JPS63304023A - Production of polyester - Google Patents
Production of polyesterInfo
- Publication number
- JPS63304023A JPS63304023A JP13953787A JP13953787A JPS63304023A JP S63304023 A JPS63304023 A JP S63304023A JP 13953787 A JP13953787 A JP 13953787A JP 13953787 A JP13953787 A JP 13953787A JP S63304023 A JPS63304023 A JP S63304023A
- Authority
- JP
- Japan
- Prior art keywords
- chips
- polyester
- phase polymerization
- acid
- solid phase
- 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 27
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- 239000007790 solid phase Substances 0.000 claims abstract description 20
- 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 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- -1 aromatic dicarboxylic acids Chemical class 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 5
- 150000002334 glycols Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 23
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-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
- 238000006068 polycondensation reaction Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- YJGUVTBNQCVSQB-UHFFFAOYSA-N 2,2-diphenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C(=O)O)C1=CC=CC=C1 YJGUVTBNQCVSQB-UHFFFAOYSA-N 0.000 description 1
- ZRPKEUVFESZUKX-UHFFFAOYSA-N 2-(2-hydroxyethoxy)benzoic acid Chemical compound OCCOC1=CC=CC=C1C(O)=O ZRPKEUVFESZUKX-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 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)
本発明はボトル用に適した透明性をイfするポリエステ
ルを固相重合法で得る製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a polyester having transparency suitable for use in bottles by solid phase polymerization.
(従来の技術)
通常、ポリエステルを固相重合法で得る際、まず溶融重
縮合反応によりポリエステルチップを得、該チップを不
活性気体の雰囲気下、融点以下の温度に加熱することに
よって高重合度のポリエステルが得られているが、ここ
で種々のニーズに応じて最終のポリエステルの固有粘度
を変更させることがあり、その際、溶融重縮合反応によ
り得られるポリエステルチップ、すなわち供給するポリ
エステルチップは同一のものを用い、同相重合条件、例
えば反応温度、滞留時間、供給窒素流量などを変更させ
ることによって行なわれている。(Prior art) Usually, when polyester is obtained by solid-phase polymerization, polyester chips are first obtained by melt polycondensation reaction, and the chips are heated to a temperature below the melting point in an inert gas atmosphere to achieve a high degree of polymerization. However, depending on various needs, the intrinsic viscosity of the final polyester may be changed, and in this case, the polyester chips obtained by the melt polycondensation reaction, that is, the polyester chips to be supplied, may be the same. This is carried out by changing the same phase polymerization conditions, such as reaction temperature, residence time, and nitrogen supply flow rate.
(発明が解決しようとする問題点)
しかしながら、前記従来技術である固相重合条件を変更
することにより、装置内に滞留したスケール及び粉末が
急激に脱落し製品中に混在するという問題が生じた。こ
の現象は反応温度及び滞留時間変更特に顕著に表われる
。そして、これら不純物が製品中に混入する事によりボ
トル成形時に透明度を著しく阻害するという欠点があっ
た。(Problems to be Solved by the Invention) However, by changing the solid-phase polymerization conditions in the prior art, a problem arose in that scale and powder that had accumulated in the device suddenly fell off and were mixed in the product. . This phenomenon becomes especially noticeable when the reaction temperature and residence time are changed. Furthermore, there is a drawback in that the incorporation of these impurities into the product significantly impedes transparency during bottle molding.
(問題点を解決するためのL段)
本発明者は前記問題点を解決するため鋭意研究努力した
結果、遂に本発明を完成するに到った。(L stage for solving the problems) As a result of intensive research efforts to solve the above-mentioned problems, the present inventor has finally completed the present invention.
すなわち本発明はテレフタル酸を主とする芳香族ジカル
ボン酸のグリコールエステル及び/又はその低重合体を
溶融重合反応後、吐出冷却してポリエステルチップに成
形し、1亥チツプを、不活性気体の雰囲気下、固相重合
して得られるポリエステルチップの固有粘度を変更させ
るに際し、固相重合条件および同相重合に供給するポリ
エステルチップの酸価を一定にし、供給するポリエステ
ルチップの固有粘度を変更させることを特徴とするポリ
エステルの製造法である。That is, in the present invention, glycol esters of aromatic dicarboxylic acids, mainly terephthalic acid, and/or their low polymers are melt-polymerized, discharged and cooled to form polyester chips, and one chip is placed in an inert gas atmosphere. Below, when changing the intrinsic viscosity of the polyester chips obtained by solid-phase polymerization, the solid-phase polymerization conditions and the acid value of the polyester chips supplied to the same phase polymerization are kept constant, and the intrinsic viscosity of the supplied polyester chips is changed. This is a characteristic method for producing polyester.
本発明において用いられる芳香族ジカルボン酸としては
テレフタル酸を主たる対象とし、そのエステル形成性誘
導体としては炭素数1〜4の低級アルキルエステルが好
ましく使用される。また、このテレフタル酸成分の一部
(通常20モル%以下)を他の二官能性カルボン酸又は
そのエステル形成性誘導体で置変えてもよい。他の二官
能性カルボン酸としてはイソフタル酸、ナフタレンジカ
ルボン酸、ジフェニルジカルボン酸、ジフェニルスルホ
ンジカルボン酸、ジフェニルメタンジカルボン酸、ジフ
ェニルエーテルジカルボン酸、ジフェノキシエタンジカ
ルボン酸、β−ヒドロキシエトキシ安安息醋酸セバシン
酸、アジピン酸、蓚酸、1.4−シクロヘキサンジカル
ボン酸の如き芳香族、脂肪族、脂環族の二官能性ジカル
ボン酸をあげることができる。The aromatic dicarboxylic acid used in the present invention is mainly terephthalic acid, and its ester-forming derivative is preferably a lower alkyl ester having 1 to 4 carbon atoms. Further, a part (usually 20 mol % or less) of this terephthalic acid component may be replaced with another difunctional carboxylic acid or an ester-forming derivative thereof. Other difunctional carboxylic acids include isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, sebacic acid, and adipine. Examples include aromatic, aliphatic, and alicyclic difunctional dicarboxylic acids such as acid, oxalic acid, and 1,4-cyclohexanedicarboxylic acid.
グリコールとしてはエチレングリコールを二したる対象
とし、その他トリメチレングリコール、テトラメチレン
グリコール、ヘキサメチレングリコール、シクロヘキサ
ン−1,4ジメチロールの如きグリコールであってもよ
く、また主たるグリコールの−・部を他のグリコール又
はジオール化合物で置換えてもよい。The glycol mainly uses ethylene glycol, and may also include other glycols such as trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and cyclohexane-1,4 dimethylol. Glycol or diol compounds may also be substituted.
かかる酸性分とグリコール成分とから芳香族ジカルボン
酸のグリコールエステル及び/又はその低重合体を製造
する具体的な方法としては、例えばポリエチレンテレフ
タレートを製造するために使用するビス−β−ヒドロキ
シエチルテレフタレート及び/又はその低重合体につい
て説明すると、テレフタル酸とエチレングリコールとを
゛直接エステル化反応せしめるか又はテレフタル酸ジメ
チルとエチレングリコールとをエステル交換反応せしめ
る方法が一般に採用される。また、これらの反応には、
必要に応じて任意の触媒を使用することができる。A specific method for producing a glycol ester of an aromatic dicarboxylic acid and/or a low polymer thereof from such an acidic component and a glycol component includes, for example, bis-β-hydroxyethyl terephthalate used for producing polyethylene terephthalate; Regarding low polymers thereof, a method is generally employed in which terephthalic acid and ethylene glycol are subjected to a direct esterification reaction, or dimethyl terephthalate and ethylene glycol are subjected to a transesterification reaction. In addition, these reactions include
Any catalyst can be used if desired.
上記芳香族ジカルボン酸のグリコールエステル及び/又
はその低重合体の溶融重合には、格別の条件を採用する
必要はな(、通常減圧下その融点以−ヒに加熱して発生
するグリコールを留去することによって行われる。この
際平均重合度が50〜140の範囲に到達するまで溶融
重合するのが好ましい。There is no need to adopt special conditions for the melt polymerization of the above-mentioned glycol esters of aromatic dicarboxylic acids and/or their low polymers. At this time, it is preferable to carry out melt polymerization until the average degree of polymerization reaches a range of 50 to 140.
溶融重合して得られる溶融杖態のポリエステルは、吐出
冷却してチップに形成される。この際−・股には線状又
はシート状に吐出し、水冷して固化させた後粒状に切断
する方法が採用され、得られたポリエステルチップは酸
価20〜50 eq/ 10°g1特に35〜40 e
q/ 100g1水分子flo、1〜0.5屯;I七%
、特に0.3〜0.4市1i1%、粒径1〜5■■、特
に2〜4.−が好ましく、前記範囲外の場合、例えば酸
価の場合は固相重合速度が低下し、チップ水分の場合は
加水分解1itの変化及び窒素ガス中への拡散litの
変化等により重合速度変動を起し又チップ粒径は重合速
度が変化するばかりでなく固相重合装置内でのチップ流
れに変化を生じ成形品透明性を阻害するスケール等が混
入するので好ましくない。なお本発明においては供給す
るポリエステルの粘度と同相重合後の粘度とを1F比例
させるためには酸価を前記範囲内で一定しておく必要が
ある。The molten rod-like polyester obtained by melt polymerization is discharged and cooled to form chips. At this time, a method is adopted in which the polyester chips are discharged in the form of a line or sheet, cooled with water to solidify, and then cut into particles, and the resulting polyester chips have an acid value of 20 to 50 eq/10°g1, especially 35 ~40 e
q/ 100g 1 water molecule flo, 1-0.5 ton; I 7%
, especially 0.3-0.4%, particle size 1-5■■, especially 2-4. - is preferable, and when the acid value is outside the above range, the solid phase polymerization rate decreases, and in the case of chip moisture, the polymerization rate changes due to changes in hydrolysis 1it and diffusion lit into nitrogen gas, etc. The particle size of the chips is not preferable because it not only changes the polymerization rate but also changes the flow of the chips in the solid phase polymerization apparatus and causes the contamination of scale and the like which impairs the transparency of the molded product. In the present invention, in order to make the viscosity of the supplied polyester and the viscosity after in-phase polymerization proportional to 1F, it is necessary to keep the acid value constant within the above range.
次に前記ポリエステルチップを固相重合するに当たって
は、格別の固相重合条件を採用する必要はなく、減圧ド
又は窒素の如き不活性ガス気流Fその融点以下の温度、
好ましくは融点より80℃低い温度以」ユ、融点より1
0℃低い温度以ドの4度に加熱することによって行われ
る。Next, when solid-phase polymerizing the polyester chips, it is not necessary to adopt special solid-phase polymerization conditions, and the temperature below the melting point of the polyester chip is
Preferably at a temperature 80°C lower than the melting point, 1° below the melting point.
This is done by heating to 4 degrees below 0 degrees Celsius.
固相重合して得られるポリエステルの固有粘度を変更す
る場合、固相重合条件は変更せず、供給されるポリエス
テルの粘度を変更すればよ(、溶融重合反応において、
温度、真空度、滞留時間、触媒41などから少なくとも
一つの条件を変更するだけでよく、その変更に伴う弊害
が全くないため容易に変更できる。When changing the intrinsic viscosity of the polyester obtained by solid phase polymerization, the viscosity of the supplied polyester can be changed without changing the solid phase polymerization conditions (in the melt polymerization reaction,
It is only necessary to change at least one condition such as temperature, degree of vacuum, residence time, catalyst 41, etc., and the change can be easily made since there are no adverse effects associated with the change.
(実施例)
本発明を以ドの実施例を用いて具体的に説明するが、本
発明はこれらに限定されるものではない。(Examples) The present invention will be specifically explained using the following Examples, but the present invention is not limited thereto.
実施例1
常法に従いテレフタル酸とエチレングリコールから、第
1表に示す固有粘度を有する種々のポリエチレンテレフ
タレート(PET)のチップを得た。なお1亥チツプは
それぞれ酸価35 eq/ 106gx水分子it 0
、3 m jrk%、粒径2〜4■■であっ′た。Example 1 Various polyethylene terephthalate (PET) chips having the intrinsic viscosities shown in Table 1 were obtained from terephthalic acid and ethylene glycol according to a conventional method. In addition, each chip has an acid value of 35 eq/106 g x water molecules it 0
, 3 mjrk%, and particle size of 2 to 4 mm.
次に前記柱々のチップを各々固相重合槽に移し200℃
で15時間滞留させて同相重合した。得られたPETの
固有粘度を第1表に併記する。Next, each of the pillar chips was transferred to a solid phase polymerization tank at 200°C.
The mixture was allowed to remain there for 15 hours to perform in-phase polymerization. The intrinsic viscosity of the obtained PET is also listed in Table 1.
また横軸に同相重合前のPETの固有粘度を、縦軸に固
相重合後の固有粘度としたグラフ(第1図)にO印とし
て示す。なお得られたPETから厚さ5IIIlの板を
作成し積分球式光線透過率1llll定装置を用いて求
めたかすみ度は各々2〜10%であった。Further, the graph (FIG. 1), in which the horizontal axis represents the intrinsic viscosity of PET before homopolymerization and the vertical axis represents the intrinsic viscosity after solid-phase polymerization, is shown as an O mark. Incidentally, a plate having a thickness of 5IIIl was prepared from the obtained PET, and the degree of haze determined using an integrating sphere type light transmittance 1lllll meter was 2 to 10%.
比較例1
実施例1において酸価が各々15〜55eq/ l00
g1で不安定なPETのチップを固相重合槽に供給した
以外は全て実施例1と同様にしてそれぞれ同相1刊合し
た。その結果を第1表に併記し、また第1図にΔ印とし
て示す。Comparative Example 1 In Example 1, the acid value was 15 to 55 eq/l00.
The same phase polymerization was carried out in the same manner as in Example 1 except that the PET chips, which were unstable in g1, were fed to the solid phase polymerization tank. The results are also listed in Table 1 and shown as Δ in FIG.
第1表
比較例2
実施例1において、同相重合槽に供給するPETとして
固有粘度0.550に固定し、同相重合槽における温度
および滞留時間を変更したところ、種々の固有粘度のP
ETが得られたが、各々のがすみ度は20〜50%と高
かった。Table 1 Comparative Example 2 In Example 1, the intrinsic viscosity of PET supplied to the in-phase polymerization tank was fixed at 0.550, and the temperature and residence time in the in-phase polymerization tank were changed.
Although ET was obtained, the degree of ease of each was as high as 20 to 50%.
(発明の効果)
以上第1表および第1図から明らかなように、固相重合
に供するポリエステルの酸価を一定にすると、同相重合
前と重合後の固有粘度が正比例するので、固相重合後の
粘度を予想することができ、また本発明方法を採用する
ことにより、透明性の高いポリエステルを得ることがで
きる。(Effects of the invention) As is clear from Table 1 and FIG. The subsequent viscosity can be predicted, and by employing the method of the present invention, a highly transparent polyester can be obtained.
第1図は実施例1および比較例1における結果を示した
グラフであり、横軸は同相重合前のPETの固有粘度、
縦軸は固相重合後のPETの固有粘度である。
特11′1出願人 東洋紡績株式会社
芥11ii!1FIG. 1 is a graph showing the results of Example 1 and Comparative Example 1, where the horizontal axis is the intrinsic viscosity of PET before homopolymerization;
The vertical axis is the intrinsic viscosity of PET after solid phase polymerization. Special 11'1 Applicant: Toyobo Co., Ltd. 11ii! 1
Claims (1)
ールエステル及び/又はその低重合体を溶融重合反応後
、吐出冷却してポリエステルチップに成形し、該チップ
を不活性気体の雰囲気下、固相重合して得られるポリエ
ステルチップの固有粘度を変更させるに際し、固相重合
条件および固相重合に供給するポリエステルチップの酸
価を一定にし、供給するポリエステルチップの固有粘度
を変更させることを特徴とするポリエステルの製造法。Glycol esters of aromatic dicarboxylic acids, mainly terephthalic acid, and/or their low polymers are melt-polymerized, discharged and cooled to form polyester chips, and the chips are solid-phase polymerized in an inert gas atmosphere. When changing the intrinsic viscosity of the polyester chips obtained by the process, the solid phase polymerization conditions and the acid value of the polyester chips supplied to the solid phase polymerization are kept constant, and the intrinsic viscosity of the polyester chips to be supplied is changed. Manufacturing method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62139537A JP2508094B2 (en) | 1987-06-03 | 1987-06-03 | Polyester manufacturing method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62139537A JP2508094B2 (en) | 1987-06-03 | 1987-06-03 | Polyester manufacturing method |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63304023A true JPS63304023A (en) | 1988-12-12 |
JP2508094B2 JP2508094B2 (en) | 1996-06-19 |
Family
ID=15247585
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62139537A Expired - Fee Related JP2508094B2 (en) | 1987-06-03 | 1987-06-03 | Polyester manufacturing method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2508094B2 (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5441993A (en) * | 1977-09-09 | 1979-04-03 | Teijin Ltd | Preparation of polyester |
JPS5592730A (en) * | 1979-01-08 | 1980-07-14 | Nippon Ester Co Ltd | Production of branched polyester |
-
1987
- 1987-06-03 JP JP62139537A patent/JP2508094B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5441993A (en) * | 1977-09-09 | 1979-04-03 | Teijin Ltd | Preparation of polyester |
JPS5592730A (en) * | 1979-01-08 | 1980-07-14 | Nippon Ester Co Ltd | Production of branched polyester |
Also Published As
Publication number | Publication date |
---|---|
JP2508094B2 (en) | 1996-06-19 |
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