JPH01266128A - Production of polyester - Google Patents
Production of polyesterInfo
- Publication number
- JPH01266128A JPH01266128A JP9652588A JP9652588A JPH01266128A JP H01266128 A JPH01266128 A JP H01266128A JP 9652588 A JP9652588 A JP 9652588A JP 9652588 A JP9652588 A JP 9652588A JP H01266128 A JPH01266128 A JP H01266128A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- diol
- polymerization
- dicarboxylic acid
- high degree
- 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.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000002009 diols Chemical class 0.000 claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 16
- 230000009477 glass transition Effects 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 abstract description 2
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- -1 Aromatic dicarboxylic acids Chemical class 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、塗料、接着剤、コーティング剤、さらには成
形材料等の用途に有利に用いることができる高重合度の
ポリエステルの製造方法に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing polyester with a high degree of polymerization, which can be advantageously used in applications such as paints, adhesives, coating agents, and even molding materials. It is.
（従来の技術）
従来、上記用途に用いられるポリエステルとしては、ジ
カルボン酸と炭素数２〜６の低分子量のジオールと炭素
数８以上の高分子量ジオールとからなり、炭素数８以上
の高分子量ジオールを９５モル％以下で含む共重合ポリ
エステルが知られている（例えば、特公昭６２−５４６
７号公報参照）。(Prior art) Conventionally, polyesters used for the above-mentioned purposes are composed of a dicarboxylic acid, a low molecular weight diol having 2 to 6 carbon atoms, and a high molecular weight diol having 8 or more carbon atoms. Copolymerized polyesters containing 95 mol% or less of
(See Publication No. 7).
（発明が解決しようとする課題）
近年２種々の用途においてポリエステルに対する要求性
能が拡大され、特定の性能が要求されている。かかるポ
リエステルとして、上記のようなジカルボン酸と主とし
て炭素数８以上の高分子量ジオールとからなるポリエス
テルが挙げられる。(Problems to be Solved by the Invention) In recent years, the performance requirements for polyester have been expanded in two various uses, and specific performance has been required. Examples of such polyesters include polyesters composed of dicarboxylic acids as described above and high molecular weight diols having mainly 8 or more carbon atoms.
特に前記のような塗料、接着剤等の用途においては、高
重合度であって１高結晶性又は高ガラス転移点等の特性
が要求される。しかしながら、かかる要求に応えること
ができるポリエステルを高分子量ジオールを主たるジオ
ール成分として製造する場合には、高分子量ジオールは
、高沸点にすぎるため１重縮合反応において１反応系外
への除去が実質的にされなかったり、されたとしても除
去速度が遅いため、高分子量のジオールを用いて高重合
度であって、高結晶性又は高ガラス転移点のポリエステ
ルを調製することは極めて困難であった。Particularly in the above-mentioned applications such as paints and adhesives, properties such as a high degree of polymerization, high crystallinity, or a high glass transition point are required. However, when producing a polyester that can meet such demands using a high molecular weight diol as the main diol component, the high molecular weight diol has a too high boiling point and cannot be substantially removed from the reaction system in a single polycondensation reaction. It has been extremely difficult to prepare a polyester with a high degree of polymerization, high crystallinity, or a high glass transition point using a high molecular weight diol because the removal rate is slow.
本発明は、上記のような問題点を解決するものであって
、その目的は高重合度であって、しかも高結晶性又は高
ガラス転移点を有するポリエステルを容易に製造するこ
とができる製造方法を提供することにある。The present invention aims to solve the above-mentioned problems, and its purpose is to provide a manufacturing method that can easily produce a polyester having a high degree of polymerization, high crystallinity, or a high glass transition point. Our goal is to provide the following.
（課題を解決するための手段）
本発明者等は、ジカルボン酸（Ａ）と主として炭素数８
以上のジオール（Ｂ）とからなる高重合度のポリエステ
ルを工業的に安定して製造するべく鋭意検討の結果、ジ
オール（Ｂ）及び炭素数４以下のジオーノ喧Ｃ）を特定
のモル比を満足する量で用いてジカルボンＩＭ（Ａ）を
エステル化することにより。(Means for Solving the Problems) The present inventors have discovered that dicarboxylic acid (A) and mainly
As a result of intensive studies to industrially and stably produce polyester with a high degree of polymerization consisting of the above diol (B), the diol (B) and dione C) having 4 or less carbon atoms satisfy a specific molar ratio. By esterifying the dicarbonate IM (A) using an amount of
上記の問題点が解決されることを見出し９本発明にに達
成した。We have found that the above problems can be solved and have achieved the present invention.
すなわち９本発明は、ジカルボン酸（Ａ）と炭素数８以
上のジオーノ喧Ｂ）を主たるジオールとする下記（１１
式を満足するモル比の高重合度のポリエステルを製造す
るにあたり、上記ジオール（Ｂ）及び炭素数４以下のジ
オール（Ｃ）を下記（２１，（３）弐を満足するモル比
で用いてジカルボン酸（Ａ）をエステル化し、続いて重
縮合反応することを特徴とするポリエステルの製造方法
を要旨のするものである。That is, 9 the present invention provides the following (11
In producing a polyester with a high degree of polymerization and a molar ratio that satisfies the formula, the diol (B) and the diol (C) having 4 or less carbon atoms are used in a molar ratio that satisfies the following (21, (3) 2) to form a dicarbonate. The gist of the present invention is a method for producing polyester, which is characterized by esterifying an acid (A) and subsequently carrying out a polycondensation reaction.
０．９６≦ｂ／ａ≦１．００ −−−−−（ｌ＋０．９
６≦ｂ／ａ≦１ 、１Ｏ−−−（３１ただし、（１）〜
（３）式において、ａ、ｂ、ｃは、それぞれ（Ａ）、（
Ｂ）、（Ｃ）のモル数を示す。0.96≦b/a≦1.00 -----(l+0.9
6≦b/a≦1, 1O---(31, however, (1)~
In formula (3), a, b, and c are (A) and (
The number of moles of B) and (C) is shown.
以下１本発明の詳細な説明する。Hereinafter, one aspect of the present invention will be explained in detail.
まず１本発明の方法を実施するにあたり用いられるジカ
ルボン酸としては、テレフタル酸、イソフタル酸、フタ
ル酸、２．６−ナフタレンジカルボン酸、２，７−ナフ
タレンジカルボン酸、１，４−ナフタレンジカルボン酸
、４．４’−ビフェニルジカルボン酸等の芳香族ジカル
ボン酸、コハク酸、アジピン酸、アゼライン酸、セバシ
ン酸、デカンニ酸。First, the dicarboxylic acids used in carrying out the method of the present invention include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 4. Aromatic dicarboxylic acids such as 4'-biphenyl dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, decanniic acid.
ドデカンニ酸等の脂肪族ジカルボン酸、１，２−シクロ
ヘキサンジカルボン酸、１．３−シクロヘキサンジカル
ボン酸、■、４−シクロヘキサンジカルボン酸等の脂環
族ジカルボン酸、さらにはＰ−オキシ安息香酸、Ｐ−オ
キシエトキシ安息香酸等のオキシ酸が挙げられる。これ
らは、単独で又は必要に応じて２種以上用いてもよい。Aliphatic dicarboxylic acids such as dodecanoic acid, alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4-cyclohexanedicarboxylic acid, and further P-oxybenzoic acid, P- Examples include oxyacids such as oxyethoxybenzoic acid. These may be used alone or in combination of two or more as necessary.
次に、炭素数８以上の高分子量ジオールとしては、オク
タンジオール、ノナンジオール、デカンジオール、ドデ
カンジオール等の脂肪族ジオール。Next, examples of high molecular weight diols having 8 or more carbon atoms include aliphatic diols such as octanediol, nonanediol, decanediol, and dodecanediol.
水添ポリブタジェングリコール、ポリエチレングリコー
ル、ポリテトラメチレングリコール、さらにはキシリレ
ングリコール、ビスフェノールＡのエチレンオキサイド
付加物、ビスフェノールＡのプロピレンオキサイド付加
物、ビスフェノールＳのエチレンオキサイド付加物、ビ
スフェノールＳのプロピレンオキサイド付加物、水添ビ
スフェノールＡのエチレンオキサイド付加物、水添ビス
フェノールＡのプロピレンオキサイド付加物、水添ビス
フェノールＳのエチレンオキサイド付加物。Hydrogenated polybutadiene glycol, polyethylene glycol, polytetramethylene glycol, xylylene glycol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol S, propylene oxide of bisphenol S adduct, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol S.
水添ビスフェノールＳのプロピレンオキサイド付加物等
が挙げられる。これらは、単独又は２種以上を併せて用
いる。Examples include propylene oxide adducts of hydrogenated bisphenol S. These may be used alone or in combination of two or more.
さらに、炭素数４以下の低分子量ジオールとしては、エ
チレングリコール、ｌ、２−プロパンジオール、１．３
−プロパンジオール、１．３−ブタンジオール、１，４
−ブタンジオール、ジエチレングリコール等が挙げられ
、これらのうちエチレングリコールが好ましい。Furthermore, examples of low molecular weight diols having 4 or less carbon atoms include ethylene glycol, 1,2-propanediol, 1.3
-Propanediol, 1,3-butanediol, 1,4
-butanediol, diethylene glycol, etc., and among these, ethylene glycol is preferred.
上記ジカルボン酸、ジオール以外に、トリメリット酸、
ピロメリット酸のごとき多価カルボン酸。In addition to the above dicarboxylic acids and diols, trimellitic acid,
Polycarboxylic acids such as pyromellitic acid.
トリメチロールエタン、トリメチロールプロパン。Trimethylol ethane, trimethylol propane.
ペンタエリスリトールのごとき多価アルコールを必要に
応じて用いることができ、これらは５モル％以下の量で
用いることは無論差し支えない。Polyhydric alcohols such as pentaerythritol can be used if necessary, and it is of course possible to use them in an amount of 5 mol% or less.
本発明の製造方法においては、上記のようなジカルボン
酸とジオールを特定の割合で用いて、常圧下または加圧
下、１５０〜２５０℃でエステル化反応させ、エステル
化反応によって生成する所定量の水を反応系外に除いて
低重合度ポリエステルを調製する０次いで、ｎ−ブチル
チタネート、三酸化アンチモン、二酸化ゲルマニウムの
ごとき重縮合触媒の存在下、に圧下で１９０〜２９０℃
で重縮合を行って、高重合度のポリエステルを調製する
ことができる。In the production method of the present invention, dicarboxylic acids and diols as described above are used in a specific ratio, and an esterification reaction is carried out at 150 to 250°C under normal pressure or under pressure, and a predetermined amount of water produced by the esterification reaction is is removed from the reaction system to prepare a low degree of polymerization polyester. Then, in the presence of a polycondensation catalyst such as n-butyl titanate, antimony trioxide, or germanium dioxide, the mixture is heated at 190 to 290°C under pressure.
A polyester with a high degree of polymerization can be prepared by performing polycondensation.
上記ジカルボン酸に代えて、ジカルボン酸低級アルキル
エステルを用い、ジオールとの間でエステル交換反応に
よって調製される低重合度ポリエステルを中間体として
、高重合度のポリエステルを調製しても無論差し支えな
い。It goes without saying that a polyester with a high degree of polymerization may be prepared by using a dicarboxylic acid lower alkyl ester instead of the above dicarboxylic acid and using a low degree of polymerization polyester prepared by transesterification with a diol as an intermediate.
本発明の方法においては１上記＋１）式を満足するモル
比の高重合度のポリエステルを製造するにあたり８モル
比ｂ ／ ａが（３）式を満足することが必要である。In the method of the present invention, it is necessary that the molar ratio b/a satisfies the formula (3) in order to produce a polyester having a high degree of polymerization and a molar ratio that satisfies the formula +1) above.
ｂ ／ ａが０．９６未満の場合は、高結晶性又は高ガ
ラス転移点を有する高重合度のポリエステルの製造が困
難になる。特に、高結晶性でシャープな融点を示す高重
合度のポリエステルを脂肪族ジカルボン酸と高分子量脂
肪族ジオールとから調製しようとする際に、 １０モル
％以上の第３の共重合成分を導入した場合、高結晶性が
大幅に阻害される。一方、前記のモル比ｂ ／ ａが１
．１０を超えると３重縮合反応にあたり、高分子量ジオ
ールの反応系外への除去が遅くなり、経済的な速度で高
重合度ポリエステルが製造できにくくなる。なお。When b/a is less than 0.96, it becomes difficult to produce a polyester with a high degree of polymerization that has high crystallinity or a high glass transition point. In particular, when attempting to prepare a polyester with a high degree of polymerization that exhibits high crystallinity and a sharp melting point from an aliphatic dicarboxylic acid and a high molecular weight aliphatic diol, 10 mol% or more of a third copolymer component was introduced. In this case, high crystallinity is significantly inhibited. On the other hand, the molar ratio b/a is 1
．． If it exceeds 10, removal of the high molecular weight diol from the reaction system during the triple condensation reaction becomes slow, making it difficult to produce a highly polymerized polyester at an economical rate. In addition.
高分子量ジオールが実質的に不揮発性の場合。If the high molecular weight diol is substantially non-volatile.
ｂ ／ ａのを１、θ以下にしなくてはならないことも
ある。Sometimes it is necessary to reduce b/a to 1.θ or less.
次に２本発明においては２モル比（ｂ＋ｃ）／ａが上記
（２）式を満足することが必要である。（ｂ４−ｃ）／
ａが１．１５未満では、経済的な速度でエステル化が困
難である。一方、ｌ、６を越えると、経済的に不利であ
るばかりでなく、相対的に低分子量ジオールの共重合比
率が高くなることがあり２本発明の目的とするポリエス
テルが得にくくなる。Next, in the present invention, it is necessary that the molar ratio (b+c)/a satisfies the above formula (2). (b4-c)/
When a is less than 1.15, it is difficult to esterify at an economical rate. On the other hand, if it exceeds 1, 6, it is not only economically disadvantageous, but also the copolymerization ratio of the low molecular weight diol becomes relatively high, making it difficult to obtain the polyester targeted by the present invention.
本発明において製造しようとする高重合度のポリエステ
ルは概ね１．３以上の相対粘度を有するものである。The polyester with a high degree of polymerization to be produced in the present invention generally has a relative viscosity of 1.3 or more.
ここで、相対粘度は、フェノールとテトラクロルエタン
の等重量混合溶媒に０．５ｇ／ｄ１の濃度で溶解し２２
０℃で測定する。Here, the relative viscosity is 22
Measure at 0°C.
（実施例）
次に、実施例と比較例とを示して本発明を具体的に説明
する。(Example) Next, the present invention will be specifically explained by showing examples and comparative examples.
以下において、ポリエステルの融点又はガラス転移点の
ごとき熱特性は、パーキンエルマー社製ＤＳＣＩＩ型デ
イファレンシャルスキャンニングカロリーメーターを用
い、２０℃／分の昇温速度で測定する。In the following, thermal properties such as melting point or glass transition point of polyester are measured using a PerkinElmer DSCII differential scanning calorimeter at a heating rate of 20° C./min.
実施例１，２及び比較例１〜３
テレフタル酸（以下ＴＰＡと略す。）とビスフェノール
Ａのエチレンオキサイド（２分子）付加物（炭素数１９
のジオールで、以下ＢＡ２ＥＯと略す。）からなる、高
ガラス転移点で高重合度のポリエステルを調製すべく、
第１表に示す壁で原料をエステル化反応缶に採り、２４
０℃で４時間エステル化反応を行って低重合度ポリエス
テルを調製した後、２Ｘ１０−’モル／ＴＰＡモルの量
で三酸化アンチモンを投入し、 ０．５ ｓ＊Ｎｇの減
圧下、２７５℃で重縮合反応を６時間行って、第１表に
示す特性値のポリエステルを１周製した。Examples 1 and 2 and Comparative Examples 1 to 3 Ethylene oxide (2 molecules) adduct of terephthalic acid (hereinafter abbreviated as TPA) and bisphenol A (carbon number 19)
diol, hereinafter abbreviated as BA2EO. ) to prepare a polyester with a high glass transition point and high degree of polymerization.
The raw materials were taken into an esterification reactor with the walls shown in Table 1, and 24 hours
After preparing a low polymerization degree polyester by carrying out an esterification reaction at 0°C for 4 hours, antimony trioxide was added in an amount of 2 x 10-' mol/TPA mol, and the reaction was carried out at 275°C under a reduced pressure of 0.5 s*Ng. The polycondensation reaction was carried out for 6 hours to produce one round of polyester having the characteristic values shown in Table 1.
なお９表中ＥＧはエチレングリコール（炭素数２のジオ
−ル）である。Note that EG in Table 9 is ethylene glycol (diol having 2 carbon atoms).
第１表
＊ ガラス転移点：°Ｃ
実施例３．４及び比較例４〜６
セバシン酸く以下ＳＥ八と略す。）と１．ｌＯ−デカン
ジオール（炭素数１０のジオールで、以下ＤＯと略す。Table 1* Glass transition point: °C Example 3.4 and Comparative Examples 4 to 6 Sebacic acid is hereinafter abbreviated as SE8. ) and 1. lO-Decanediol (a diol with 10 carbon atoms, hereinafter abbreviated as DO).
）とからなる高結晶性ポリエステルを調製するべく、第
２表に示す原料をエステル化反応缶に採り、実施例１と
同様にエステル化反応を行った後、触媒としてｎ−ブチ
ルチタネートを２×ｌ０−４モル／ＳＥＡモル加え、０
．５龍１１ｇの減圧下。) In order to prepare a highly crystalline polyester consisting of l0-4 mol/SEA mol added, 0
．． Under reduced pressure of 5 dragons 11g.
２４５℃で重縮合反応を６時間行って、第２表に示す特
性値のポリエステルを調製した。A polycondensation reaction was carried out at 245° C. for 6 hours to prepare a polyester having the characteristic values shown in Table 2.
第２表
実施例１，２と比較例１〜３と比較する。実施例１，２
は、高重合度（高い相対粘度）で、かつ高いガラス転移
点を有するポリエステルを容易に製造し得ることを示す
。比較例１は、高重合度化は可能であるものの、高いガ
ラス転移点のポリエステルを調製する目的にそぐわない
。また、比較例２，３のごとく、低分子量のジオールを
併用しない系では、はとんど重合度の上昇は期待できな
い。Table 2 Examples 1 and 2 and Comparative Examples 1 to 3 are compared. Examples 1 and 2
shows that a polyester having a high degree of polymerization (high relative viscosity) and a high glass transition point can be easily produced. Comparative Example 1 is not suitable for the purpose of preparing a polyester with a high glass transition point, although it is possible to achieve a high degree of polymerization. Further, in systems such as those in Comparative Examples 2 and 3, in which a low molecular weight diol is not used in combination, an increase in the degree of polymerization cannot be expected.
また、実施例３，４と比較例４〜６を比較すると、実施
例３，４は、結晶性（シャープな融点を示す。）で高重
合度（高い相対粘度）のポリエステルが容易に製造でき
ることを示す。比較例４は。Moreover, when comparing Examples 3 and 4 and Comparative Examples 4 to 6, it is found that in Examples 3 and 4, polyester with crystallinity (showing a sharp melting point) and high degree of polymerization (high relative viscosity) can be easily produced. shows. Comparative example 4 is.
低分子量ジオールを併用しないと、高重合度化が困難な
ことを示す。なお２比較例４のポリエステルを調製する
にあたり２重縮合で生成するＤｏが減圧ラインで凝固し
、閉塞したため５重縮合反応を中断し、閉塞Ｄｏを除去
した後、再開した。比較例５は、低分子量ジオールを過
剰に用い、ジカルボン酸に対するジオールの比を過大に
したため。This indicates that it is difficult to achieve a high degree of polymerization unless a low molecular weight diol is used in combination. In preparing the polyester of Comparative Example 4, the Do produced by double condensation coagulated and blocked the vacuum line, so the pentacondensation reaction was interrupted and restarted after removing the blocked Do. In Comparative Example 5, an excessive amount of low molecular weight diol was used and the ratio of diol to dicarboxylic acid was made excessive.
高重合度化は容易であるものの、目的とする高結晶性を
示さない（融点を示さない。）。比較例６は、ジカルボ
ン酸に対するジオールの比が過小なため、エステル化が
不十分となり、高重合度のポリエステルが調製できなか
ったことを示す。Although it is easy to increase the degree of polymerization, it does not exhibit the desired high crystallinity (it does not exhibit a melting point). Comparative Example 6 shows that because the ratio of diol to dicarboxylic acid was too small, esterification was insufficient and a polyester with a high degree of polymerization could not be prepared.
（発明の効果）
本発明の方法は、ジカルボン酸と高分子量ジオールを主
たるジオール成分とする高重合度のポリエステルを容易
に製造することができ、高分子量ジオールの選択によっ
て、相対的に高いガラス転移点あるいは高い結晶性等の
特徴を有するポリエステルを容易に製造することができ
る。(Effects of the Invention) The method of the present invention can easily produce a polyester with a high degree of polymerization whose main diol components are a dicarboxylic acid and a high molecular weight diol, and by selecting a high molecular weight diol, a polyester with a relatively high glass transition can be produced. Polyesters having characteristics such as crystallinity or high crystallinity can be easily produced.
かかるポリエステルは、塗料、接着剤、コーティング剤
、さらには成形材料等として好適に用いることができる
。Such polyesters can be suitably used as paints, adhesives, coating agents, and even molding materials.
特許出願人 ユニ亭力株式会社Patent applicant: Uni-Tei Riki Co., Ltd.
Claims (1)
Ｂ）を主たるジオールとする下記（１）式を満足するモ
ル比の高重合度のポリエステルを製造するにあたり、上
記ジオール（Ｂ）及び炭素数４以下のジオール（Ｃ）を
下記（２）、（３）式を満足するモル比で用いてジカル
ボン酸（Ａ）をエステル化し、続いて重縮合反応するこ
とを特徴とするポリエステルの製造方法。 ０．９６≦ｂ／ａ≦１．００−−−−−−−（１） １．１５≦（ｂ＋ｃ）／ａ≦１．６−−−−−−−（２
） ０．９６≦ｂ／ａ≦１．１０−−−−−−−（３） ただし、（１）〜（３）式において、ａ、ｂ、ｃは、そ
れぞれ（Ａ）、（Ｂ）、（Ｃ）のモル数を示す。(1) Dicarboxylic acid (A) and diol having 8 or more carbon atoms (
In producing a polyester having a high degree of polymerization and having a molar ratio satisfying the following formula (1) in which B) is the main diol, the above diol (B) and a diol having 4 or less carbon atoms (C) are mixed with the following (2), ( 3) A method for producing polyester, which comprises esterifying dicarboxylic acid (A) using the formula at a molar ratio that satisfies the formula, followed by polycondensation reaction. 0.96≦b/a≦1.00---(1) 1.15≦(b+c)/a≦1.6---(2
) 0.96≦b/a≦1.10 (3) However, in formulas (1) to (3), a, b, and c are respectively (A), (B), The number of moles of (C) is shown.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63096525A JP2602892B2 (en) | 1988-04-18 | 1988-04-18 | Polyester production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63096525A JP2602892B2 (en) | 1988-04-18 | 1988-04-18 | Polyester production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01266128A true JPH01266128A (en) | 1989-10-24 |
| JP2602892B2 JP2602892B2 (en) | 1997-04-23 |
Family
ID=14167555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63096525A Expired - Fee Related JP2602892B2 (en) | 1988-04-18 | 1988-04-18 | Polyester production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2602892B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012162648A (en) * | 2011-02-07 | 2012-08-30 | Teijin Ltd | Aromatic copolyester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50100124A (en) * | 1973-12-18 | 1975-08-08 | ||
| JPS5239792A (en) * | 1975-09-25 | 1977-03-28 | Mitsubishi Chem Ind Ltd | Preparation of polyesters |
-
1988
- 1988-04-18 JP JP63096525A patent/JP2602892B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50100124A (en) * | 1973-12-18 | 1975-08-08 | ||
| JPS5239792A (en) * | 1975-09-25 | 1977-03-28 | Mitsubishi Chem Ind Ltd | Preparation of polyesters |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012162648A (en) * | 2011-02-07 | 2012-08-30 | Teijin Ltd | Aromatic copolyester |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2602892B2 (en) | 1997-04-23 |
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