JPH02158620A - Production of polyester copolymer - Google Patents
Production of polyester copolymerInfo
- Publication number
- JPH02158620A JPH02158620A JP31102888A JP31102888A JPH02158620A JP H02158620 A JPH02158620 A JP H02158620A JP 31102888 A JP31102888 A JP 31102888A JP 31102888 A JP31102888 A JP 31102888A JP H02158620 A JPH02158620 A JP H02158620A
- Authority
- JP
- Japan
- Prior art keywords
- esterification reaction
- component
- acid
- mol
- reaction product
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920000728 polyester Polymers 0.000 title description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 53
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 42
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005886 esterification reaction Methods 0.000 claims abstract description 37
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 19
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 18
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 5
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 2
- 239000002904 solvent Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920001634 Copolyester Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 dimethyl dicarboxylic acid ester Chemical class 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- NICCTRIZSSAXQY-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;2,2-dimethylpropane-1,3-diol;ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OCC(C)(C)CO.OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=CC(C(O)=O)=C1 NICCTRIZSSAXQY-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Substances OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は）８剤可溶型共重合ポリエステルの直重法によ
る製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an 8-component soluble copolyester by a direct loading method.
テレフタル酸とイソフタル酸を主たるジカルボン酸成分
としエチレングリコールとネオペンチルグリコールを主
たる多価アルコール成分とする共重合ポリエステル樹脂
は、従来、おもにジカルボン酸ジメチルエステルと多価
アルコール成分とのエステル交換反応を経て重縮合を行
ない製造されていた。Copolymerized polyester resins containing terephthalic acid and isophthalic acid as the main dicarboxylic acid components and ethylene glycol and neopentyl glycol as the main polyhydric alcohol components have traditionally been produced through a transesterification reaction between dimethyl dicarboxylic acid ester and a polyhydric alcohol component. It was produced by polycondensation.
一方、テレフタル酸とイソフタル酸を主たるジカルボン
酸成分とし、エチレングリコールを主たる多価アルコー
ル成分とする共重合ポリエステル樹脂を直重法によって
、すなわち、エステル化反応を経て重縮合を行な・う場
合、テレフタル酸の溶解度が低く、２３０’Ｃ以上の反
応温度が必要となるが、この条件でエステル化反応を行
なうと構造ははっきりしないがネオペンチルグリコール
の一部が変成し、重縮合が妨げられる。On the other hand, when a copolyester resin containing terephthalic acid and isophthalic acid as the main dicarboxylic acid components and ethylene glycol as the main polyhydric alcohol component is polycondensed by a direct polymerization method, that is, through an esterification reaction, Terephthalic acid has low solubility and requires a reaction temperature of 230'C or higher, but if the esterification reaction is carried out under these conditions, part of the neopentyl glycol is denatured, although the structure is not clear, and polycondensation is hindered.
〔発明が解決しようとする課Ｂ］
すなわち、上記のような組成をもつ共重合ポリエステル
樹脂を直重法によって製造するに際し、芳香族ジカルボ
ン酸成分とネオペンチルグリコールを主とする多価アル
コール成分とのエステル化反応を２４０〜２６０’Ｃと
いう一般的な温度条件で行なうと、反応混合物のカルボ
ン酸末端濃度ｃ以下、「酸価」と呼ぶ）が高いためネオ
ペンチルグリコールの一部が変成し重縮合をさまたげる
。[Problem B to be Solved by the Invention] That is, when producing a copolyester resin having the above composition by a direct polymerization method, an aromatic dicarboxylic acid component and a polyhydric alcohol component mainly consisting of neopentyl glycol and When the esterification reaction is carried out under the general temperature conditions of 240 to 260'C, part of the neopentyl glycol is denatured and becomes heavy because the reaction mixture has a high carboxylic acid end concentration c or less (referred to as the "acid value"). Prevents condensation.
本発明の目的は、直重法により上記のような組成をもつ
共重合ポリエステルを製造するに際し遭遇する課題を解
決し、円滑に、重縮合を行うことができる製造方法を提
供するにある。An object of the present invention is to solve the problems encountered when producing a copolymerized polyester having the above-mentioned composition by the direct loading method, and to provide a production method that allows polycondensation to be carried out smoothly.
本発明の直重法による共重合′ポリエステルの製造方法
ハ、テレフタル酸３０モル％〜７０モル％とイソフタル
酸３０モル％〜７０モル％とからなるジカルボン酸成分
と、エチレングリコール２０モル％〜８０モル％と、ネ
オペンチルグリコール２０モル％〜８０モル％とからな
る多価アルコール成分から共重合ポリエステル樹脂を製
造するに際し、
イソフタル酸とネオペンチルグリコールまたはネオペン
チルグリコールを主とする多価アルコール成分とを２３
０℃以下でエステル化反応を行ないカルボン酸末端の濃
度が９００ｍｅｑ／ｋｇ以下のエステル化反応生成物と
し、このエステル化反応生成物と、カルボン酸末端の濃
度が９００ｍｅｑ ／ ｋｇ以下であるテレフタル酸と
エチレングリコールとのエステル化反応生成物とを混合
したのち、重縮合を行なうことを特徴とする。Method for producing copolymerized polyester by direct loading method of the present invention C. A dicarboxylic acid component consisting of 30 mol% to 70 mol% of terephthalic acid and 30 mol% to 70 mol% of isophthalic acid, and 20 mol% to 80 mol% of ethylene glycol. When producing a copolymerized polyester resin from a polyhydric alcohol component consisting of isophthalic acid and neopentyl glycol or a polyhydric alcohol component mainly consisting of neopentyl glycol, 23
An esterification reaction is carried out at 0°C or lower to obtain an esterification reaction product with a carboxylic acid terminal concentration of 900 meq/kg or less, and this esterification reaction product and terephthalic acid whose carboxylic acid terminal concentration is 900 meq/kg or less. It is characterized in that polycondensation is performed after mixing the esterification reaction product with ethylene glycol.
本発明の直重法による共重合ポリエステル樹脂の製造方
法の要点は、そのエステル化反応にある。The key point of the method for producing a copolyester resin by the direct loading method of the present invention is the esterification reaction.
すなわち、イソフタル酸とネオペンチルグリコールまた
はネオペンチルグリコールを主とした多価アルコール成
分とのエステル化反応を２３０℃以下で行なう。このイ
ソフタル酸のエステル化反応段階において、ジカルボン
酸成分としてテレフタル酸を併用するとテレフタル酸の
反応性が低いためこの温度条件ではエステル化反応を完
結させることができない。また、エステル化反応温度を
２３０゛Ｃより高くするとエステル化反応自身の反応時
間は短かくなるが、重縮合の進行が遅くなり、場合によ
っては重縮合が全く進まなくなる。That is, the esterification reaction between isophthalic acid and neopentyl glycol or a polyhydric alcohol component mainly consisting of neopentyl glycol is carried out at 230°C or lower. In this esterification reaction step of isophthalic acid, if terephthalic acid is used in combination as a dicarboxylic acid component, the esterification reaction cannot be completed under this temperature condition because the reactivity of terephthalic acid is low. Furthermore, if the esterification reaction temperature is made higher than 230°C, the reaction time of the esterification reaction itself will be shortened, but the progress of polycondensation will be slowed down, and in some cases, polycondensation will not proceed at all.
なお、ジカルボン酸成分として、イソフタル酸およびテ
レフタル酸の他に、脂肪族ジカルボン酸、例えば、グル
タル酸、アジピン酸、ピメリン酸、スヘリン酸、アゼラ
イン酸、セパシン酸などを用いることができる。これら
の脂肪族ジカルボン酸はイソフタル酸とともに最初のエ
ステル化反応段階において反応系に加える。脂肪族ジカ
ルボン酸の量は一般に、ジカルボン酸合計重量に基づき
５０重量％以下である。In addition to isophthalic acid and terephthalic acid, aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, schelic acid, azelaic acid, and sepacic acid can be used as the dicarboxylic acid component. These aliphatic dicarboxylic acids are added to the reaction system together with isophthalic acid in the first esterification reaction step. The amount of aliphatic dicarboxylic acid is generally up to 50% by weight, based on the total weight of dicarboxylic acids.
上記イソフタル酸のエステル化反応に用いる多価アルコ
ール成分はネオペンチルグリコールまたはネオペンチル
グリコールを主成分とする他の多価アルコールとの混合
物である。ネオペンチルグリコールと併用できる多価ア
ルコールとしては、エチレングリコール以外の、例えば
、ジエチレングリコール、トリエチレングリコール、１
，４シクロヘキサンジメタツール、１，４−ビス（２ヒ
ドロキシエトキシ）ヘンゼン、１．４−ビス（２−ヒド
ロキシプロピルオキシ）ヘンゼン、２．２−ビス（１−
（２−ヒドロキシエトキシ）フェニル）プロパン、２．
２−ビス（４−（２ヒドロキシプロピルオキシ）フェニ
ル）プロパン、２．２−ビス（４−ヒドロキシシクロへ
キシル）プロパン、１．２−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、グリセリ
ン、トリメチロールプロパン、ペンタエリスリトール等
が挙げられる。ネオペンチルグリコールに併用できる多
価アルコールの許容割合は一般に５０重量％以下である
。イソフタル酸のエステル化反応において、ジカルボン
酸成分と多価アルコール成分とのモル比は１：１．１０
〜１：２．００がよく、好ましくは１ ： １．１５〜
ｌ：１．８０である。The polyhydric alcohol component used in the esterification reaction of isophthalic acid is neopentyl glycol or a mixture containing neopentyl glycol as a main component and other polyhydric alcohols. Polyhydric alcohols that can be used in combination with neopentyl glycol include alcohols other than ethylene glycol, such as diethylene glycol, triethylene glycol,
, 4-cyclohexane dimetatool, 1,4-bis(2-hydroxyethoxy)henzene, 1.4-bis(2-hydroxypropyloxy)henzene, 2.2-bis(1-
(2-hydroxyethoxy)phenyl)propane, 2.
2-bis(4-(2hydroxypropyloxy)phenyl)propane, 2.2-bis(4-hydroxycyclohexyl)propane, 1.2-propanediol, 1.3
-butanediol, 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol and the like. The permissible proportion of polyhydric alcohol that can be used in combination with neopentyl glycol is generally 50% by weight or less. In the esterification reaction of isophthalic acid, the molar ratio of dicarboxylic acid component and polyhydric alcohol component is 1:1.10.
~1:2.00 is good, preferably 1:1.15~
l: 1.80.
エステル化反応の終点はエステル化反応生成物の酸価が
９００ｍｅｑ／ｋｇ以下になった時点とする。ジカルボ
ン酸成分と多価アルコール成分のモル比がいずれの場合
でも、例えば２２０℃では反応混合物が透明化（均一と
なる）してのち３０分後にはこのレベルに達している。The end point of the esterification reaction is when the acid value of the esterification reaction product becomes 900 meq/kg or less. Regardless of the molar ratio of the dicarboxylic acid component and the polyhydric alcohol component, at 220° C., for example, this level is reached 30 minutes after the reaction mixture becomes transparent (becomes homogeneous).
本発明の製造方法では、上記イソフタル酸のエステル化
反応で得られたエステル化反応生成物と、別途調製した
テレフタル酸とエチレングリコールとのエステル化反応
生成物とを混合したのち重縮合を行なう。テレフタル酸
とエチレングリコールとのエステル化反応生成物は公知
の方法で調製することができ、その酸価は、９０抛ｅｑ
／ ｋｇ以下のものである。また、そのテレフタル酸
単位とエチレングリコール単位のモル比は１：１．１０
〜１：２．００の範囲であり、反応を終えたものを直接
用いてもよいし、エチレングリコールで解重合してエチ
レングリコール単位のモル比を高めたものでも良い。In the production method of the present invention, the esterification reaction product obtained from the above-mentioned isophthalic acid esterification reaction and the separately prepared esterification reaction product of terephthalic acid and ethylene glycol are mixed, and then polycondensation is performed. The esterification reaction product of terephthalic acid and ethylene glycol can be prepared by a known method, and its acid value is 90 eq.
/ kg or less. In addition, the molar ratio of terephthalic acid units and ethylene glycol units is 1:1.10.
~1:2.00, and the reacted product may be used directly, or it may be depolymerized with ethylene glycol to increase the molar ratio of ethylene glycol units.
重縮合触媒としては一般的なアンチモン化合物やゲルマ
ニウム化合物等を使用することができる。As the polycondensation catalyst, common antimony compounds, germanium compounds, etc. can be used.
重縮合は最終的に１＋ｎ＋＋＋ｌ１ｇ以下の真空度で２
５０〜２８５℃で行なうことが望ましい。Polycondensation is finally carried out at a vacuum level of 1+n+++l1g or less.
It is desirable to carry out the reaction at a temperature of 50 to 285°C.
以下、実施例について本発明を更に具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.
分子量は東ソー（株） Ｇ −３０００１１十Ｇ −５
０００１１カラムを用いてＧＰＣ法により測定したポリ
スチレン換算値である。また、ポリマー中の各成分のモ
ル比はポリマーをアルカリ水溶液で分解したのち、テレ
フタル酸とイソフタル酸はＨＰＬＣで、エチレングリコ
ールとネオペンチルグリコールはＣＬＣにて分析した結
果である。酸価はヘンシルアルコール中でメチルレッド
を指示薬として１１５ＯＮＫＯＨ−ベンジルアルコール
で滴定して求めた。Molecular weight is Tosoh Corporation G-3000110G-5
This is a polystyrene equivalent value measured by GPC method using a 00011 column. Moreover, the molar ratio of each component in the polymer is the result of decomposing the polymer with an aqueous alkali solution, and then analyzing terephthalic acid and isophthalic acid by HPLC, and ethylene glycol and neopentyl glycol by CLC. The acid value was determined by titration with 115ONKOH-benzyl alcohol in Hensyl alcohol using methyl red as an indicator.
実施例１
イソフタル酸２４９２ｇ（１５，０モル）、ネオペンチ
ルグリコール１８７６ｇ（１８，０モル）を反応器に仕
込み、窒素気流下に加熱、撹拌して常圧にてエステル化
反応を行なった。 １５０分かけて内温を１３０℃から
２２０″Ｃまで上昇させたのち、２２０’Ｃで９０分間
保持した。Example 1 2492 g (15.0 mol) of isophthalic acid and 1876 g (18.0 mol) of neopentyl glycol were placed in a reactor, heated and stirred under a nitrogen stream, and an esterification reaction was carried out at normal pressure. After raising the internal temperature from 130°C to 220'C over 150 minutes, it was held at 220'C for 90 minutes.
このエステル化反応生成物に２５０℃のテレフタル酸−
エチレングリコールエステル化反応物３０００ｇを投入
し、混合した。投入直前のテレフタル酸−エチレングリ
コールエステル化物中のテレフタル酸単位は５．００モ
ル／ｋｇ、エチレングリコール単位は５．５０モル／ｋ
ｇ、酸価は２５０ｍｅｑ ／ ｋｇであった。また、こ
の時のイソフタル酸−ネオベンチルグリコールエステル
化反応物の酸価は４３０ｍｅｑ／ｋｇであった。This esterification reaction product was mixed with terephthalic acid at 250°C.
3000 g of ethylene glycol esterification reaction product was added and mixed. The terephthalic acid unit in the terephthalic acid-ethylene glycol ester product immediately before feeding is 5.00 mol/kg, and the ethylene glycol unit is 5.50 mol/k.
g, and the acid value was 250 meq/kg. Further, the acid value of the isophthalic acid-neobentyl glycol esterification reaction product at this time was 430 meq/kg.
反応混合物を２０分かけて２６０″Ｃまで昇温し、２．
０ｇの三酸化アンチモンを加え、最終的に１ｍｍ１１ｇ
の真空度、２７０’Ｃで重縮合を１８０分間行なった。The reaction mixture was heated to 260″C over 20 minutes; 2.
Add 0g of antimony trioxide and finally make 1mm and 11g
Polycondensation was carried out for 180 minutes at a vacuum degree of 270'C.
得られた共重合ポリエステルのＶ７は１２，２ｏｏ、ｒ
ｗは３４，３００であった。また、この共重合ポリエス
テルの組成を分析したところ、テレフタル酸／イソフタ
ル酸−５０１５０、エチレングリコール／ネオペンチル
グリコール＝ ４３１５７のモル比であった。V7 of the obtained copolymerized polyester is 12,2oo, r
w was 34,300. Further, when the composition of this copolymerized polyester was analyzed, it was found that the molar ratio was terephthalic acid/isophthalic acid -50,150 and ethylene glycol/neopentyl glycol =43,157.
実施例２〜５
共重合ポリエステル樹脂の酸成分および多価アルコール
成分量を第１表に示したように変化させた以外は実施例
１と全く同じ操作を行なった。結果は表１に示す。Examples 2 to 5 The same operations as in Example 1 were carried out except that the amounts of the acid component and polyhydric alcohol component of the copolymerized polyester resin were changed as shown in Table 1. The results are shown in Table 1.
比較例１
イソフタルＭ２４９２ｇ（１５，０モル）、ネオペンチ
ルグリコール１８７６ｇ（１８，０モル）を反応器に仕
込み窒素で３ｋｇ／ｃ＋１１の圧力をかけ、加熱、撹拌
してエステル化反応を行なった。４５分かけて内温を２
６０℃まで上昇させ、２６０℃で３０分間保持した。そ
の後内温を保ったまま３０分かけて大気圧にもどした。Comparative Example 1 2492 g (15.0 mol) of Isophthal M and 1876 g (18.0 mol) of neopentyl glycol were placed in a reactor, a pressure of 3 kg/c+11 was applied with nitrogen, and an esterification reaction was carried out by heating and stirring. Over 45 minutes, reduce the internal temperature to 2.
The temperature was raised to 60°C and held at 260°C for 30 minutes. Thereafter, the pressure was returned to atmospheric pressure over 30 minutes while maintaining the internal temperature.
この時点でのエステル化反応生成物の酸価は２］Ｏｍｅ
ｑ／ｋｇであった。The acid value of the esterification reaction product at this point is 2]Ome
q/kg.
このエステル化物に２５０℃のテレフタル酸−エチレン
グリコールエステル化物３０００ ｇを投入し混合した
。反応混合物を５分かけて２６０℃まで昇温し、２、Ｏ
ｇの三酸化アンチモンを加え最終的に１ｍｍ１１ｇの真
空度、２７０“Ｃで重縮合を進行させようとしたが、７
時間反応させても溶融粘度の上昇、すなわち、重縮合の
進行は見られなかった。To this esterified product, 3000 g of terephthalic acid-ethylene glycol esterified product at 250°C was added and mixed. The reaction mixture was heated to 260°C over 5 minutes, and 2,0
I added 1 g of antimony trioxide and tried to proceed with polycondensation at 270"C with a final vacuum of 1 mm and 11 g, but the result was 7.
No increase in melt viscosity, that is, no progress of polycondensation was observed even after the reaction was allowed to proceed for a long time.
比較例２
テレフタル酸２４９２ｇ （１５，０モル）、イソフタ
ル酸２４９２ｇ （１５，０モル）、エチレングリコー
ル］ｌＬ８ｇ（１８，０モル）、ネオペンチルグリコー
ル１８７６ｇ（１８，０モル）を反応器に仕込み、窒素
で３ｋｇ／ｃ４の圧力をかけ、加熱撹拌してエステル化
反応を行なった。４５分かけて内温を２６０℃まで上昇
させ、２６０℃で３０分間保持した。その後内温を保っ
たまま３０分かけて大気圧にもどした。この時点でのエ
ステル化反応生成物の酸価は３８０ｍｅｑ ／ ｋｇで
あった。Comparative Example 2 2492 g (15.0 mol) of terephthalic acid, 2492 g (15.0 mol) of isophthalic acid, 8 g (18.0 mol) of ethylene glycol, and 1876 g (18.0 mol) of neopentyl glycol were charged into a reactor. An esterification reaction was carried out by applying a pressure of 3 kg/c4 with nitrogen and heating and stirring. The internal temperature was raised to 260°C over 45 minutes and held at 260°C for 30 minutes. Thereafter, the pressure was returned to atmospheric pressure over 30 minutes while maintaining the internal temperature. The acid value of the esterification reaction product at this point was 380 meq/kg.
２、Ｏｇの三酸化アンチモンを加え最終的に１ｍｍｔ１
ｇの真空度、２７０℃で重縮合を進行させようとしたが
、７時間反応させても溶融粘度の上昇、すなわち、重縮
合の進行は見られなかった。2. Add Og of antimony trioxide and finally 1mmt1
Although an attempt was made to proceed with polycondensation at a vacuum degree of 270° C., an increase in melt viscosity, that is, no progress of polycondensation was observed even after 7 hours of reaction.
比較例１および２の結果を表１にあわせて示す。The results of Comparative Examples 1 and 2 are also shown in Table 1.
表 １゜
実施例１
実施例２ 実施例３ 実施例４ 実施例５ 比較例１比
較例２
ＩＰＡ量（モル）
ＴＰＡ量（モル）
ＥＧ量（モル）
ＮＰＧ量（モル）
１５．０
１８．０
１５．０
１５．０
１０．５
１９．５
１５．０
６．３
１１．７
２７．０
１８．９
８．２
１５．２
１８．０
１５．０
１５．０
１８．０
１８．０
量（ｇ）
ＴＰＡ単位（モル）
ＥＧ単位（モル）
縮合時間（分）
１５．０
１８．０
１５、Ｏ
１８，０
１５，０
１８，０
１９，５
２３，４
１０，５
１２，６
１５，０
１８，０
４２０以上
４２０以上
実施例１
実施例２
実施例３
実施例４
実施例５
比較例１
比較例２
ポリマー組成
ＴＰＡ／ＩＰＡモル比
ＥＧ／ＮＰＧモル比
５０１５０ ５０１５０ ５０１５０ ４
９１５１ ５１／４９ ５０１５０ ５０
１５０４３１５７ ６１／３９ ３４／６６
４８１５２ ５１／４９ ４２１５８
４３１５７分子量
Ｍ「
Ｖ「
３４．３００ ４２，７００
１２．２００ １６７００
４０．１００
１６．６００
＊
ＩＰ＾ ：
ＴＰＡ ：
ＥＧ ：
ＮＰＧ ：
イソフタル酸
テレフタル酸
エチレングリコール
ネオペンチルグリコール
〔発明の効果〕
本発明の方法によれば、テレフタル酸とイソフタル酸を
主たるジカルボン酸成分とし、エチレングリコールとネ
オペンチルグリコールを主たる多価アルコール成分とす
る共重合ポリエステル樹脂を直重法によって工業的有利
に製造することができる。Table 1゜Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 IPA amount (mol) TPA amount (mol) EG amount (mol) NPG amount (mol) 15.0 18.0 15.0 15.0 10.5 19.5 15.0 6.3 11.7 27.0 18.9 8.2 15.2 18.0 15.0 15.0 18.0 18.0 Amount ( g) TPA units (mol) EG units (mol) Condensation time (min) 15.0 18.0 15,O 18,0 15,0 18,0 19,5 23,4 10,5 12,6 15,0 18,0 420 or more 420 or more Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Polymer composition TPA/IPA molar ratio EG/NPG molar ratio 50150 50150 50150 4
9151 51/49 50150 50
15043157 61/39 34/66
48152 51/49 42158
43157 Molecular weight M"V" 34.300 42,700 12.200 16700 40.100 16.600 * IP^: TPA: EG: NPG: Ethylene glycol neopentyl glycol isophthalate terephthalate [Effects of the invention] Method of the present invention According to , a copolyester resin containing terephthalic acid and isophthalic acid as the main dicarboxylic acid components and ethylene glycol and neopentyl glycol as the main polyhydric alcohol components can be industrially advantageously produced by a direct polymerization method.
Claims (1)
酸３０モル％〜７０モル％とからなるジカルボン酸成分
と、エチレングリコール２０モル％〜８０モル％と、ネ
オペンチルグリコール２０モル％〜８０モル％とからな
る多価アルコール成分から共重合ポリエステル樹脂を製
造するに際し、イソフタル酸とネオペンチルグリコール
またはネオペンチルグリコールを主とする多価アルコー
ル成分とを２３０℃以下でエステル化反応を行ないカル
ボン酸末端の濃度が９００ｍｅｑ／ｋｇ以下のエステル
化反応生成物とし、このエステル化反応生成物と、カル
ボン酸末端の濃度が９００ｍｅｑ／ｋｇ以下であるテレ
フタル酸とエチレングリコールとのエステル化反応生成
物とを混合したのち、重縮合を行なうことを特徴とする
共重合ポリエステル樹脂の製造方法。1. A dicarboxylic acid component consisting of 30 mol% to 70 mol% of terephthalic acid and 30 mol% to 70 mol% of isophthalic acid, 20 mol% to 80 mol% of ethylene glycol, and 20 mol% to 80 mol% of neopentyl glycol. When producing a copolymerized polyester resin from a polyhydric alcohol component consisting of An esterification reaction product having a concentration of 900 meq/kg or less was prepared, and this esterification reaction product was mixed with an esterification reaction product of terephthalic acid and ethylene glycol having a carboxylic acid terminal concentration of 900 meq/kg or less. A method for producing a copolymerized polyester resin, which is then subjected to polycondensation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31102888A JP2648191B2 (en) | 1988-12-10 | 1988-12-10 | Method for producing copolyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31102888A JP2648191B2 (en) | 1988-12-10 | 1988-12-10 | Method for producing copolyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02158620A true JPH02158620A (en) | 1990-06-19 |
| JP2648191B2 JP2648191B2 (en) | 1997-08-27 |
Family
ID=18012242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31102888A Expired - Lifetime JP2648191B2 (en) | 1988-12-10 | 1988-12-10 | Method for producing copolyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2648191B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016125829A1 (en) * | 2015-02-06 | 2016-08-11 | 東洋紡株式会社 | Copolyester resin, and method for producing same |
| CN115516003A (en) * | 2020-06-01 | 2022-12-23 | 韩国商东丽先端素材株式会社 | Organic solvent-soluble copolyester, composition for forming ultrafiltration membrane comprising same, and highly water-permeable reverse osmosis membrane prepared from same |
-
1988
- 1988-12-10 JP JP31102888A patent/JP2648191B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016125829A1 (en) * | 2015-02-06 | 2016-08-11 | 東洋紡株式会社 | Copolyester resin, and method for producing same |
| US10266645B2 (en) | 2015-02-06 | 2019-04-23 | Toyobo Co., Ltd. | Copolymerized polyester resin and method for producing the same |
| CN115516003A (en) * | 2020-06-01 | 2022-12-23 | 韩国商东丽先端素材株式会社 | Organic solvent-soluble copolyester, composition for forming ultrafiltration membrane comprising same, and highly water-permeable reverse osmosis membrane prepared from same |
| JP2023513148A (en) * | 2020-06-01 | 2023-03-30 | トーレ アドバンスト マテリアルズ コリア インク． | Organic solvent-soluble copolyester, ultrafiltration membrane-forming composition containing the same, and high water permeability reverse osmosis membrane produced therefrom |
| CN115516003B (en) * | 2020-06-01 | 2024-03-19 | 韩国商东丽先端素材股份有限公司 | Organic solvent-soluble copolyester, composition for forming ultrafiltration membrane comprising same, and high-permeability reverse osmosis membrane prepared from same |
| EP4159786A4 (en) * | 2020-06-01 | 2024-07-03 | Toray Advanced Mat Korea Inc | Organic solvent-soluble copolymer polyester, composition for forming ultrafiltration membrane comprising same, and high water permeability reverse osmosis membrane prepared therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2648191B2 (en) | 1997-08-27 |
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