JPH08217879A - Heat resistant resin and method for producing the same - Google Patents
Heat resistant resin and method for producing the sameInfo
- Publication number
- JPH08217879A JPH08217879A JP4931595A JP4931595A JPH08217879A JP H08217879 A JPH08217879 A JP H08217879A JP 4931595 A JP4931595 A JP 4931595A JP 4931595 A JP4931595 A JP 4931595A JP H08217879 A JPH08217879 A JP H08217879A
- Authority
- JP
- Japan
- Prior art keywords
- resistant resin
- resin
- water
- heat resistant
- prepolymer
- 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
- 229920006015 heat resistant resin Polymers 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 12
- 125000003003 spiro group Chemical group 0.000 abstract description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 2
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 2
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 2
- 229920001155 polypropylene Polymers 0.000 abstract 1
- 229920005573 silicon-containing polymer Polymers 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229920001187 thermosetting polymer Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000002597 Solanum melongena Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- -1 poly (dichlorosylpropylene) Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
(57)【要約】
【目的】 300℃以上の耐熱性を備えた、再溶融賦形が
可能で、かつ、有機溶媒に可溶な熱可塑性樹脂を得るこ
と。
【構成】 ポリシルプロピレンポリマーを加水分解し、
六員環スピロ構造を有する熱可塑性で、かつ、耐熱性を
備えた新規なシリコンポリマーを得る。(57) [Summary] [Purpose] To obtain a thermoplastic resin which has a heat resistance of 300 ° C or more, can be remelted and is soluble in an organic solvent. [Constitution] Polysil propylene polymer is hydrolyzed,
To obtain a novel silicone polymer having a six-membered ring spiro structure, which is thermoplastic and has heat resistance.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、再溶融賦形することが
でき、高い熱安定性を有し、かつ、有機溶剤に可溶な耐
熱性樹脂およびその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant resin which can be remelted and shaped, has high thermal stability and is soluble in an organic solvent, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来より、高耐熱性樹脂としては、耐薬
品性、機械的性質をともに備えていることが要求される
ことから、熱硬化型樹脂の開発を中心とした研究が広く
進められている。 400℃を越える熱分解温度を有する耐
熱性樹脂としては、全芳香族ポリイミドが知られている
が、その成形、硬化に極めて高度な技術が必要である。2. Description of the Related Art Conventionally, a high heat resistant resin has been required to have both chemical resistance and mechanical properties. Therefore, research centering on the development of thermosetting resins has been widely promoted. ing. A wholly aromatic polyimide is known as a heat-resistant resin having a thermal decomposition temperature of more than 400 ° C., but an extremely advanced technique is required for its molding and curing.
【０００３】また、他の耐熱性に優れた熱硬化型樹脂と
しては、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、従来開発されたシ
リコーン樹脂では 400℃を越える熱分解温度を有するも
のは得られておらず、またオルガノシロキサンの脱水縮
合反応による架橋硬化反応に際しては、その硬化反応時
に副生物が生成し、これが得られる樹脂の特性を低下さ
せるという問題点を有していた。As another thermosetting resin having excellent heat resistance, polyorganosiloxane, a so-called silicone resin, is known. However, conventionally developed silicone resins have not been obtained that have a thermal decomposition temperature of over 400 ° C, and during the cross-linking curing reaction by the dehydration condensation reaction of organosiloxane, by-products are generated during the curing reaction. This has a problem that the characteristics of the obtained resin are deteriorated.
【０００４】そこで、本出願人は、特開平６−２９８９
３８号公報、特開平６−２９８９３９号公報に示すよう
な硬化反応時や縮合反応を伴わない素反応を利用して、
耐熱性に優れた樹脂でありながら、その成形、硬化が容
易な熱硬化型樹脂として一般式（３）に示した構造を有
する重合体を見い出した。また、特開平３−１３９５２
７号公報においても一般式（３）と類似の骨格単位を有
する熱硬化型樹脂が提案されている。Therefore, the applicant of the present invention has filed Japanese Patent Application Laid-Open No. 6-2989.
No. 38, JP-A-6-298939, the elementary reaction without the curing reaction or the condensation reaction is utilized.
We have found a polymer having the structure shown in the general formula (3) as a thermosetting resin which is a resin having excellent heat resistance and which can be easily molded and cured. In addition, JP-A-3-13952
No. 7 publication also proposes a thermosetting resin having a skeleton unit similar to that of the general formula (3).
【化３】 Embedded image
【０００５】ところがこのような構造を有する化合物で
ある耐熱性を備えた樹脂は熱硬化型樹脂であり、加熱に
より初めて３次元架橋が起きるため、繰り返し溶融賦形
することは困難であるという難点を有している。However, a resin having a heat resistance, which is a compound having such a structure, is a thermosetting resin, and it is difficult to repeatedly perform melt shaping because three-dimensional crosslinking occurs only when heated. Have
【０００６】[0006]
【発明が解決しようとする課題】上述したごとく、従来
開発されてきた高い熱安定性を有する樹脂は、熱硬化型
樹脂であり、加熱処理を行わないとその耐熱性が発現せ
ず、しかも一度溶融処理により樹脂内に架橋構造が形成
されると、再溶融賦形することが困難であるため、その
用途が限られるという難点がある。そこで耐熱性を備え
ながらも再溶融賦形可能な樹脂の開発が待たれている現
状にある。As described above, the resin having a high thermal stability that has been developed so far is a thermosetting resin, and its heat resistance does not develop unless heat treatment is performed. When a crosslinked structure is formed in the resin by the melt processing, it is difficult to perform remelt shaping, and thus there is a drawback that its use is limited. Therefore, the development of a resin that can be remelted while having heat resistance is awaited.
【０００７】[0007]
【課題を解決するための手段】そこで、本発明者等は、
上記要望に応え得る耐熱性樹脂を開発することを目的と
して検討した結果、本発明を完成したものであり、本発
明の要旨は、一般式（１）で示される繰り返し単位を有
する耐熱性樹脂と、一般式（２）に表される重合体中の
クロロ基１モルに対し 0.5モル以上の水を反応させて一
般式（１）で示される耐熱性樹脂の製造方法にある。Therefore, the present inventors have
As a result of studies aimed at developing a heat-resistant resin that can meet the above demands, the present invention has been completed. The gist of the present invention is to provide a heat-resistant resin having a repeating unit represented by the general formula (1). The method for producing the heat resistant resin represented by the general formula (1) is the reaction of 0.5 mol or more of water with 1 mol of the chloro group in the polymer represented by the general formula (2).
【化４】 [Chemical 4]
【化５】 Embedded image
【０００８】以下、本発明をさらに詳しく説明する。The present invention will be described in more detail below.
【０００９】本発明の耐熱性樹脂は、一般式（１）で示
される構造を有している。これは、従来開発されてきた
炭素−炭素結合、あるいは、炭素−窒素結合のような炭
素系の結合を主鎖骨格とする熱硬化型樹脂に比べて、結
合エネルギーの大きいシロキサン結合（Si-O-Si ）を主
鎖骨格として有し、さらに環状構造を有するため、高い
熱安定性を発現する。また、本発明の耐熱性樹脂は熱可
塑性であることを特徴とし、再溶融賦形が可能である。The heat-resistant resin of the present invention has a structure represented by the general formula (1). This is because a siloxane bond (Si-O) having a larger bond energy than a thermosetting resin having a carbon-carbon bond or a carbon-based bond such as a carbon-nitrogen bond as a main chain skeleton that has been conventionally developed. -Si) as the main chain skeleton and further has a cyclic structure, and thus exhibits high thermal stability. Further, the heat-resistant resin of the present invention is characterized by being thermoplastic, and can be remelted and shaped.
【００１０】一般に樹脂が熱可塑性を備えたものとする
には、加熱により枝分かれを起こさない分子構造とする
ことが必要であり、本発明の耐熱性樹脂は、一般式
（１）で表される骨格を有しており、この条件を満足し
ている。本発明の耐熱性樹脂の製造方法は、とくに限定
しないが、一般式（２）に示される重合体（以下、プレ
ポリマーと称する。）を加水分解／縮合することにより
得ることが好ましい。Generally, in order for a resin to have thermoplasticity, it is necessary to have a molecular structure that does not cause branching by heating, and the heat-resistant resin of the present invention is represented by the general formula (1). It has a skeleton and satisfies this condition. The method for producing the heat resistant resin of the present invention is not particularly limited, but it is preferably obtained by hydrolyzing / condensing the polymer represented by the general formula (2) (hereinafter referred to as a prepolymer).
【００１１】一般式（２）で示されるプレポリマーの製
造方法は、特願平６−１３１９９１号公報に示されてい
るが、一般式（１）で示される構造を有する耐熱性樹脂
を得るための好ましいプレポリマーの製造方法について
以下に説明をする。A method for producing the prepolymer represented by the general formula (2) is disclosed in Japanese Patent Application No. 6-131991, but in order to obtain a heat resistant resin having a structure represented by the general formula (1). The preferred method for producing the prepolymer will be described below.
【００１２】一般式（２）で示されるプレポリマーは、
例えば、ポリ（ジフェニルシルプロピレン）（以下、原
料ポリマーと称する。）をクロロ化することによって得
られる。原料ポリマーの分子量は、 1,000〜100,000 で
あることが好ましい。この分子量が 1,000未満の原料ポ
リマーを用いると、純度向上のため原料ポリマーをメタ
ノールなどによる再沈殿処理を行なったときに溶解して
しまい、精製に供した原料ポリマーが回収できなくな
る。また、分子量が 100,000を越えた原料ポリマーを用
いると、そのフェニル基をクロロ基に置き換える反応の
際、架橋してしまうため好ましくない。より好ましい原
料ポリマーの分子量は、 2,000〜20,000である。The prepolymer represented by the general formula (2) is
For example, it can be obtained by chlorinating poly (diphenylsilpropylene) (hereinafter referred to as a raw material polymer). The molecular weight of the raw material polymer is preferably 1,000 to 100,000. If the raw material polymer having a molecular weight of less than 1,000 is used, the raw material polymer will be dissolved when reprecipitation treatment with methanol or the like is performed to improve the purity, and the raw material polymer used for purification cannot be recovered. In addition, it is not preferable to use a raw material polymer having a molecular weight of more than 100,000 because it will be crosslinked during the reaction of replacing the phenyl group with a chloro group. A more preferable raw material polymer has a molecular weight of 2,000 to 20,000.
【００１３】また、この原料ポリマー合成の際に、白金
系化合物を触媒として使用した場合は、原料ポリマー中
の残存触媒によるものと思われる着色が生じている。こ
の原料ポリマーの着色を、濾紙による濾過、あるいは再
沈殿による精製を行なって除去することは困難である。
この着色の除去は、例えば、上記原料ポリマー溶液を金
属イオンを吸着する働きのあるアルミナなどを充填した
カラムクロマトグラフィーで処理することにより行うこ
とができる。理由は明らかではないが、この原料ポリマ
ーの着色が原料ポリマーへのクロロ基の導入に際し、副
反応を引き起こす場合があるため、原料ポリマーの着色
は完全に除去するのが好ましい。Further, when a platinum compound is used as a catalyst during the synthesis of the raw material polymer, coloring which is thought to be due to the residual catalyst in the raw material polymer occurs. It is difficult to remove the coloring of the raw material polymer by filtration with filter paper or purification by reprecipitation.
The removal of the coloring can be performed by, for example, treating the raw material polymer solution by column chromatography packed with alumina or the like having a function of adsorbing metal ions. Although the reason is not clear, it is preferable to completely remove the coloring of the raw material polymer, because the coloring of the raw material polymer may cause a side reaction when the chloro group is introduced into the raw material polymer.
【００１４】Si-Cl 基を有する化合物は、一般に水によ
り容易に加水分解反応を受け、シラノール基を生成す
る。生成したシラノール基はさらに縮合し、シロキサン
結合を形成することが知られている。A compound having a Si-Cl group is generally easily hydrolyzed by water to form a silanol group. It is known that the silanol groups produced are further condensed to form siloxane bonds.
【００１５】本発明の耐熱性樹脂の合成方法は、プレポ
リマーを有機溶媒で希釈し、その溶液に水をゆっくり添
加して、加水分解／縮合反応をする方法により得ること
ができる。以下、具体的に説明する。The method for synthesizing the heat resistant resin of the present invention can be obtained by diluting the prepolymer with an organic solvent and slowly adding water to the solution to carry out a hydrolysis / condensation reaction. Hereinafter, a specific description will be given.
【００１６】本発明の耐熱性樹脂の製造方法では、ま
ず、プレポリマ−を有機溶媒で希釈してプレポリマー溶
液を調製する。ここで用いる有機溶媒は、水との親和性
が高いものを使用することが好ましく、例えばテトラヒ
ドロフラン、ジオキサンなどを用いればよい。また、こ
れら有機溶媒は、モレキュラ−シ−ブスなどの乾燥剤を
加えて脱水処理をしたり、および／または、蒸留するな
どして、十分乾燥させたものがとくに好ましい。In the method for producing a heat resistant resin of the present invention, first, a prepolymer is diluted with an organic solvent to prepare a prepolymer solution. The organic solvent used here is preferably one having a high affinity for water, such as tetrahydrofuran or dioxane. Further, it is particularly preferable that these organic solvents are sufficiently dried by adding a desiccant such as molecular sieves to dehydration treatment and / or distillation.
【００１７】プレポリマ−溶液の濃度は、プレポリマ−
溶液の重量に対して30wt％以下であることが好ましい。
30wt％を越えたプレポリマ−溶液は、水を添加したとき
に反応が急速に進み、得られる樹脂中に橋かけ反応が起
こりやすく、目的とする熱可塑性樹脂が得られない。The concentration of the prepolymer solution depends on the prepolymer.
It is preferably 30 wt% or less based on the weight of the solution.
When the prepolymer solution exceeds 30 wt%, the reaction proceeds rapidly when water is added, and a crosslinking reaction easily occurs in the obtained resin, so that the desired thermoplastic resin cannot be obtained.
【００１８】次にプレポリマー溶液に水を添加して、加
水分解／縮合反応を行い、本発明の耐熱性樹脂を得る。
この水の添加量は、プレポリマー中のSi-Cl 基１モルに
対し、 0.5モル以上、好ましくは 0.6モル以上である。
Si-Cl 基１モルに対し、 0.5モル以上加えることによ
り、賦形した成形品は強靱で優れた耐熱性を有した樹脂
を得ることができる。Si-Cl 基１モルに対し、0.5 モル
より少ない水の量では、加水分解反応が十分に進行せ
ず、これを賦形した成型品は十分な機械的強度を付与で
きない。Next, water is added to the prepolymer solution to carry out a hydrolysis / condensation reaction to obtain the heat resistant resin of the present invention.
The amount of water added is 0.5 mol or more, preferably 0.6 mol or more, based on 1 mol of the Si—Cl 2 group in the prepolymer.
By adding 0.5 mol or more with respect to 1 mol of the Si-Cl group, a shaped molded product can obtain a resin that is tough and has excellent heat resistance. If the amount of water used is less than 0.5 mol per mol of the Si-Cl group, the hydrolysis reaction will not proceed sufficiently, and the molded product formed from this will not have sufficient mechanical strength.
【００１９】また、プレポリマ−溶液に加える水の添加
量は、プレポリマ−の重量に対し、200ppm以下、さらに
好ましくは 50ppm以下である。水の含有量がプレポリマ
−に対し200ppmを越える量であると、プレポリマ−溶液
中でプレポリマ−が凝集しやすくなる。なお、好ましい
水の添加速度は、スケ−ルによって変動する。The amount of water added to the prepolymer solution is 200 ppm or less, more preferably 50 ppm or less, based on the weight of the prepolymer. If the water content is more than 200 ppm with respect to the prepolymer, the prepolymer easily aggregates in the prepolymer solution. The preferable addition rate of water varies depending on the scale.
【００２０】上記反応において、Si-Cl 基を含むプレポ
リマ−溶液に水を直接添加すると、プレポリマ−が架橋
してしまうため、水を有機溶媒で希釈したもの（以下、
混合液と称する。）を用いることが好ましい。ここで用
いる有機溶媒は、プレポリマ−を希釈するのに用いたも
のと同様、例えばテトラヒドロフラン、ジオキサンな
ど、水と親和性の高い種類のものを用いればよい。好ま
しい混合液中の水の濃度は、攪拌の程度にもよるが、急
速な架橋を防ぐ上で、有機溶媒の量に対し５wt％以下に
することが好ましい。In the above reaction, when water is directly added to the prepolymer solution containing Si-Cl groups, the prepolymer is cross-linked. Therefore, water diluted with an organic solvent (hereinafter,
It is called a mixed solution. ) Is preferably used. The organic solvent used here may be the one having a high affinity with water, such as tetrahydrofuran or dioxane, as in the case of diluting the prepolymer. The preferred concentration of water in the mixed solution depends on the degree of stirring, but is preferably 5 wt% or less with respect to the amount of the organic solvent in order to prevent rapid crosslinking.
【００２１】上記反応により得られた本発明の耐熱性樹
脂は、 300℃以上の温度で、繰り返し溶融賦形すること
ができ、その成形物は強靱であり、種々の用途に用いる
ことができる。The heat-resistant resin of the present invention obtained by the above reaction can be repeatedly melt-molded at a temperature of 300 ° C. or higher, and its molded product is tough and can be used for various purposes.
【００２２】また、本発明の耐熱性樹脂は、ベンゼン、
トルエン、クロロホルム、テトロヒドロフラン等、有機
溶媒に可溶である。The heat-resistant resin of the present invention is benzene,
It is soluble in organic solvents such as toluene, chloroform and tetrohydrofuran.
【００２３】以下、本発明を実施例により詳しく説明す
る。The present invention will be described in detail below with reference to examples.
【００２４】［参考例］（プレポリマーの製造） 乾燥した分子量約12,000のポリ（ビスジフェニルシルプ
ロピレン）11.1ｇを脱水乾燥したベンゼン 100mlに溶解
した。塩化水素ガス注入管と塩化水素ガス排出管を取り
付けた 100mlの２口ナスフラスコに該ポリマー溶液を加
え、さらに触媒として昇華精製した三塩化アルミニウム
約 0.2ｇを加えて、さらに乾燥塩化水素ガスをSi−フェ
ニル基モル数の約10倍量吹き込み、クロロ化反応を行
い、ポリ（ジクロロシルプロピレン）のベンゼン溶液を
得た。回収した該反応生成物を1H−ＮＭＲ測定した結
果、反応前はδ＝ 120〜140ppmにSi−フェニル基結合の
ピークが見られたのに対し、反応生成物はそれらのピー
クは、ほぼ完全に消失したことから（図１）、原料ポリ
マー中のフェニル基の90モル％以上がクロロ基に置換さ
れていることを確かめた。Reference Example (Production of Prepolymer) 11.1 g of dried poly (bisdiphenylsilpropylene) having a molecular weight of about 12,000 was dissolved in 100 ml of dehydrated and dried benzene. The polymer solution was added to a 100 ml 2-necked eggplant flask equipped with a hydrogen chloride gas injection pipe and a hydrogen chloride gas discharge pipe, and about 0.2 g of sublimed and purified aluminum trichloride was added as a catalyst, and dry hydrogen chloride gas was further added to Si. A benzene solution of poly (dichlorosylpropylene) was obtained by injecting an amount of about 10 times the number of moles of phenyl groups and performing a chlorination reaction. As a result of 1 H-NMR measurement of the recovered reaction product, a peak of Si-phenyl group bond was observed at δ = 120 to 140 ppm before the reaction, whereas those of the reaction product showed almost complete peaks. Since it disappeared (Fig. 1), it was confirmed that 90 mol% or more of the phenyl groups in the raw material polymer were substituted with chloro groups.
【００２５】[0025]
【実施例１】参考例で得たポリ（ジクロロシルプロピレ
ン）のベンゼン溶液40ml（ポリマー中に含まれるSi-Cl
基量；0.02mol ）をモレキュラーシーブス４Ａで脱水し
たテトラヒドロフラン 500mlに溶解した。２Ｌナスフラ
スコ中に該ポリマー溶液を加え、さらに室温下にナスフ
ラスコに水1.82ｇ（0.1mol）とピリジン4.71ｇ（0.06mo
l ）とテトラヒドロフラン 500mlの混合溶液を20時間か
けて滴下をし、加水分解を行った。該反応溶液を溶媒除
去したあと、10mlの水で洗浄することによりピリジン塩
酸塩、未反応ピリジンなどを除去した。得られた生成物
に対してさらに水10mlを加え、窒素雰囲気下90℃で加熱
した後、さらに 150℃で30分加熱することによって残留
するSi-Cl 基をほぼ完全にSi-O-Si 結合に変換した生成
物Ａを得た。得られた生成物Ａについて、ＩＲを測定し
たところ1200〜900cm-1 にシロキサン結合由来のピ−ク
（図２）が確認され、1H−ＮＭＲの測定から、ポリ（ジ
フェニルシルプロピレン）では１〜1.5ppm付近に現れた
シルエチレン由来のピ−クがそれぞれシフトし、ブロ−
ドとなっていること（図３）から、一般式（１）に示し
た六員環スピロ構造を大量に含んでいることが確かめら
れた。Example 1 40 ml of a benzene solution of poly (dichlorosylpropylene) obtained in Reference Example (Si-Cl contained in the polymer)
A base amount of 0.02 mol) was dissolved in 500 ml of tetrahydrofuran dehydrated with Molecular Sieves 4A. The polymer solution was added to a 2 L eggplant flask, and 1.82 g (0.1 mol) of water and 4.71 g (0.06 mol) of pyridine were added to the eggplant flask at room temperature.
l) and tetrahydrofuran (500 ml) were added dropwise over 20 hours for hydrolysis. After removing the solvent from the reaction solution, pyridine hydrochloride and unreacted pyridine were removed by washing with 10 ml of water. After adding 10 ml of water to the obtained product and heating it at 90 ° C in a nitrogen atmosphere, and further heating it at 150 ° C for 30 minutes, the remaining Si-Cl groups were almost completely bonded to Si-O-Si. The product A converted to was obtained. When IR of the obtained product A was measured, a peak derived from a siloxane bond (FIG. 2) was confirmed at 1200 to 900 cm −1 , and 1 H-NMR measurement showed that poly (diphenylsilpropylene) was 1 The peaks derived from silethylene, which appeared in the vicinity of ~ 1.5 ppm, were each shifted and
It is confirmed from the fact that it contains a large amount of the 6-membered ring spiro structure represented by the general formula (1) from the fact that it is in the mode (Fig. 3).
【００２６】つぎに、得られた生成物Ａを 350℃で溶融
賦形したところ強靱な板状成形物を得た。この成形物
は、ベンゼン、トルエン、クロロホルム、テトラヒドロ
フランに可溶であり、また繰り返し溶融賦形可能であっ
た。なお、得られた成形物は、ＴＧＡ分析（熱重量分
析）したところ、窒素雰囲気下の５％重量減少温度が 5
50℃であった。また、この得られた成形物を、 100℃の
沸騰水中に５分間浸漬したところ、外観、形状に全く変
化は見られなかった。このように、生成物Ａから得られ
る耐熱性樹脂は、良好な耐水性と耐熱性を有することが
わかった。Next, the obtained product A was melt-shaped at 350 ° C. to obtain a tough plate-shaped molded product. This molded product was soluble in benzene, toluene, chloroform, and tetrahydrofuran, and could be repeatedly melt-shaped. The TGA analysis (thermogravimetric analysis) of the obtained molded product revealed that the 5% weight loss temperature in a nitrogen atmosphere was 5%.
It was 50 ° C. Further, when the obtained molded product was immersed in boiling water at 100 ° C. for 5 minutes, no change in appearance or shape was observed. Thus, it was found that the heat resistant resin obtained from the product A has good water resistance and heat resistance.
【００２７】[0027]
【発明の効果】本発明の耐熱性樹脂は、優れた耐熱性、
耐水性を有し、かつ、再溶融賦形ができるため、成形時
の取り扱いが容易であり、広い用途に用いることができ
る。また、本発明の製造方法では、高耐熱性樹脂を温和
な条件下で安定に製造することができる。The heat resistant resin of the present invention has excellent heat resistance,
Since it has water resistance and can be remelted and shaped, it can be easily handled during molding and can be used for a wide range of purposes. Further, according to the production method of the present invention, the high heat resistant resin can be produced stably under mild conditions.
【図１】本発明の耐熱性樹脂の 13C−ＮＭＲのチャ−ト
である。FIG. 1 is a 13 C-NMR chart of a heat resistant resin of the present invention.
【図２】本発明の耐熱性樹脂のＩＲ（ＫＢｒ法）のチャ
ートである。FIG. 2 is an IR (KBr method) chart of the heat-resistant resin of the present invention.
【図３】本発明の耐熱性樹脂の1C−ＮＭＲのチャ−トで
ある。FIG. 3 is a 1 C-NMR chart of the heat-resistant resin of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大迫 信行 広島県大竹市御幸町20番１号三菱レイヨン 株式会社中央研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuyuki Osako 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Central Research Laboratory
Claims (2)
位を含有し、有機溶媒に可溶な耐熱性樹脂。 【化１】 1. A heat resistant resin containing a repeating unit represented by the following general formula (1) and soluble in an organic solvent. Embedded image
れるクロロ基１モルに対して 0.5モル以上の水を反応せ
しめて一般式（１）の樹脂を得ることを特徴とする請求
項１記載の耐熱性樹脂の製造方法。 【化２】 2. A resin of the general formula (1) is obtained by reacting 0.5 mol or more of water with 1 mol of a chloro group contained in the polymer represented by the general formula (2). The method for producing a heat resistant resin according to claim 1. Embedded image
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4931595A JPH08217879A (en) | 1995-02-15 | 1995-02-15 | Heat resistant resin and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4931595A JPH08217879A (en) | 1995-02-15 | 1995-02-15 | Heat resistant resin and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08217879A true JPH08217879A (en) | 1996-08-27 |
Family
ID=12827537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4931595A Pending JPH08217879A (en) | 1995-02-15 | 1995-02-15 | Heat resistant resin and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08217879A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005076031A (en) * | 2003-09-01 | 2005-03-24 | Samsung Electronics Co Ltd | Novel siloxane resin and semiconductor interlayer insulating film using the same |
| JP5013045B2 (en) * | 2004-01-16 | 2012-08-29 | Ｊｓｒ株式会社 | Method for producing polymer |
| JP5105041B2 (en) * | 2004-01-16 | 2012-12-19 | Ｊｓｒ株式会社 | Insulating film forming composition and method for producing the same, and silica-based insulating film and method for forming the same |
-
1995
- 1995-02-15 JP JP4931595A patent/JPH08217879A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005076031A (en) * | 2003-09-01 | 2005-03-24 | Samsung Electronics Co Ltd | Novel siloxane resin and semiconductor interlayer insulating film using the same |
| JP5013045B2 (en) * | 2004-01-16 | 2012-08-29 | Ｊｓｒ株式会社 | Method for producing polymer |
| JP5105041B2 (en) * | 2004-01-16 | 2012-12-19 | Ｊｓｒ株式会社 | Insulating film forming composition and method for producing the same, and silica-based insulating film and method for forming the same |
| JP5110243B2 (en) * | 2004-01-16 | 2012-12-26 | Ｊｓｒ株式会社 | Method for producing polymer |
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