JPH0345604A - Production of methyl methacrylate resin of excellent heat decomposition resistance - Google Patents
Production of methyl methacrylate resin of excellent heat decomposition resistanceInfo
- Publication number
- JPH0345604A JPH0345604A JP18155889A JP18155889A JPH0345604A JP H0345604 A JPH0345604 A JP H0345604A JP 18155889 A JP18155889 A JP 18155889A JP 18155889 A JP18155889 A JP 18155889A JP H0345604 A JPH0345604 A JP H0345604A
- Authority
- JP
- Japan
- Prior art keywords
- methyl methacrylate
- methacrylate resin
- decomposition resistance
- ozone
- heat decomposition
- 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000465 moulding Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 abstract 1
- 238000005949 ozonolysis reaction Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 11
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐熱分解性が大巾に改善されたメチルメタク
リレート系樹脂の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a methyl methacrylate resin whose thermal decomposition resistance is greatly improved.
メチルメタクリレート系樹脂は透明性、意匠性、成形加
工性に優れ、また機械的強度、耐熱性など比較的バラン
スのとれた性能を有しているため照明器具用カバー 水
槽、装飾品、雑貨、ショーウィンドウ用ガラス、自動車
用内・外装部品などの分野で使用されて会り、更に用途
開発も進められてしる。Methyl methacrylate resin has excellent transparency, design, and moldability, and has relatively well-balanced performance such as mechanical strength and heat resistance, so it can be used for covers for lighting equipment, aquariums, ornaments, miscellaneous goods, shows, etc. It is used in fields such as window glass and interior and exterior parts for automobiles, and further applications are being developed.
ところで、現在工業レベルで一生産されているメチルメ
タクリレート系樹脂は、ラジカル重合法によってしるた
め、ポリマー末端に炭素・炭素二重結合（Ｃ＝Ｃ）がポ
リマー分子当り１〜１０ ｍｏｂ ’Ｉｓ生威生成その
ため熱分解開始温度は２７０℃〜３００℃程度であり、
成型温度領域が狭く、耐熱分解性向上に対する要求には
根強しものがある。By the way, methyl methacrylate resin, which is currently produced at an industrial level, is produced by radical polymerization, so there are 1 to 10 mob'Is carbon-carbon double bonds (C=C) at the polymer end per polymer molecule. Therefore, the temperature at which thermal decomposition starts is about 270°C to 300°C,
The molding temperature range is narrow, and there is a persistent demand for improved thermal decomposition resistance.
メチルメタクリレート系樹脂の耐熱分解性向上の方法と
しては、重合触媒、重合媒体、重合温度、連鎖移動剤な
どの重合条件を変える方法が提案されている。As a method for improving the thermal decomposition resistance of methyl methacrylate resins, a method has been proposed that involves changing polymerization conditions such as the polymerization catalyst, polymerization medium, polymerization temperature, and chain transfer agent.
しかしながら、上述の提案されている方法では、得られ
るポリマーの末端二重結合の量を、ホＩＪマー分子当り
１ｍｏｔ４以下にすることができず、問題の根本的な解
決はなされていないのが現状である。However, with the above-mentioned proposed method, it is not possible to reduce the amount of terminal double bonds in the obtained polymer to 1 mot4 or less per polymer molecule, and the fundamental solution to the problem has not yet been achieved. It is.
そこで本発明者は、メチルメタクリレート系樹脂の有す
る優れた特性を保持しつつ、耐熱分解性の向上したメチ
ルメタクリレート系樹脂の製造方法を開発すべく鋭意検
討した結果、本発明に至った。Therefore, the present inventor conducted intensive studies to develop a method for producing a methyl methacrylate resin that has improved heat decomposition resistance while maintaining the excellent properties of the methyl methacrylate resin, and as a result, the present invention was achieved.
即ち、本発明はメチルメタクリレート系樹脂のポリマー
末端二重結合をオゾン処理することにより娑禦尤、カル
ボニル基又はカルボキシル基に変えることを特徴とする
耐熱分解性の優れたメチルメタクリレート系樹脂の製造
方法である。That is, the present invention provides a method for producing a methyl methacrylate resin with excellent heat decomposition resistance, which is characterized by converting the terminal double bond of the polymer of the methyl methacrylate resin into a carbonyl group or a carboxyl group by treating the polymer with ozone. It is.
本発明の製造方法は、メチルメタクリレート系樹脂を溶
媒に溶解させ、次いでオゾン処理を施し、ポリマー末端
の二重結合にオゾンを付加し、生成するオシニドを過剰
のオゾンで分解し、カルボニル基又はカルボキシル基に
変換し、末端二重結合をなくすことを特徴とする。The production method of the present invention involves dissolving methyl methacrylate resin in a solvent, then treating it with ozone, adding ozone to the double bond at the end of the polymer, decomposing the generated osinide with excess ozone, and converting it into a carbonyl group or carboxyl group. It is characterized by converting it into a group and eliminating the terminal double bond.
本発明にかいて使用されるメチルメタクリレート系樹脂
は、メチルメタクリレートを主成分とするものであり、
公知の重合方法で製造されたものであればよい。The methyl methacrylate resin used in the present invention has methyl methacrylate as its main component,
Any material may be used as long as it is produced by a known polymerization method.
メチルメタクリレート系樹脂を溶解する溶媒としては塩
化メチレン、クロロホルムなどが挙げられるが、塩化メ
チレン単独又は塩化メチレンとクロロホルムの５０１５
０ （体積）の混合溶液が好適に用いられる。ポリマー
溶液濃度は５〜５０ｆｒ′Ｊ１４、好ましくは１０〜３
０Ｍ−ｊｉ４である。Examples of solvents for dissolving methyl methacrylate resin include methylene chloride and chloroform, but methylene chloride alone or methylene chloride and chloroform 5015
A mixed solution of 0 (volume) is preferably used. Polymer solution concentration is 5-50 fr'J14, preferably 10-3
It is 0M-ji4.
また、オゾン処理条件は上記溶液を好１しくば一６０℃
以下の温度に冷却し、オゾンを含む空気を５分〜２００
分間程度通じさせることにより行なう。In addition, the ozone treatment conditions are preferably -60℃ for the above solution.
Cool to the following temperature and blow air containing ozone for 5 minutes to 200 ml.
This is done by allowing it to pass for about a minute.
上述の如くして得られた、末端二重結合がカルボニル基
又はカルボキシル基に変換された樹脂は、熱分解開始温
度が５００℃を越えるものとすることができる。The resin obtained as described above, in which the terminal double bond is converted to a carbonyl group or a carboxyl group, can have a thermal decomposition initiation temperature exceeding 500°C.
以下、実施例により本発明を更に詳細に説明するが、本
発明は実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples.
慶か、実施例中の熱分解開始温度は、第２精工社■製、
５ｓｃ−ｓｏｏｎ、τＧ−２００型を用い、熱重量分析
（ＴＧＡ）法により、重合体の１優減量温度を測定した
。Keika, the thermal decomposition start temperature in the examples is manufactured by Daini Seiko Co., Ltd.
Using a 5sc-soon, τG-200 model, the temperature at which the polymer was subjected to one weight loss was measured by thermogravimetric analysis (TGA).
実施例１
？？［のメチルメタクリレート系樹脂（三菱レイヨン■
製、アクリベットＶＨ）１０９を塩化メチレン１００−
に溶解させ、反応容器に移し、外周をドライアイス／エ
タノールで一７８℃に冷却し、１時間後オゾン含有空気
（２，Ｏｆ／ｈｒ）を６０分間通気し、更に６０分間空
気を通じた。Example 1? ? [Methyl methacrylate resin (Mitsubishi Rayon ■
Acryvet VH) 109 to methylene chloride 100-
The mixture was dissolved in water, transferred to a reaction vessel, and the outer periphery was cooled to -78°C with dry ice/ethanol. After 1 hour, ozone-containing air (2, Of/hr) was bubbled through it for 60 minutes, and air was passed through it for an additional 60 minutes.
その後塩化メチレンを蒸発させポリマーを回収した。Thereafter, methylene chloride was evaporated and the polymer was recovered.
回収したポリマーは１２０℃で８時間真空乾燥し、ＴＧ
Ａ分析用試料とした。結果を表−１に示した。The recovered polymer was vacuum dried at 120°C for 8 hours, and TG
This was used as a sample for analysis A. The results are shown in Table-1.
実施例２〜６、比較例１
オゾン通気時間を変えた以外は、実施例１と同様に実験
を行なった。結果を表−１に示す。Examples 2 to 6, Comparative Example 1 An experiment was conducted in the same manner as in Example 1, except that the ozone ventilation time was changed. The results are shown in Table-1.
表
〔発明の効果〕
本発明の方法によれば、メチルメタクリレート系樹脂の
耐熱分解性を大巾に改善することができ、成形温度域が
広がるとともに高温領域での使用を可能とするため、工
業上優れた効果を奏する。Table [Effects of the Invention] According to the method of the present invention, the heat decomposition resistance of methyl methacrylate resin can be greatly improved, the molding temperature range is expanded, and use in high temperature ranges is possible. It has excellent effects.
Claims (1)
ン処理することにより、カル ボニル基又はカルボキシル基に変えることを特徴とする
耐熱分解性の優れたメチルメタクリレート系樹脂の製造
方法。[Scope of Claims] A method for producing a methyl methacrylate resin having excellent heat decomposition resistance, which comprises converting the molecular terminal double bond of the methyl methacrylate resin into a carbonyl group or a carboxyl group by treating it with ozone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18155889A JPH0345604A (en) | 1989-07-13 | 1989-07-13 | Production of methyl methacrylate resin of excellent heat decomposition resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18155889A JPH0345604A (en) | 1989-07-13 | 1989-07-13 | Production of methyl methacrylate resin of excellent heat decomposition resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0345604A true JPH0345604A (en) | 1991-02-27 |
Family
ID=16102890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18155889A Pending JPH0345604A (en) | 1989-07-13 | 1989-07-13 | Production of methyl methacrylate resin of excellent heat decomposition resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0345604A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5571907A (en) * | 1990-12-07 | 1996-11-05 | Hawaiian Sugar Planters' Association | Epoxy monomers from sucrose |
| DE19520840B4 (en) * | 1994-06-20 | 2007-03-29 | Sergeij Pavlovič Prof. Prokoptšuk | Process for the preparation of modified polymers |
-
1989
- 1989-07-13 JP JP18155889A patent/JPH0345604A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5571907A (en) * | 1990-12-07 | 1996-11-05 | Hawaiian Sugar Planters' Association | Epoxy monomers from sucrose |
| DE19520840B4 (en) * | 1994-06-20 | 2007-03-29 | Sergeij Pavlovič Prof. Prokoptšuk | Process for the preparation of modified polymers |
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