JPH06298938A - Thermosetting polymer and its production - Google Patents
Thermosetting polymer and its productionInfo
- Publication number
- JPH06298938A JPH06298938A JP8476793A JP8476793A JPH06298938A JP H06298938 A JPH06298938 A JP H06298938A JP 8476793 A JP8476793 A JP 8476793A JP 8476793 A JP8476793 A JP 8476793A JP H06298938 A JPH06298938 A JP H06298938A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polymer
- reaction
- carbon atoms
- water
- 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.)
- Pending
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性に優れた硬化物
の原料となる熱硬化性重合体及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting polymer as a raw material for a cured product having excellent heat resistance and a method for producing the same.
【０００２】[0002]
【従来の技術】フェノール樹脂、不飽和ポリエステル、
エポキシ樹脂等の熱硬化性樹脂は、耐熱性、耐薬品性、
機械的性質が優れているため、電子、電気、自動車等様
々な分野で幅広く利用されている。2. Description of the Related Art Phenolic resin, unsaturated polyester,
Thermosetting resin such as epoxy resin has heat resistance, chemical resistance,
Due to its excellent mechanical properties, it is widely used in various fields such as electronics, electricity and automobiles.
【０００３】しかしながら、熱硬化性樹脂の耐熱性硬化
後は、熱可塑性樹脂に比べると確かに優れてはいるもの
の、耐熱性の指標となる熱分解温度を見てみるとフェノ
ール樹脂で３００〜３５０℃、不飽和ポリエステルで１
５０〜２００℃、エポキシ樹脂で２００〜２５０℃とな
っており、用途によってはまだ充分な耐熱性を有してい
るとは言い難い。However, after heat-curing the thermosetting resin, although it is certainly superior to the thermoplastic resin, the thermal decomposition temperature, which is an index of the heat resistance, is 300 to 350 for the phenol resin. ℃, 1 with unsaturated polyester
The temperature is 50 to 200 ° C., and the epoxy resin temperature is 200 to 250 ° C., and it is hard to say that the resin still has sufficient heat resistance depending on the application.
【０００４】[0004]
【発明が解決しようとする課題】耐熱性を改良した熱硬
化性樹脂として、全芳香族ポリイミドが知られている
が、４００℃を超える熱分解温度を有するものの、成形
・硬化に極めて高度な技術が必要であるという問題点を
有している。Although a wholly aromatic polyimide is known as a thermosetting resin having improved heat resistance, it has an extremely high technique for molding / curing although it has a thermal decomposition temperature of more than 400 ° C. Is necessary.
【０００５】他の耐熱性に優れた熱硬化性樹脂としてポ
リオルガノシロキサンいわゆるシリコーン樹脂が知られ
ている。しかしながら、シリコーン樹脂によっても４０
０℃を超える熱分解温度は得られておらず、また架橋反
応が脱水縮合反応であるため、硬化反応時に本質的に副
生物が生成するという問題点を有している。As another thermosetting resin having excellent heat resistance, polyorganosiloxane so-called silicone resin is known. However, even with silicone resin, 40
Since a thermal decomposition temperature exceeding 0 ° C. has not been obtained and the crosslinking reaction is a dehydration condensation reaction, there is a problem that by-products are essentially generated during the curing reaction.
【０００６】縮合反応を伴わないケイ素化合物の素反応
として、シラシクロブタンの開環重合反応が知られてい
る（Ｊ．Ｏ．Ｃ．，３０，２６１８，（１９６５））。
この反応は加熱により進行し、副生成を生じない反応で
ある。しかしながら、ケイ素上の置換基がメチル基、フ
ェニル基であるシラシクロブタンの反応は速やかに進行
するものの、加水分解可能なエトキシ基、アミノ基を有
するシラシクロブタンの開環重合は進行し難く、架橋ポ
リマーの合成反応として応用し難いという問題点を有し
ている。A ring-opening polymerization reaction of silacyclobutane is known as an elementary reaction of a silicon compound without a condensation reaction (JOC, 30 , 2618, (1965)).
This reaction is a reaction that proceeds by heating and does not generate by-products. However, although the reaction of silacyclobutane having a methyl group or a phenyl group as a substituent on silicon proceeds rapidly, ring-opening polymerization of silacyclobutane having a hydrolyzable ethoxy group or an amino group is difficult to proceed, and thus a crosslinked polymer. It has a problem that it is difficult to apply it as a synthetic reaction.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、上述した
問題点を解決した耐熱性に優れながら、成形・硬化の容
易な熱硬化性樹脂について、鋭意検討を重ねた結果、一
般式（１）で示す構造を有する重合体が上記目的を達成
できることを見出し本発明に到達した。Means for Solving the Problems The inventors of the present invention have conducted extensive studies as to a thermosetting resin which is excellent in heat resistance and which is easy to mold and cure, and which has been solved by the general formula ( The present inventors have found that a polymer having a structure shown in 1) can achieve the above object and reached the present invention.
【０００８】本発明の要旨は下記の一般式（１）で示さ
れる数平均分子量が５００以上の重合体にあり、又、下
記の一般式（２）で示される化合物と水とを反応させる
前記重合体の製造方法にある。The gist of the present invention resides in a polymer represented by the following general formula (1) and having a number average molecular weight of 500 or more. Further, the compound represented by the following general formula (2) is reacted with water. There is a method for producing a polymer.
【０００９】[0009]
【化３】 [Chemical 3]
【００１０】（但し、Ｒ1 及びＲ2 はそれぞれ独立に水
酸基、クロロ基、ブロモ基、炭素数１〜４のアルコキシ
基、炭素数１〜４のジアルキルアミノ基、水素原子又は
炭素数１〜４のトリアルキルシロキシ基を表わす。）(However, R 1 and R 2 are each independently a hydroxyl group, a chloro group, a bromo group, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group having 1 to 4 carbon atoms, a hydrogen atom or 1 to 4 carbon atoms. Represents a trialkylsiloxy group.)
【００１１】[0011]
【化４】 [Chemical 4]
【００１２】（但し、Ｒ3 及びＲ4 はそれぞれ独立にク
ロロ基、ブロモ基、炭素数１〜４のアルコキシ基、炭素
数１〜４のジアルキルアミノ基又は水素を表わす。）式
（１）で示される本発明の重合体は、常温（２５℃）で
流動性を有するため、成形・硬化の際の取扱いが容易で
ある。また、常温での保存安定性にも優れ、２５℃密閉
下でのポットライフ、即ち固化せず流動性を保持し有る
期間は３０日以上である。(Wherein R 3 and R 4 each independently represents a chloro group, a bromo group, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group having 1 to 4 carbon atoms or hydrogen). Since the polymer of the present invention shown has fluidity at room temperature (25 ° C.), it can be easily handled during molding and curing. Further, it has excellent storage stability at room temperature, and has a pot life in a closed condition of 25 ° C., that is, a period in which it does not solidify and retains fluidity for 30 days or more.
【００１３】本発明の重合体は数平均分子量５００以上
であり、耐熱性の良好な架橋重合体の原料として適して
いる。即ち、本発明の重合体は、加熱硬化反応により副
生物を生成することなく、優れた耐熱性、具体的には４
００℃を超える熱分解温度を有する硬化物（架橋重合
体）を与えることができる。The polymer of the present invention has a number average molecular weight of 500 or more and is suitable as a raw material for a crosslinked polymer having good heat resistance. That is, the polymer of the present invention has excellent heat resistance, specifically 4
A cured product (crosslinked polymer) having a thermal decomposition temperature of higher than 00 ° C can be provided.
【００１４】本発明の重合体は、式（２）で表される化
合物を溶媒の存在下、あるいは無溶媒で加水分解・重縮
合させることにより合成できる。反応させる水の量は特
に限定されないが、式（２）の化合物１モルに対して
０．９〜１０．０モルであることが好ましい。水の量が
１０．０モルを超える場合は、側鎖のシクロトリメチレ
ン環の加水分解反応が副反応として起き易くなる。ま
た、水の量が０．９モル未満の場合は、重合体の分子量
を上げることが困難になる。反応させる水の量は式
（２）の化合物１モルに対して、１．０〜４．０モルで
あることが特に好ましい。The polymer of the present invention can be synthesized by subjecting the compound represented by the formula (2) to hydrolysis / polycondensation in the presence of a solvent or in the absence of a solvent. The amount of water to be reacted is not particularly limited, but it is preferably 0.9 to 10.0 mol with respect to 1 mol of the compound of the formula (2). When the amount of water exceeds 10.0 mol, the hydrolysis reaction of the side chain cyclotrimethylene ring is likely to occur as a side reaction. When the amount of water is less than 0.9 mol, it becomes difficult to increase the molecular weight of the polymer. The amount of water to be reacted is particularly preferably 1.0 to 4.0 mol with respect to 1 mol of the compound of the formula (2).
【００１５】式（２）中のＲ3 及びＲ4 は加水分解可能
な官能基であり、クロロ基、ブロモ基、炭素数１〜４の
アルコキシ基、炭素数１〜４のジアルキルアミノ基、水
素原子から選ばれる。上記官能基のうち、クロロ基、ブ
ロモ基は特に反応性が高く、加水分解反応が容易である
ため好ましい。R 3 and R 4 in the formula (2) are hydrolyzable functional groups, such as chloro group, bromo group, alkoxy group having 1 to 4 carbon atoms, dialkylamino group having 1 to 4 carbon atoms, and hydrogen. Selected from atoms. Of the above-mentioned functional groups, a chloro group and a bromo group are particularly preferable because they have high reactivity and the hydrolysis reaction is easy.
【００１６】尚、化合物（２）中のＲ3 とＲ4 が共にク
ロロ基の場合は反応は例えば次のように進行する。即
ち、（３）式のようにまず加水分解反応が起こり、続い
て（４）式のように脱水縮合反応が起こり、この脱水縮
合反応の進行により式（１）の重合体が得られる。When R 3 and R 4 in the compound (2) are both chloro groups, the reaction proceeds as follows, for example. That is, a hydrolysis reaction occurs first as in formula (3), and then a dehydration condensation reaction occurs as in formula (4), and the polymer of formula (1) is obtained by the progress of this dehydration condensation reaction.
【００１７】[0017]
【化５】 [Chemical 5]
【００１８】Ｒ3 ，Ｒ4 がクロロ基又はブロモ基である
場合、合成反応時に副生するハロゲン化水素の捕捉剤と
して塩基を用いることができる。塩基としては、ピリジ
ン等のアミン類を式（２）の化合物１モルに対して２モ
ル以上即ち副生するハロゲン化水素に対して当量以上用
いることが好ましい。When R 3 and R 4 are a chloro group or a bromo group, a base can be used as a scavenger for hydrogen halide produced as a by-product during the synthetic reaction. As the base, it is preferable to use amines such as pyridine in an amount of 2 mol or more with respect to 1 mol of the compound of the formula (2), that is, equivalent amount or more with respect to hydrogen halide produced as a by-product.
【００１９】また、前記反応の際には必要に応じてヘキ
サメチルジシラザン、ヘキサメチルジシロキサン、トリ
メチルクロロシラン等の末端封止剤を添加することがで
きる。Further, in the above reaction, an end capping agent such as hexamethyldisilazane, hexamethyldisiloxane, trimethylchlorosilane can be added if necessary.
【００２０】[0020]
【実施例】以下に実施例を挙げて本発明を更に具体的に
説明する。実施例における測定装置及び測定方法は以下
の通りである。 １）分子量 ゲルパーミエーションクロマトグラフ（以下ＧＰＣと称
する）にてクロロホルムを溶媒とし、ポリメチルメタク
リレート換算の分子量として求めた。 ２） 1Ｈ−ＮＭＲ ＦＴ−ＮＭＲスペクトロメーターにて重クロロホルムを
溶媒として求めた。 ３）熱分解温度 熱重量測定装置にて、Ｎ2 中、１０℃／分の昇温速度で
測定した時の１％重量減少温度から求めた。EXAMPLES The present invention will be described in more detail with reference to the following examples. The measuring device and the measuring method in the examples are as follows. 1) Molecular Weight The molecular weight was determined by gel permeation chromatography (hereinafter referred to as GPC) using chloroform as a solvent and the molecular weight in terms of polymethylmethacrylate. 2) It was determined using 1 H-NMR FT-NMR spectrometer with deuterated chloroform as a solvent. 3) Pyrolysis temperature It was determined from the 1% weight loss temperature when measured with a thermogravimetric instrument in N 2 at a temperature rising rate of 10 ° C./min.
【００２１】実施例１ 滴下ロート、Ｎ2 導入管、Ｎ2 排出管を取りつけた容量
３００ｍｌの四つ口フラスコに、１，１−ジクロロ−１
−シラシクロブタン２８．２ｇ（２００ｍｍｏｌ）、ヘ
キサメチルジシラザン１．１１ｇ（６．９ｍｍｏｌ）、
ベンゼン（ＣａＨ2 存在下で蒸留精製したもの）１００
ｍｌを入れ、マグネチックスターラーで攪拌し、氷冷し
ながらＮ2 気流下で水３．６ｇ（２００ｍｍｏｌ）、ピ
リジン（ＣａＨ2 存在下で蒸留精製したもの）３１．６
ｇ（４００ｍｍｏｌ）、テトラヒドロフラン（モレキュ
ラシーブスにて予備乾燥したもの）５０ｍｌの混合物を
３時間かけて滴下した。滴下終了後、Ｎ2 気流下、室温
で更に２２時間攪拌した。反応終了後、無水硫酸マグネ
シウムを少量添加、攪拌して反応溶液を脱水乾燥した。
生成した白濁等を濾別し、溶媒を除去したところ、生成
物として無色透明な室温で流動性のある液体が得られ
た。Example 1 A 1-dichloro-1 was placed in a four-necked flask having a capacity of 300 ml equipped with a dropping funnel, an N 2 introducing tube and an N 2 discharging tube.
28.2 g (200 mmol) silacyclobutane, 1.11 g (6.9 mmol) hexamethyldisilazane,
Benzene (distilled and purified in the presence of CaH 2 ) 100
ml, stirred with a magnetic stirrer, while cooling with ice, in an N 2 stream, 3.6 g of water ( 200 mmol) and pyridine (distilled and purified in the presence of CaH 2 ) 31.6.
A mixture of g (400 mmol) and tetrahydrofuran (preliminarily dried with molecular sieves) (50 ml) was added dropwise over 3 hours. After the completion of the dropping, the mixture was further stirred at room temperature under N 2 gas flow for 22 hours. After completion of the reaction, a small amount of anhydrous magnesium sulfate was added and stirred to dehydrate and dry the reaction solution.
The resulting white turbidity was filtered off, and the solvent was removed. As a result, a colorless transparent liquid having room temperature fluidity was obtained.
【００２２】得られた生成物の 1Ｈ−ＮＭＲを測定した
ところ、δ＝１．４６ｐｐｍの位置にシクロトリメチレ
ン環のマルチプレットピーク、δ＝０．１６ｐｐｍの位
置にトリメチルシリル基のシングレットピークが観察さ
れた。ＧＰＣ測定による数平均分子量は、１８００であ
った。又、この生成物を、２５℃にて密栓したサンプル
瓶中に放置しておいたところ、３０日後も固化すること
なく、流動性が保持されており、ポットライフが３０日
以上であることがわかった。When the 1 H-NMR of the obtained product was measured, a multiplet peak of the cyclotrimethylene ring was observed at the position of δ = 1.46 ppm, and a singlet peak of the trimethylsilyl group was observed at the position of δ = 0.16 ppm. Was done. The number average molecular weight measured by GPC was 1800. Further, when the product was left in a sample bottle tightly stoppered at 25 ° C., it did not solidify even after 30 days, fluidity was maintained, and pot life was 30 days or more. all right.
【００２３】実施例２ 実施例１と同様の反応装置を用い、水の量を７．２ｇ
（４００ｍｍｏｌ）とした他は同一の原料組成、手順で
滴下を行った。滴下終了後、室温で３０分攪拌してから
無水硫酸マグネシウムを約１５ｇ添加して更に室温で２
０時間攪拌した。反応終了後、白濁を濾別して溶媒を除
去したところ、無色透明な室温で流動性のある液体が得
られた。生成物の 1Ｈ−ＮＭＲを測定したところ、δ＝
１．４６ｐｐｍにシクロトリメチレン環のマルチプレッ
トピーク、δ＝０．１６ｐｐｍにトリメチルシリル基の
シングレットピークが観測された。ＧＰＣ測定による数
平均分子量は３５００であった。得られた生成物のポッ
トライフは３０日以上であった。Example 2 Using the same reactor as in Example 1, the amount of water was 7.2 g.
Other than that (400 mmol), the same material composition and procedure were used for dropping. After the dropping is completed, the mixture is stirred at room temperature for 30 minutes, then about 15 g of anhydrous magnesium sulfate is added and the mixture is further stirred at room temperature for 2 minutes.
Stir for 0 hours. After the reaction was completed, the white turbidity was filtered off and the solvent was removed. As a result, a colorless transparent fluid liquid at room temperature was obtained. When 1 H-NMR of the product was measured, δ =
A multiplet peak of the cyclotrimethylene ring was observed at 1.46 ppm, and a singlet peak of the trimethylsilyl group was observed at δ = 0.16 ppm. The number average molecular weight measured by GPC was 3,500. The pot life of the obtained product was 30 days or more.
【００２４】実施例３ 水の量を１４．４ｇ（８００ｍｍｏｌ）としそれ以外は
実施例２と同様の原料組成、反応装置手順で反応を行っ
た。得られた生成物は実施例１と同様に室温で流動性の
ある無色透明の液体であり、同様のＮＭＲスペクトルが
観察された。又、数平均分子量は４５００であり、ポッ
トライフは３０日以上であった。Example 3 The reaction was carried out by the same raw material composition and reaction apparatus procedure as in Example 2 except that the amount of water was 14.4 g (800 mmol). The obtained product was a colorless and transparent liquid having fluidity at room temperature as in Example 1, and the same NMR spectrum was observed. The number average molecular weight was 4,500 and the pot life was 30 days or longer.
【００２５】[0025]
【発明の効果】本発明の重合体は常温で流動性を有する
ため、成形・硬化時の取扱いが容易である。またこの重
合体を原料に使用すれば副生物を生成することなく耐熱
性に優れた硬化物を得ることができる。また本発明の重
合体は水との簡単な反応によって製造することができ
る。Since the polymer of the present invention has fluidity at room temperature, it is easy to handle during molding and curing. Further, when this polymer is used as a raw material, a cured product having excellent heat resistance can be obtained without producing by-products. The polymer of the present invention can also be produced by a simple reaction with water.
Claims (2)
子量が５００以上の重合体。 【化１】 （但し、Ｒ1 及びＲ2 はそれぞれ独立に水酸基、クロロ
基、ブロモ基、炭素数１〜４のアルコキシ基、炭素数１
〜４のジアルキルアミノ基、水素原子又は炭素数１〜４
のトリアルキルシロキシ基を表わす。）1. A polymer having a number average molecular weight of 500 or more, which is represented by the following general formula (1). [Chemical 1] (However, R 1 and R 2 are each independently a hydroxyl group, a chloro group, a bromo group, an alkoxy group having 1 to 4 carbon atoms, and a 1 carbon atom.
~ 4 dialkylamino group, hydrogen atom or 1 to 4 carbon atoms
Represents a trialkylsiloxy group. )
水とを反応させる請求項１記載の重合体の製造方法。 【化２】 （但し、Ｒ3 及びＲ4 はそれぞれ独立にクロロ基、ブロ
モ基、炭素数１〜４のアルコキシ基、炭素数１〜４のジ
アルキルアミノ基又は水素を表わす。）2. The method for producing a polymer according to claim 1, wherein the compound represented by the following general formula (2) is reacted with water. [Chemical 2] (However, R 3 and R 4 each independently represent a chloro group, a bromo group, an alkoxy group having 1 to 4 carbon atoms, a dialkylamino group having 1 to 4 carbon atoms, or hydrogen.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8476793A JPH06298938A (en) | 1993-04-12 | 1993-04-12 | Thermosetting polymer and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8476793A JPH06298938A (en) | 1993-04-12 | 1993-04-12 | Thermosetting polymer and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06298938A true JPH06298938A (en) | 1994-10-25 |
Family
ID=13839837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8476793A Pending JPH06298938A (en) | 1993-04-12 | 1993-04-12 | Thermosetting polymer and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06298938A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012506147A (en) * | 2008-10-20 | 2012-03-08 | ダウ コーニング コーポレーション | CVD precursor |
-
1993
- 1993-04-12 JP JP8476793A patent/JPH06298938A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012506147A (en) * | 2008-10-20 | 2012-03-08 | ダウ コーニング コーポレーション | CVD precursor |
| JP2014017502A (en) * | 2008-10-20 | 2014-01-30 | Dow Corning Corp | Cvd precursor |
| US8772524B2 (en) | 2008-10-20 | 2014-07-08 | Dow Corning Corporation | CVD precursors |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5037861A (en) | Novel highly reactive silicon-containing epoxides | |
| US6072016A (en) | Silphenylene polymer and composition containing same | |
| JPH0517927B2 (en) | ||
| CN112409401B (en) | Preparation method of silsesquioxane containing silicon hydride and corresponding polymer thereof | |
| JP2843620B2 (en) | One-terminal branched aminoalkyl group-blocked organopolysiloxane and method for producing the same | |
| JPH0848780A (en) | Production of crosslinked siloxane by disproportionation | |
| JPH07228701A (en) | Preparation of silicone resin containing hydrogen atom bonded to silicon atom | |
| JP2000044687A (en) | Ultra-branched polymer containing silicon atom | |
| JPH03190929A (en) | Preparation of silicone oligomer by nonaqueous system | |
| JPH0730093B2 (en) | Siloxaneimide diol and siloxaneimide organic block polymer obtained therefrom | |
| JP2008013766A (en) | Method for producing amino-functional siloxane | |
| JPS62225533A (en) | Organopolysiloxane modified with alkoxysilylalkyl polyoxyalkylene | |
| JPH06298938A (en) | Thermosetting polymer and its production | |
| JPH0345629A (en) | Organopolysiloxane polymer or copolymer and preparation thereof | |
| JPH06298939A (en) | Production of cross-linked alkylenesiloxane polymer | |
| JPS61236830A (en) | Production of alkoxy group-containing organopolysiloxane | |
| JPS5853655B2 (en) | Process for preparing epoxy-functional polysiloxane polymers | |
| JP2017171832A (en) | Manufacturing method of organopolysiloxane having arylene group in main chain | |
| JPH07278309A (en) | Modified polysioxane and its production | |
| JP2651359B2 (en) | Method for producing heat-resistant silicon-containing polymer | |
| US3896079A (en) | Iminoxyorganosilanes | |
| JPH0465428A (en) | Polysilethylene siloxane | |
| JP2806216B2 (en) | Silicon compound | |
| JPH0493326A (en) | Production of alkoxy-functional organopolysiloxane and alkoxy-functional organopolysiloxane obtained thereby | |
| JPH05239218A (en) | Production of branched polysiloxane |