonia.
である特許請求の範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, wherein the hydrogen chloride acceptor is N,N-dimethylacetamide.
特許請求の範囲第１項記載の製造方法。(3) The manufacturing method according to claim 1, wherein the chlorosilane compound is tetrachlorosilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4146786A JPS62199623A (en) | 1986-02-28 | 1986-02-28 | Production of polymer having cyclic polymethyl silazane structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4146786A JPS62199623A (en) | 1986-02-28 | 1986-02-28 | Production of polymer having cyclic polymethyl silazane structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62199623A true JPS62199623A (en) | 1987-09-03 |
| JPH0576970B2 JPH0576970B2 (en) | 1993-10-25 |
Family
ID=12609174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4146786A Granted JPS62199623A (en) | 1986-02-28 | 1986-02-28 | Production of polymer having cyclic polymethyl silazane structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62199623A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0266918A2 (en) * | 1986-11-04 | 1988-05-11 | Dow Corning Corporation | A method for the preparation of preceramic polymers derived from cyclic silazanes and halosilanes |
| JPH01118528A (en) * | 1987-10-31 | 1989-05-11 | Res Dev Corp Of Japan | Preparation of methyl polysilazane |
| EP0351747A2 (en) * | 1988-07-20 | 1990-01-24 | Hoechst Aktiengesellschaft | Method of making a ceramic material containing silicon nitride from polymeric hydridochlorosilazanes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62156136A (en) * | 1985-11-28 | 1987-07-11 | ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク | Two-process production of organopolysilazane reticulated polymer having improved heat resistance and usable especially as ceramic precursor |
-
1986
- 1986-02-28 JP JP4146786A patent/JPS62199623A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62156136A (en) * | 1985-11-28 | 1987-07-11 | ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク | Two-process production of organopolysilazane reticulated polymer having improved heat resistance and usable especially as ceramic precursor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0266918A2 (en) * | 1986-11-04 | 1988-05-11 | Dow Corning Corporation | A method for the preparation of preceramic polymers derived from cyclic silazanes and halosilanes |
| JPH01118528A (en) * | 1987-10-31 | 1989-05-11 | Res Dev Corp Of Japan | Preparation of methyl polysilazane |
| EP0351747A2 (en) * | 1988-07-20 | 1990-01-24 | Hoechst Aktiengesellschaft | Method of making a ceramic material containing silicon nitride from polymeric hydridochlorosilazanes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0576970B2 (en) | 1993-10-25 |
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