WO1997024384A1 - Process for the preparation of stabilized polyacetal resin - Google Patents
Process for the preparation of stabilized polyacetal resin Download PDFInfo
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- WO1997024384A1 WO1997024384A1 PCT/JP1996/003879 JP9603879W WO9724384A1 WO 1997024384 A1 WO1997024384 A1 WO 1997024384A1 JP 9603879 W JP9603879 W JP 9603879W WO 9724384 A1 WO9724384 A1 WO 9724384A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/30—Chemical modification by after-treatment
Definitions
- the present invention relates to a method for producing a stabilized polyacetal resin. More specifically, the present invention relates to a method for producing a stable polyacetal resin by removing unstable terminals of a crude polyacetal copolymer after polymerization.
- the polyacetal resin can be obtained as a homopolymer or a copolymer by polymerizing trioxane alone or trioxane and cyclic ether in the presence of an acidic catalyst.
- resins called copolymers include some that have unstable terminals, and when decomposed during injection molding or the like, formaldehyde gas is generated and adheres and accumulates on molds. It is known to cause a worsening of the work environment. Therefore, in general, in the step of removing carboxyl used after decomposing and removing the unstable terminal, a weakly basic compound represented by an aqueous solution of triethylamine or the like is used as an aqueous solution or as it is.
- the present inventors have conducted intensive studies to solve the above problems, and as a result, by adding a boric acid compound to a crude polyacetal copolymer and melt-kneading it, almost no reduction in molecular weight was caused.
- the inventors have found a method for removing an unstable terminal, and have completed the present invention.
- the present invention relates to a method of adding (B) 0.001 to 1 part by weight of a boric acid compound to 100 parts by weight of a crude polyacetal copolymer having an unstable terminal portion and reducing the amount of the unstable terminal portion by melt-kneading. This is a method for producing a stabilized polyacetal resin.
- the (A) crude polyacetylene copolymer of the present invention is obtained by copolymerizing trioxane as a main monomer, using cyclic ether or cyclic formal as a comonomer, and using an acidic catalyst as a polymerization initiator.
- Cyclic ether or cyclic formal is a cyclic compound having at least one pair of a connecting carbon atom and an oxygen atom represented by the following general formula.
- Rt, R 2 , R 3 and R 4 represent a hydrogen atom or an alkyl group, which may be the same or different, but are generally a hydrogen atom.
- R 5 is a methylene group or oxymethylene Group, methylene group or oxymethylene group substituted by an alkyl group (in this case, p represents an integer of 0 to 3) or a formula
- comonomers include ethylene oxide, 1,3-dioxolan, 1,3-trioxepane, diethylene glycol formal, 1,4-butanediol formal, 1,3-dioxane, propylene oxide and the like.
- preferred comonomers are ethylene oxide, 1,3-dioxolan, 1,4-butanediol formal, and diethylene glycol formal.
- the amount used is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on trioxane.
- an appropriate molecular weight regulator may be used if necessary.
- the polymerization catalyst is deactivated by an ordinary method.
- the (A) crude polyacetylene copolymer thus obtained partially contains an unstable terminal portion and has the above-mentioned problems.
- the present invention is characterized in that (A) a crude polyacetal copolymer is added with (B) a boric acid compound and melt-kneaded, whereby the unstable terminal is removed with almost no decrease in molecular weight. .
- boric acid compound (B) used in the present invention examples include: boric acids such as orthoboric acid, metaboric acid and tetraboric acid; boron oxides such as diboron trioxide; metal salts of boric acid; And esters with aliphatic alcohols.
- boric acids such as orthoboric acid, metaboric acid and tetraboric acid
- boron oxides such as diboron trioxide
- metal salts of boric acid And esters with aliphatic alcohols.
- orthoboric acid, metaboric acid, tetraboric acid and diboron trioxide, alkali metal borates, and alkaline earth metal borates have high effects and are preferably used.
- Commercially available boric compounds can be used, and there is no particular limitation on the particle size and the like.
- the amount of the boric acid compound as the component (B) is 0.001 to 1 part by weight, preferably 0.005 to 0.5 part by weight, more preferably 0.5 to 0.5 part by weight, per 100 parts by weight of the crude polyacetal copolymer (A). 01 to 0.2 parts by weight. If the amount is too small, the effect of removing the unstable terminal, which is the object of the present invention, cannot be sufficiently obtained, and if the amount is too large, the acidity becomes too high and the molecular weight decreases. May be rubbed.
- the addition of (C) an antioxidant in combination with (B) a boric acid compound is a preferable method for suppressing the decomposition of the polyacetal resin during melt-kneading.
- the antioxidant a sterically hindered phenol compound, a sterically hindered amine compound, a phosphorus-based compound, a sulfur-based compound and the like are not particularly limited, but a sterically hindered phenol compound is more effective.
- Examples of such compounds include sterically hindered phenol compounds such as triethyleneglycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and pentaerythrityl-tetrakis. [3- (3,5-z-t-butyl-4-hydroxyphenyl) probionate] and 2,2'-methylen-bis (4-methyl-6-t-butyl pentanol) and the like are sterically hindered.
- Examples of phosphorus compounds include 41-acetoxy-1,2,6,6-tetramethylpiperidine and 4-stearoyloxy-2,2,4,6-tetramethylpiperidine.
- Tetrakis (2,4-di-tert-butylphenyl) -1,4,4-bisphenylenephosphonite, distearylpentaerythritol diphosphite, etc. are sulfur compounds. And dilauryl thiodipropionate.
- the addition amount is preferably 0.01 to 3 parts by weight, particularly preferably 0.03 to 1 part by weight, per 100 parts by weight of the crude polyacetal copolymer (A). If the amount is less than 0.01 parts by weight, the effect of suppressing the decomposition of the polyacetal resin is small, and if the amount is more than 3 parts by weight, the effect of increasing the amount is not observed, which is economically disadvantageous. .
- the melt-kneading method of the present invention is carried out by adding the above-mentioned boric acid compound and, in some cases, an antioxidant to a crude copolymer which has been subjected to a catalyst deactivation treatment, preferably a pulverized treatment.
- a catalyst deactivation treatment preferably a pulverized treatment.
- the equipment and conditions used but preferably, after adding the boric acid compound to the crude copolymer, it is fed to a single or twin screw extruder or mixer, A method is used in which the mixture is heated or melted and kneaded dynamically or statically while heating to 170 to 230 ° C and sucking out generated gas using a venting device.
- various stabilizers and filler sugar components are further added to the polyester resin stabilized by removing the unstable terminal portion by the method of the present invention as described above.
- a stabilizer or filler is added to the latter half of the same apparatus, and the product is melted in one melting step. Can also be manufactured.
- a boric acid compound and optionally an antioxidant were added to the crude copolymer at the ratios shown in Tables 1 and 2, and the mixture was supplied to a vented twin-screw extruder.
- the melt was continuously processed under the condition of a vacuum of 450 mmHg in the vent area to obtain the final product.
- 1 g of the copolymer is placed in 100 ml of an aqueous solution containing 0.5 g of ammonia and 50% methanol, heated in a closed container for 170 and 45 minutes, and quantitatively analyzed for the amount of formaldehyde decomposed and eluted in the solution And expressed as a percentage by weight relative to the polymer. This amount was defined as the amount of unstable terminal abundance.
- the melted copolymer is melted, and the resin discharged under a load is molded into a plate with a thickness of about three jobs sandwiched between glass plates.
- the b value was measured using a colorimeter.
- C-1 triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate)
- C-2 pentaerythrityl-tetrakis [3- (3,5-di- Butyl 4-propenylate)
- D-1 triethylamine
- C1 Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxypropyl) propionate]
- C-2 Pentaerythrityl-tetrakis [3- (3.5-t-butyl-4 Droxyphenyl) propionate]
- D-1 Triethylamine
- the obtained polyacetal resin has higher whiteness, fewer unstable parts, and melts compared to the conventional method. Since the decrease in molecular weight during processing is small, the processing efficiency is high and the final product obtained has high thermal stability.
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Abstract
A stable polyacetal resin is prepared by adding 0.001 to 1 part by weight of (B) a boric acid compound to 100 parts by weight of (A) a crude polyacetal copolymer having unstable terminal moieties, and melt-kneading the resulting mixture to decrease the content of the unstable terminal moieties.
Description
明細書 安定化ポリァセタール樹脂の製造法 発明の背景 Description Method for producing stabilized polyacetal resin Background of the Invention
発明の分野 Field of the invention
本発明は安定化ポリアセタール樹脂の製造法に関する。 更に詳細には、 重合後 の粗ポリァセタールコポリマーの不安定末端を除去して、 安定なポリァセタール 樹脂を製造する方法に関するものである。 The present invention relates to a method for producing a stabilized polyacetal resin. More specifically, the present invention relates to a method for producing a stable polyacetal resin by removing unstable terminals of a crude polyacetal copolymer after polymerization.
関連技術の記述 Description of related technology
ポリアセタール樹脂は、 トリオキサン単独、 或いは卜リオキサンと環状エーテ ル等を酸性触媒の存在下で重合させることにより、 ホモポリマー又はコポリマー として得られる。 そのうちコポリマーと呼ばれる樹脂は、 不安定な末端部を有す るものを一部含んでおり、 射出成形時等にお 、て分解するとホルムアルデヒドガ スを発生して、 金型に付着堆積したり、 作業環境を悪化させたりする原因となる ことが知られている。 従って、 一般にはその不安定末端を分解除去した後に使用 されるカ^ その除去工程においてはトリェチルアミンの水溶液等に代表される弱 塩基性の化合物を水溶液またはそのままで用いることが行われている。 The polyacetal resin can be obtained as a homopolymer or a copolymer by polymerizing trioxane alone or trioxane and cyclic ether in the presence of an acidic catalyst. Among them, resins called copolymers include some that have unstable terminals, and when decomposed during injection molding or the like, formaldehyde gas is generated and adheres and accumulates on molds. It is known to cause a worsening of the work environment. Therefore, in general, in the step of removing carboxyl used after decomposing and removing the unstable terminal, a weakly basic compound represented by an aqueous solution of triethylamine or the like is used as an aqueous solution or as it is.
しかしながら、 このような塩基性化合物の使用はしばしばポリァセタール樹脂 に着色をもたらし、 また、 不安定末端除去効果が十分でなく、 更にはポリマーを 溶融させた時の主鎖の熱分解を防止する働きがないので、 分子量低下を避けるこ とができなかった。 発明の開示 However, the use of such a basic compound often causes coloration of the polyacetal resin, has an insufficient effect of removing unstable terminals, and further has a function of preventing thermal decomposition of the main chain when the polymer is melted. No molecular weight reduction could be avoided. Disclosure of the invention
発明の概要
本発明者等は、 上記の如き問題点を解決すべく鋭意検討を行った結果、 粗ポリ ァセタールコポリマ一にホウ酸化合物を添加し溶融混練することによって、 分子 量低下をほとんど引き起こすことなく、 不安定末端を除去する方法を見出し、 本 発明を完成するに至ったものである。 Summary of the Invention The present inventors have conducted intensive studies to solve the above problems, and as a result, by adding a boric acid compound to a crude polyacetal copolymer and melt-kneading it, almost no reduction in molecular weight was caused. The inventors have found a method for removing an unstable terminal, and have completed the present invention.
即ち本発明は、 （A) 不安定末端部分を有する粗ポリアセタールコポリマー 100 重量部に（B) ホウ酸化合物 0.001〜1重量部を添加し、 溶融混練処理して不安定 末端部分を減少させることを特徴とする安定化ポリァセタール樹脂の製造法であ る。 That is, the present invention relates to a method of adding (B) 0.001 to 1 part by weight of a boric acid compound to 100 parts by weight of a crude polyacetal copolymer having an unstable terminal portion and reducing the amount of the unstable terminal portion by melt-kneading. This is a method for producing a stabilized polyacetal resin.
発明の詳細な説明 Detailed description of the invention
以下本発明についての詳細な説明を行う。 Hereinafter, the present invention will be described in detail.
本発明の（A) 粗ポリアセ夕一ルコポリマーとは、 トリオキサンを主モノマーと し、 環状エーテル又は環状ホルマ一ルをコモノマーに使用し、 酸性触媒を重合開 始剤として共重合することによって得られる。 環状エーテル、 或いは、 環状ホル マールは、 下記一般式で表される少なくとも一組の連結炭素原子と酸素原子を有 する環状化合物である。
The (A) crude polyacetylene copolymer of the present invention is obtained by copolymerizing trioxane as a main monomer, using cyclic ether or cyclic formal as a comonomer, and using an acidic catalyst as a polymerization initiator. . Cyclic ether or cyclic formal is a cyclic compound having at least one pair of a connecting carbon atom and an oxygen atom represented by the following general formula.
I ！ I!
R「C- (Rs)pR `` C- (R s ) p
(式中、 Rt、 R2、 R3及び R4は水素原子又はアルキル基を意味し、 各々同一でも異 なっていてもよいが、 一般には水素原子である。 R5はメチレン基、 ォキシメチレ ン基、 アルキル基で置換されたメチレン基もしくはォキシメチレン基 （この場合 、 p は 0〜 3の整数を表す） 或いは式 (Wherein, Rt, R 2 , R 3 and R 4 represent a hydrogen atom or an alkyl group, which may be the same or different, but are generally a hydrogen atom. R 5 is a methylene group or oxymethylene Group, methylene group or oxymethylene group substituted by an alkyl group (in this case, p represents an integer of 0 to 3) or a formula
-(CH2)q- 0CH2_又は-（0-CH2-CH2)q-0CH2-
で表される二価の基 （この場合、 P は 1、 q は 1〜4の整数を表す） を意味する。 ） かかるコモノマーとしては、 例えばエチレンォキシド、 1, 3 —ジォキソラン、 1, 3 —トリオキセパン、 ジエチレングリコールホルマール、 1, 4 一ブタンジォー ルホルマール、 1, 3 —ジォキサン、 プロピレンォキシド等があげられる。 中でも 好ましいコモノマーは、 エチレンォキシド、 1, 3 —ジォキソラン、 1, 4 一ブタン ジオールホルマール、 ジエチレングリコールホルマール、 である。 その使用量は 卜リオキサンに対して 0. 1〜10重量％、 好ましくは 0. 2〜5重量％でぁる。 又、 ポリァセタール共重合体の分子量調節のために、 必要ならば適当な分子量調節剤 を使用しても良い。 -(CH 2 ) q -0CH 2 _ or-(0-CH 2 -CH 2 ) q -0CH 2- (In this case, P represents 1 and q represents an integer of 1 to 4). Examples of such comonomers include ethylene oxide, 1,3-dioxolan, 1,3-trioxepane, diethylene glycol formal, 1,4-butanediol formal, 1,3-dioxane, propylene oxide and the like. Among them, preferred comonomers are ethylene oxide, 1,3-dioxolan, 1,4-butanediol formal, and diethylene glycol formal. The amount used is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on trioxane. In order to control the molecular weight of the polyacetal copolymer, an appropriate molecular weight regulator may be used if necessary.
上記の如くコポリマー重合後、 常法により重合触媒の失活化が行われる。 After the copolymerization as described above, the polymerization catalyst is deactivated by an ordinary method.
このようにして得られた（A) 粗ポリアセ夕一ルコポリマーは、 不安定な末端部 を有するものを一部含んでおり、 前述の如き問題点を有するものである。 The (A) crude polyacetylene copolymer thus obtained partially contains an unstable terminal portion and has the above-mentioned problems.
そこで本発明では、 （A) 粗ポリアセタールコポリマーに（B) ホウ酸化合物を添 加し溶融混練することによって、 分子量低下をほとんど引き起こすことなく、 不 安定末端を除去することを特徴とするものである。 Thus, the present invention is characterized in that (A) a crude polyacetal copolymer is added with (B) a boric acid compound and melt-kneaded, whereby the unstable terminal is removed with almost no decrease in molecular weight. .
本発明に用いる（B) 成分のホウ酸化合物としては、 オルトホウ酸、 メタホウ酸、 四ホウ酸等のホウ酸類、 三酸化二ホウ素等の酸化ホウ素類、 ホウ類酸の金属塩、 脂肪族 '芳香族アルコールとのエステル類などが挙げられる。 中でも、 オルトホ ゥ酸、 メタホウ酸、 四ホウ酸及び三酸化二ホウ素、 アルカリ金属ホウ酸塩、 アル カリ土類金属ホウ酸塩は効果が高く、 好ましく用いられる。 これらのホウ酸化合 物は市販品を用いることが出来、 粒径等に特に制限はない。 Examples of the boric acid compound (B) used in the present invention include: boric acids such as orthoboric acid, metaboric acid and tetraboric acid; boron oxides such as diboron trioxide; metal salts of boric acid; And esters with aliphatic alcohols. Among them, orthoboric acid, metaboric acid, tetraboric acid and diboron trioxide, alkali metal borates, and alkaline earth metal borates have high effects and are preferably used. Commercially available boric compounds can be used, and there is no particular limitation on the particle size and the like.
(B) 成分のホウ酸化合物の添加量は、 （A) 粗ポリアセタールコポリマー 100重 量部に対し 0· 001~ 1重量部、 好ましくは 0. 005〜0. 5 重量部、 更に好ましくは 0. 01 〜0. 2 重量部である。 過少の場合は本発明の目的とする不安定末端の除去 効果が充分得られず、 また過大であると酸性度が増しすぎて分子量低下を弓 Iき起
こす場合がある。 The amount of the boric acid compound as the component (B) is 0.001 to 1 part by weight, preferably 0.005 to 0.5 part by weight, more preferably 0.5 to 0.5 part by weight, per 100 parts by weight of the crude polyacetal copolymer (A). 01 to 0.2 parts by weight. If the amount is too small, the effect of removing the unstable terminal, which is the object of the present invention, cannot be sufficiently obtained, and if the amount is too large, the acidity becomes too high and the molecular weight decreases. May be rubbed.
本発明では必ずしも必須とされる成分ではないが、 （C) 酸化防止剤を（B) ホウ 酸化合物と併用添加することは、 溶融混練時におけるポリアセタール樹脂の分解 を抑制する上で、 好ましい方法である。 この酸化防止剤としては、 立体障害性フ ェノール化合物、 立体障害性ァミン化合物、 リン系化合物、 硫黄系化合物などが 使用でき特に制限はないが、 立体障害性フェノール化合物がより効果的である。 このような化合物の例を挙げると、 立体障害性フエノール化合物としては、 トリ エチレングリコール一ビス 〔3— ( 3 - tーブチルー 5—メチルー 4ーヒ ドロキ シフエ二ル） プロピオネート〕 、 ペンタエリスリチルーテトラキス 〔3— (3, 5 ージー t—ブチルー 4 一ヒ ドロキシフヱニル） プロビオネ一ト〕 、 2, 2'—メチレ ンービス一 （4—メチル— 6— t 一プチルーフヱノール） 等が、 立体障害性ァミ ン化合物としては、 4一ァセ卜キシ一 2, 2. 6, 6 —テトラメチルピペリジン、 4— ステアロイルォキシ— 2, 2, 4, 6 —テトラメチルピペリジン等が、 リン系化合物と しては、 テトラキス （2, 4 —ジー t—ブチルフエニル） 一 4， 4 —ビスフヱニレン ホスホナイ ト、 ジステアリルペンタエリスリ トールジホスフアイ 卜等が、 硫黄系 化合物としては、 ジラウリルチオジプロビオネ一ト等である。 Although not an essential component in the present invention, the addition of (C) an antioxidant in combination with (B) a boric acid compound is a preferable method for suppressing the decomposition of the polyacetal resin during melt-kneading. is there. As the antioxidant, a sterically hindered phenol compound, a sterically hindered amine compound, a phosphorus-based compound, a sulfur-based compound and the like are not particularly limited, but a sterically hindered phenol compound is more effective. Examples of such compounds include sterically hindered phenol compounds such as triethyleneglycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and pentaerythrityl-tetrakis. [3- (3,5-z-t-butyl-4-hydroxyphenyl) probionate] and 2,2'-methylen-bis (4-methyl-6-t-butyl pentanol) and the like are sterically hindered. Examples of phosphorus compounds include 41-acetoxy-1,2,6,6-tetramethylpiperidine and 4-stearoyloxy-2,2,4,6-tetramethylpiperidine. Tetrakis (2,4-di-tert-butylphenyl) -1,4,4-bisphenylenephosphonite, distearylpentaerythritol diphosphite, etc. are sulfur compounds. And dilauryl thiodipropionate.
(C) 成分の酸化防止剤を併用する場合の添加量は、 （A) 粗ポリアセタールコポ リマ一 100重量部に対し 0. 01〜 3重量部が好ましく、 特に好ましくは 0. 03〜1重 量部である 0. 01 重量部より過少の場合はポリアセタール樹脂の分解を抑制する 効果が小さく、 また 3重量部より過大に添加しても増量の影響が見られず、 経済 的にも不利となる。 When the antioxidant of the component (C) is used in combination, the addition amount is preferably 0.01 to 3 parts by weight, particularly preferably 0.03 to 1 part by weight, per 100 parts by weight of the crude polyacetal copolymer (A). If the amount is less than 0.01 parts by weight, the effect of suppressing the decomposition of the polyacetal resin is small, and if the amount is more than 3 parts by weight, the effect of increasing the amount is not observed, which is economically disadvantageous. .
本発明の溶融混練処理方法は、 触媒失活処理がなされた、 好ましくは粉砕処理 された粗共重合体に、 上記ホゥ酸化合物と場合によつては酸化防止剤を添加して 行われる。 使用される装置、 条件等に特に制限はないが、 好ましくは、 粗共重合 体にホウ酸化合物を添加した後、一軸又は二軸の押出機或いはミキサーに供給し、
170〜230 °Cに加熱し、 ベン卜装置を使って発生するガスを吸引しながら、 動的 或いは静的に溶融混練する方法が用いられる。 The melt-kneading method of the present invention is carried out by adding the above-mentioned boric acid compound and, in some cases, an antioxidant to a crude copolymer which has been subjected to a catalyst deactivation treatment, preferably a pulverized treatment. There are no particular restrictions on the equipment and conditions used, but preferably, after adding the boric acid compound to the crude copolymer, it is fed to a single or twin screw extruder or mixer, A method is used in which the mixture is heated or melted and kneaded dynamically or statically while heating to 170 to 230 ° C and sucking out generated gas using a venting device.
上記の如き本発明の方法により不安定末端部分が除去され安定化されたポリァ セ夕一ル樹脂には、 一般には目的に応じた各種の安定剤や充填剤糖の成分が更に 配合される。 かかる成分を配合するにあたっては、 不安定末端部分が除去された 溶融状態のポリアセタール樹脂を一旦冷却してペレツト等にして取り出し、 これ に各種成分を混合して再度溶融混練する方法が一般的であるが、一軸又は二軸の 押出機を用いた場合には、 本発明の溶融処理に続いて、 同じ装置内の後半部に安 定剤又は充填剤を添加して、 一回の溶融行程で製品を製造することもできる。 Generally, various stabilizers and filler sugar components according to the purpose are further added to the polyester resin stabilized by removing the unstable terminal portion by the method of the present invention as described above. When compounding such components, it is common practice to once cool the polyacetal resin from which the unstable terminal portions have been removed, remove it into a pellet, etc., mix it with various components, and melt-knead again. However, when a single-screw or twin-screw extruder is used, following the melt processing of the present invention, a stabilizer or filler is added to the latter half of the same apparatus, and the product is melted in one melting step. Can also be manufactured.
実施例 Example
以下、 実施例により、 本発明を具体的に説明するが、 本発明はこれに限定され るものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.
実施例 1〜11及び比較例 1〜10 Examples 1 to 11 and Comparative Examples 1 to 10
コモノマ一として 1, 3 —ジォキソランを 3重量％含むトリオキサンに、 三フッ 化ホウ素ブチルエーテラートを全モノマ一に対して 60ppm添加し、 ジャケット温 度 80°Cにて二軸の連続式混合反応機で重合させた。 吐出口から排出された反応生 成物に直ちに、 トリェチルァミンの 0. 1重量％水溶液を添加し 60分間室温下で攪 拌した。 その後遠心分離し、 110°Cで乾燥して粗共重合体を得た。 To trioxane containing 3% by weight of 1,3-dioxolane as a comonomer, boron trifluoride butyl etherate was added at 60 ppm based on all monomers, and a biaxial continuous mixing reactor at a jacket temperature of 80 ° C. And polymerized. Immediately, a 0.1% by weight aqueous solution of triethylamine was added to the reaction product discharged from the discharge port, and the mixture was stirred at room temperature for 60 minutes. Thereafter, the mixture was centrifuged and dried at 110 ° C to obtain a crude copolymer.
この粗共重合体に対して、 表 1及び表 2に示す割合で、 ホウ酸化合物と場合に よって酸化防止剤を加え、 ベント付き二軸押出し機に供給して、 ヒータ一温度 200°C、 ベント部真空度 - 450mmHg の条件下で連続的に溶融処理を行い、 最終生成 物を得た。 A boric acid compound and optionally an antioxidant were added to the crude copolymer at the ratios shown in Tables 1 and 2, and the mixture was supplied to a vented twin-screw extruder. The melt was continuously processed under the condition of a vacuum of 450 mmHg in the vent area to obtain the final product.
比較のため、 ホウ酸化合物を添加しない場合と他の添加物を使用した場合につ いても同様の処理を行った。 For comparison, the same treatment was performed when no boric acid compound was added and when another additive was used.
これらのものについて、 下記の評価を行った。 結果をあわせて表 1及び表 2に
示す。 The following evaluation was performed for these materials. The results are shown in Tables 1 and 2. Show.
〔評価項目〕 〔Evaluation item〕
くメノレトインデックス > Kumenoleto Index>
190°C、 荷重 2160 gで測定したメルトインデックスの値 〔g Z10分〕 を分子量 に対応する特性値として評価した。 The value of the melt index [g Z10 minutes] measured at 190 ° C under a load of 2160 g was evaluated as a characteristic value corresponding to the molecular weight.
<ァルカリ分解率 > <Alkali decomposition rate>
共重合体 1 gを、 0. 5 gのアンモニアと 50%のメタノールを含む水溶液 100ml に入れ、 密閉容器中で 170 、 45分間加熱した後、 液中に分解溶出したホルムァ ルデヒドの量を定量分析し、 重合物に対する重量％で示した。 この量を不安定末 端存在量とした。 1 g of the copolymer is placed in 100 ml of an aqueous solution containing 0.5 g of ammonia and 50% methanol, heated in a closed container for 170 and 45 minutes, and quantitatively analyzed for the amount of formaldehyde decomposed and eluted in the solution And expressed as a percentage by weight relative to the polymer. This amount was defined as the amount of unstable terminal abundance.
<黄色度〉 <Yellowness>
前述のメルトインデックス評価と同様の条件、 方法で、 溶融処理後の共重合体 を溶融させ、 荷重をかけて吐出させた樹脂を、 ガラス板に挟んで厚さ約 3職の板 状物に成形し、 測色計を用いて b値を測定した。
Under the same conditions and method as the melt index evaluation described above, the melted copolymer is melted, and the resin discharged under a load is molded into a plate with a thickness of about three jobs sandwiched between glass plates. The b value was measured using a colorimeter.
*1 メルトインデックス： 9.4 、 アルカリ分解率 =1.2%、 黄色度 =】.5 * 1 Melt index: 9.4, Alkali decomposition rate = 1.2%, Yellowness =】. 5
13 1：オルトホウ酸 13 1: orthoboric acid
13-2：四ホウ酸 13-2: Tetraboric acid
B-3：ホウ酸ナトリウム B-3: Sodium borate
C-1： トリエチレングリコール—ビス 〔 3— (3 - t -プチル- 5ーメチル- 4—ヒドロキシフヱニル） プロピオネート） C-2：ペンタエリスリチルーテトラキス 〔3— (3,5 ージ— い プチルー 4 - ヒドロキシフエニル） プロピオネート〕 D- 1： 卜リエチルァミン C-1: triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate) C-2: pentaerythrityl-tetrakis [3- (3,5-di- Butyl 4-propenylate) D-1: triethylamine
D-2：炭酸ナトリウム
D-2: Sodium carbonate
表 2 Table 2
oooo
*1 メノレトインデックス = 9.4 、 アルカリ分解率 =1.2%、 黄色度 = 1.5 * 1 Menoleto index = 9.4, alkali decomposition rate = 1.2%, yellowness = 1.5
B-1： オルトホウ酸 B-1: Orthoboric acid
B-2： 四ホウ酸 B-2: Tetraboric acid
B-3： ホウ酸ナ卜リゥム B-3: sodium borate
C 1： トリエチレングリコール—ビス [3— （3— t -ブチルー 5—メチル— 4ーヒ ドロキシフヱニル） プロピオネート〕 C-2： ペンタエリスリチルーテトラキス 〔 3— (3.5 ージー t一プチル— 4ーヒ ドロキシフヱニル） プロピオネート〕 D-1： トリエチルァミン C1: Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxypropyl) propionate] C-2: Pentaerythrityl-tetrakis [3- (3.5-t-butyl-4 Droxyphenyl) propionate] D-1: Triethylamine
D-2：炭酸ナトリウム
D-2: Sodium carbonate
表 1及び表 2に示した結果からも明らかなように、 本発明の方法によれば、 従 来の方法と比較して、 得られるポリアセタール樹脂の白色度が高く、 不安定部分 が少なく、 溶融処理中の分子量低下も小さいので、 処理効率が高く、 また、 得ら れる最終製品の熱安定性も高い。
As is evident from the results shown in Tables 1 and 2, according to the method of the present invention, the obtained polyacetal resin has higher whiteness, fewer unstable parts, and melts compared to the conventional method. Since the decrease in molecular weight during processing is small, the processing efficiency is high and the final product obtained has high thermal stability.
Claims
1 . (A) 不安定末端部分を有する粗ポリアセタールコポリマー 100重量部に (B) ホウ酸化合物 0. 001〜 1重量部を添加し、 溶融混練処理して不安定末端部分 を減少させることを特徴とする安定化ポリァセタール樹脂の製造法。 1. It is characterized in that 0.001 to 1 part by weight of (B) boric acid compound is added to 100 parts by weight of crude polyacetal copolymer (A) having an unstable terminal part, and melt kneading treatment is performed to reduce the unstable terminal part. A method for producing a stabilized polyacetal resin.
2 . (A) 成分、 （B) 成分に加え（C) 成分として酸化防止剤 0. 01〜3重量部 (対 (A) 成分 100重量部） を添加することを特徴とする請求項 1記載の安定化ポ リアセタール樹脂の製造法。 2. The method according to claim 1, wherein 0.01 to 3 parts by weight of an antioxidant (100 parts by weight of the component (A)) is added as the component (C) in addition to the component (A) and the component (B). A method for producing a stabilized polyacetal resin.
3 . (B) ホウ酸化合物が、 オルトホウ酸、 メタホウ酸、 四ホウ酸、 三酸化二 ホウ素、 ホウ酸類の金属塩から選ばれた少なくとも一種である請求項 1記載の安 定化ポリァセタール樹脂の製造法。
3. The production of the stabilized polyacetal resin according to claim 1, wherein the (B) boric acid compound is at least one selected from orthoboric acid, metaboric acid, tetraboric acid, diboronic trioxide, and metal salts of boric acids. Law.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34040695A JPH09176446A (en) | 1995-12-27 | 1995-12-27 | Production of stabilized polyacetal resin |
| JP7/340406 | 1995-12-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997024384A1 true WO1997024384A1 (en) | 1997-07-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1996/003879 WO1997024384A1 (en) | 1995-12-27 | 1996-12-27 | Process for the preparation of stabilized polyacetal resin |
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| JP (1) | JPH09176446A (en) |
| WO (1) | WO1997024384A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8354495B2 (en) | 2008-04-16 | 2013-01-15 | Ticona Gmbh | Process for the preparation of oxymethylene polymers and apparatus suitable for this purpose |
| US8993709B2 (en) | 2011-07-15 | 2015-03-31 | Ticona Gmbh | Process for producing oxymethylene polymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1143583A (en) * | 1997-07-28 | 1999-02-16 | Polyplastics Co | Polyoxymethylene composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02283709A (en) * | 1989-04-25 | 1990-11-21 | Toray Ind Inc | Production of stabilized oxymethylene copolymer |
| JPH0570538A (en) * | 1991-09-13 | 1993-03-23 | Toray Ind Inc | Production of oxymethylene copolymer |
| JPH0733953A (en) * | 1993-07-23 | 1995-02-03 | Mitsubishi Gas Chem Co Inc | Polyacetal resin composition |
| JPH07233231A (en) * | 1993-12-28 | 1995-09-05 | Asahi Chem Ind Co Ltd | Method of stabilizing terminal of oxymethylene copolymer |
-
1995
- 1995-12-27 JP JP34040695A patent/JPH09176446A/en active Pending
-
1996
- 1996-12-27 WO PCT/JP1996/003879 patent/WO1997024384A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02283709A (en) * | 1989-04-25 | 1990-11-21 | Toray Ind Inc | Production of stabilized oxymethylene copolymer |
| JPH0570538A (en) * | 1991-09-13 | 1993-03-23 | Toray Ind Inc | Production of oxymethylene copolymer |
| JPH0733953A (en) * | 1993-07-23 | 1995-02-03 | Mitsubishi Gas Chem Co Inc | Polyacetal resin composition |
| JPH07233231A (en) * | 1993-12-28 | 1995-09-05 | Asahi Chem Ind Co Ltd | Method of stabilizing terminal of oxymethylene copolymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8354495B2 (en) | 2008-04-16 | 2013-01-15 | Ticona Gmbh | Process for the preparation of oxymethylene polymers and apparatus suitable for this purpose |
| US8993709B2 (en) | 2011-07-15 | 2015-03-31 | Ticona Gmbh | Process for producing oxymethylene polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09176446A (en) | 1997-07-08 |
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