JPH07102047A - Production of polyester - Google Patents
Production of polyesterInfo
- Publication number
- JPH07102047A JPH07102047A JP27765493A JP27765493A JPH07102047A JP H07102047 A JPH07102047 A JP H07102047A JP 27765493 A JP27765493 A JP 27765493A JP 27765493 A JP27765493 A JP 27765493A JP H07102047 A JPH07102047 A JP H07102047A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- added
- esterification
- ppm
- reaction
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、反応速度が速く、生成
物の色調の優れたポリエステル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 method for producing a polyester having a high reaction rate and an excellent product color tone.
【０００２】[0002]
【従来の技術】従来、ポリ１，４−シクロヘキシレンジ
メチレンテレフタレートは、テレフタル酸と、エチレン
グリコール及び１，４−シクロヘキサンジメタノールの
ジオール混合物のエステル化反応によって得られる反応
生成物を、重縮合させることにより製造される。2. Description of the Related Art Conventionally, poly (1,4-cyclohexylene dimethylene terephthalate) is obtained by polycondensing terephthalic acid and a reaction product obtained by an esterification reaction of a diol mixture of ethylene glycol and 1,4-cyclohexanedimethanol. It is manufactured by
【０００３】これ迄に、ポリ１，４−シクロヘキシレン
ジメチレンテレフタレートを製造する際、Ｔｉ含有化合
物を添加する方法として、特開平２−１９４９３６号公
報等が知られているが、この方法では色調改善の面で限
界があり、速い反応速度で、色調の優れた製品を得るこ
とに対して、必ずしも満足できる方法とは言いがたかっ
た。As a method for adding a Ti-containing compound in the production of poly (1,4-cyclohexylene dimethylene terephthalate), Japanese Patent Laid-Open No. 194936/1990 has been known. There is a limit in terms of improvement, and it is hard to say that this method is necessarily satisfactory for obtaining a product having a fast reaction rate and an excellent color tone.
【０００４】本発明者らは、上記欠点を改善すべく鋭意
研究の結果、本発明を完成したものである。The present inventors have completed the present invention as a result of earnest research to improve the above drawbacks.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的とすると
ころは、ポリ１，４−シクロヘキシレンジメチレンテレ
フタレートの製造に際し、反応速度が速く色調の優れた
樹脂を工業的容易に製造する方法を提供するにある。DISCLOSURE OF THE INVENTION An object of the present invention is to provide a method for industrially and easily producing a resin having a fast reaction rate and an excellent color tone when producing poly (1,4-cyclohexylene dimethylene terephthalate). To provide.
【０００６】[0006]
【課題を解決するための手段】即ち、本発明は酸成分が
１００モル％のテレフタル酸、ジオール成分が６０〜７
５モル％のエチレングリコールおよび２５〜４０モル％
の１，４−シクロヘキサンジメタノールからなるポリエ
ステルを製造するに際し、エステル化が終了するまでの
間にグリコール可溶性コバルト化合物を添加し、エステ
ル化終了後、Ｔｉ含有化合物と三酸化アンチモンを添加
して重縮合反応させることを特徴とするポリエステルの
製造方法である。That is, according to the present invention, terephthalic acid having an acid component of 100 mol% and diol component of 60 to 7 are used.
5 mol% ethylene glycol and 25-40 mol%
In producing the polyester consisting of 1,4-cyclohexanedimethanol, a glycol-soluble cobalt compound is added until the esterification is completed, and after the completion of the esterification, a Ti-containing compound and antimony trioxide are added to produce a heavy polymer. A method for producing a polyester, which is characterized by carrying out a condensation reaction.
【０００７】本発明で使用されるグリコール可溶性コバ
ルト化合物としては、塩化コバルト、酢酸コバルト、硝
酸コバルト、安息香酸コバルト、クロム酸コバルト、コ
バルトアセチルアセトネート（II、III ）等がある。な
かでも酢酸コバルト四水和物が好ましい。Examples of the glycol-soluble cobalt compound used in the present invention include cobalt chloride, cobalt acetate, cobalt nitrate, cobalt benzoate, cobalt chromate, cobalt acetylacetonate (II, III) and the like. Of these, cobalt acetate tetrahydrate is preferable.
【０００８】本発明で使用されるＴｉ含有化合物として
は、シュウ酸チタニルのリチウム塩、カリウム塩、ナト
リウム塩、カルシウム塩、マグネシウム塩、ストロンチ
ウム塩、バリウム塩、亜鉛塩、コバルト塩、マンガン
塩、アンモニウム塩などがある。なかでもシュウ酸チタ
ニルカリウムが好ましい。Examples of the Ti-containing compound used in the present invention include lithium, potassium, sodium, calcium, magnesium, strontium, titanyl oxalate, barium, zinc, cobalt, manganese, and ammonium salts. There is salt etc. Of these, potassium titanyl oxalate is preferred.
【０００９】本発明のポリエステルの製造に際しては、
例えばテレフタル酸と、１，４−シクロヘキサンジメタ
ノールおよびエチレングリコールのジオール混合物を所
望割合で仕込み、エステル化触媒の存在下に２３０〜２
５０℃でエステル化し、かつこのようにして得た反応生
成物を重合触媒の存在下において、高真空雰囲気化２５
０〜２８５℃で重縮合せしめることにより製造すること
ができる。In producing the polyester of the present invention,
For example, terephthalic acid and a diol mixture of 1,4-cyclohexanedimethanol and ethylene glycol are charged at a desired ratio, and 230 to 2 are added in the presence of an esterification catalyst.
The reaction product thus obtained was esterified at 50 ° C., and the reaction product thus obtained was subjected to a high vacuum atmosphere in the presence of a polymerization catalyst.
It can be produced by polycondensation at 0 to 285 ° C.
【００１０】また、本発明のポリエステルを製造する際
に、酸成分に対するジオール成分の仕込比率（モル比）
を１．３〜２．３として反応を行うことも重合速度が速
くなり好ましい方法である。When the polyester of the present invention is produced, the charging ratio (molar ratio) of the diol component to the acid component is
It is also a preferable method to carry out the reaction with 1.3 to 2.3 because the polymerization rate becomes faster.
【００１１】本発明はグリコール可溶性コバルト化合物
の存在下で、エステル化反応を行う。コバルト化合物の
添加量は、色調改善及び安全衛生の点から、ポリエステ
ルに対して７０〜９５ｐｐｍ（Ｃｏ量）が好ましい。ま
た、本発明は、Ｔｉ含有化合物と三酸化アンチモンから
なる触媒系の存在下で重縮合反応を行う。Ｔｉ含有化合
物の添加量は、重合速度や色調の点から、ポリエステル
に対して３０〜６０ｐｐｍ（Ｔｉ量）が好ましい。三酸
化アンチモンは、色調及び安全衛生の点から、ポリエス
テルに対して２００〜３５０ｐｐｍ（Ｓｂ量）が好まし
い。本発明では、エステル化終了後にＴｉ含有化合物と
三酸化アンチモンを添加する。エステル化終了前に添加
すると、重合触媒としての活性が低下し、重合促進の妨
げとなる。In the present invention, the esterification reaction is carried out in the presence of a glycol-soluble cobalt compound. From the viewpoint of improving the color tone and safety and hygiene, the amount of the cobalt compound added is preferably 70 to 95 ppm (Co amount) with respect to the polyester. The present invention also performs the polycondensation reaction in the presence of a catalyst system consisting of a Ti-containing compound and antimony trioxide. From the viewpoint of polymerization rate and color tone, the addition amount of the Ti-containing compound is preferably 30 to 60 ppm (Ti amount) with respect to the polyester. From the viewpoint of color tone and safety and hygiene, antimony trioxide is preferably 200 to 350 ppm (Sb amount) relative to polyester. In the present invention, a Ti-containing compound and antimony trioxide are added after the completion of esterification. If it is added before the completion of esterification, the activity as a polymerization catalyst decreases, which hinders the promotion of polymerization.
【００１２】本発明の方法ではエステル化が終了するま
での間にリン系化合物を反応混合物中に用いるのが好ま
しく、このリン系化合物は本発明に従って製造されるポ
リ１，４−シクロヘキシレンジメチレンテレフタレート
の色調安定剤として作用する。好ましいリン系化合物は
リン酸トリメチルである。In the method of the present invention, it is preferable to use a phosphorus compound in the reaction mixture until the esterification is completed, and the phosphorus compound is the poly (1,4-cyclohexylene dimethylene) produced according to the present invention. It acts as a color stabilizer for terephthalate. A preferred phosphorus compound is trimethyl phosphate.
【００１３】[0013]
【発明の効果】本発明のポリエステルは優れた色調を有
している。また、本発明の製造方法は通常のポリエステ
ルの製造条件及び装置で工業的に容易に製造できるもの
である。The polyester of the present invention has an excellent color tone. Further, the production method of the present invention can be easily produced industrially under ordinary polyester production conditions and equipment.
【００１４】[0014]
【実施例】以下、実施例によって本発明を具体的に説明
する。EXAMPLES The present invention will be specifically described below with reference to examples.
【００１５】極限粘度〔η〕は、フェノール／テトラク
ロルエタン＝６／４（重量比）溶媒中２０℃で測定し
た。ポリマー色調ハンタースケールｂ値は黄色味を示す
尺度であってペレットの状態で測定したものである。ｂ
値が小さい程、色調が良好であることを示す。The intrinsic viscosity [η] was measured at 20 ° C. in a solvent of phenol / tetrachloroethane = 6/4 (weight ratio). The polymer color hunter scale b value is a scale showing yellowness and is measured in the state of pellets. b
The smaller the value, the better the color tone.
【００１６】実施例１ テレフタル酸１００モル％に３３モル％の１，４−シク
ロヘキサンジメタノール及び６７モル％のエチレングリ
コールを添加し、さらに酢酸コバルト四水和物７６ｐｐ
ｍ Ｃｏ（対ポリエステル）及びリン酸トリメチル２４
ｐｐｍ Ｐ（対ポリエステル）を添加し窒素雰囲気下２
３０〜２５０℃に加熱してエステル化反応を行い、生成
する水を連続的に系外に留出させた。反応開始後３時間
でエステル化反応が完了し、得られた生成物に、シュウ
酸チタニルカリウム３０ｐｐｍＴｉ（対ポリエステル）
及び三酸化アンチモン２５０ｐｐｍ Ｓｂ（対ポリエス
テル）を加えて反応系を徐々に減圧し、最終的には２８
５℃、１ｍｍＨｇで１時間５０分で重縮合を終了した。Example 1 To 100 mol% of terephthalic acid, 33 mol% of 1,4-cyclohexanedimethanol and 67 mol% of ethylene glycol were added, and further cobalt acetate tetrahydrate of 76 pp was added.
m Co (against polyester) and trimethyl phosphate 24
ppm P (against polyester) is added and under nitrogen atmosphere 2
The esterification reaction was carried out by heating to 30 to 250 ° C., and the produced water was continuously distilled out of the system. The esterification reaction was completed 3 hours after the start of the reaction, and the obtained product was treated with potassium titanyl oxalate 30 ppm Ti (versus polyester).
And antimony trioxide 250 ppm Sb (against polyester) were added to gradually reduce the pressure of the reaction system to 28
The polycondensation was completed in 1 hour and 50 minutes at 5 ° C. and 1 mmHg.
【００１７】実施例２ テレフタル酸１００モル％に３３モル％の１，４−シク
ロヘキサンジメタノール及び６７モル％のエチレングリ
コールを添加し、さらに酢酸コバルト四水和物９０ｐｐ
ｍ Ｃｏ（対ポリエステル）及びリン酸トリメチル６０
ｐｐｍ Ｐ（対ポリエステル）を添加し、窒素雰囲気下
２３０〜２５０℃に加熱してエステル化反応を行い、生
成する水を連続的に系外に留出させた。反応開始後２時
間半でエステル化反応が完了し、得られた生成物にシュ
ウ酸チタニルカリウム４０ｐｐｍＴｉ（対ポリエステ
ル）及び三酸化アンチモン２５０ｐｐｍ Ｓｂ（対ポリ
エステル）を加えて反応系を徐々に減圧し、最終的には
２８５℃、１ｍｍＨｇで２時間１０分で重縮合を終了し
た。Example 2 To 100 mol% of terephthalic acid, 33 mol% of 1,4-cyclohexanedimethanol and 67 mol% of ethylene glycol were added, and further cobalt acetate tetrahydrate of 90 pp was added.
m Co (against polyester) and trimethyl phosphate 60
ppm P (relative to polyester) was added, the mixture was heated to 230 to 250 ° C. in a nitrogen atmosphere to carry out an esterification reaction, and the produced water was continuously distilled out of the system. Two and a half hours after the start of the reaction, the esterification reaction is completed, and potassium titanyl oxalate 40 ppm Ti (against polyester) and antimony trioxide 250 ppm Sb (against polyester) are added to the resulting product to gradually reduce the pressure of the reaction system, Finally, the polycondensation was completed in 2 hours and 10 minutes at 285 ° C. and 1 mmHg.
【００１８】実施例３ リン酸トリメチルを添加しないこと以外は実施例１と同
様に行った。Example 3 Example 1 was repeated except that trimethyl phosphate was not added.
【００１９】比較例１ 実施例１において、酢酸コバルト四水和物の添加量を２
０ｐｐｍ Ｃｏ（対ポリエステル）とし、リン酸トリメ
チルの添加量を７ｐｐｍ Ｐ（対ポリエステル）とする
以外は実施例１と全く同様にエステル化を行ったとこ
ろ、エステル化反応に２時間４５分を要した。この反応
生成物にチタンテトラブトキサイド３０ｐｐｍ Ｔｉ
（対ポリエステル）を添加し、反応系を徐々に減圧し、
最終的には２８０℃、１ｍｍＨｇで２時間で重縮合を終
了した。Comparative Example 1 In Example 1, the amount of cobalt acetate tetrahydrate added was 2
Esterification was performed in exactly the same manner as in Example 1 except that 0 ppm Co (relative to polyester) was used and the amount of trimethyl phosphate added was 7 ppm P (relative to polyester). The esterification reaction took 2 hours and 45 minutes. . Titanium tetrabutoxide 30 ppm Ti was added to this reaction product.
(To polyester) is added, the reaction system is gradually depressurized,
Finally, the polycondensation was completed in 2 hours at 280 ° C. and 1 mmHg.
【００２０】比較例２ 実施例１において酢酸コバルト四水和物を酢酸カルシウ
ム１８４ｐｐｍ Ｃａ（対ポリエステル）に変更する以
外は、実施例１と全く同様にエステル化を行い、次いで
三酸化アンチモン２９２ｐｐｍ Ｓｂ（対ポリエステ
ル）及びリン酸トリメチル５０ｐｐｍ Ｐ（対ポリエス
テル）を添加し重縮合を行った。重縮合は４時間５２分
で終了した。以上の結果を表１に記す。Comparative Example 2 Esterification was carried out in the same manner as in Example 1 except that cobalt acetate tetrahydrate was changed to calcium acetate 184 ppm Ca (against polyester) in Example 1, and then antimony trioxide 292 ppm Sb ( Polyester) and trimethyl phosphate 50 ppm P (against polyester) were added for polycondensation. The polycondensation was completed in 4 hours and 52 minutes. The above results are shown in Table 1.
【００２１】[0021]
【表１】 [Table 1]
【００２２】表１から明らかなように、実施例品は、比
較例品に比べて優れた色調及び優れた重合速度を有して
いる。As is clear from Table 1, the product of the example has an excellent color tone and an excellent polymerization rate as compared with the product of the comparative example.
Claims (3)
ジオール成分が６０〜７５モル％のエチレングリコール
および２５〜４０モル％の１，４−シクロヘキサンジメ
タノールからなるポリエステルを製造するに際し、エス
テル化が終了するまでの間にグリコール可溶性コバルト
化合物を添加し、エステル化終了後、Ｔｉ含有化合物と
三酸化アンチモンを添加して重縮合反応させることを特
徴とするポリエステルの製造方法。1. A terephthalic acid containing 100 mol% of an acid component,
In producing a polyester having a diol component of 60 to 75 mol% ethylene glycol and 25 to 40 mol% of 1,4-cyclohexanedimethanol, a glycol-soluble cobalt compound is added until esterification is completed, After the completion of the esterification, a Ti-containing compound and antimony trioxide are added to carry out a polycondensation reaction, which is a method for producing a polyester.
足するように添加することを特徴とする請求項１記載の
方法。 ７０≦Ｃｏ≦９５ （式中Ｃｏは金属コバルト ｐｐｍ対ポリエステルを示
す。）2. The method according to claim 1, wherein glycol-soluble cobalt is added so as to satisfy the following formula. 70 ≦ Co ≦ 95 (wherein Co represents metallic cobalt ppm vs. polyester)
記式を満足するように添加することを特徴とする請求項
１記載の方法。 ３０≦Ｔｉ≦６０ ２００≦Ｓｂ≦３５０ （式中Ｔｉは金属チタン ｐｐｍ対ポリエステル、Ｓｂ
は金属アンチモン ｐｐｍ対ポリエステルを示す。）3. The method according to claim 1, wherein the Ti-containing compound and antimony trioxide are added so as to satisfy the following formula. 30 ≦ Ti ≦ 60 200 ≦ Sb ≦ 350 (where Ti is metallic titanium ppm vs. polyester, Sb
Indicates metal antimony ppm to polyester. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27765493A JPH07102047A (en) | 1993-10-07 | 1993-10-07 | Production of polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27765493A JPH07102047A (en) | 1993-10-07 | 1993-10-07 | Production of polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07102047A true JPH07102047A (en) | 1995-04-18 |
Family
ID=17586445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27765493A Pending JPH07102047A (en) | 1993-10-07 | 1993-10-07 | Production of polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07102047A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001131275A (en) * | 1999-10-08 | 2001-05-15 | Atofina Chemicals Inc | Polycondensation of polyester using lithium titanyl oxalate catalyst |
| US10072118B2 (en) | 2014-10-23 | 2018-09-11 | Sk Chemicals Co., Ltd. | Polycyclohexylenedimethylene terephthalate resin having enhanced crystallization speed and method for preparing same |
-
1993
- 1993-10-07 JP JP27765493A patent/JPH07102047A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001131275A (en) * | 1999-10-08 | 2001-05-15 | Atofina Chemicals Inc | Polycondensation of polyester using lithium titanyl oxalate catalyst |
| US10072118B2 (en) | 2014-10-23 | 2018-09-11 | Sk Chemicals Co., Ltd. | Polycyclohexylenedimethylene terephthalate resin having enhanced crystallization speed and method for preparing same |
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