JPS63199222A - Production of polyester - Google Patents
Production of polyesterInfo
- Publication number
- JPS63199222A JPS63199222A JP3168287A JP3168287A JPS63199222A JP S63199222 A JPS63199222 A JP S63199222A JP 3168287 A JP3168287 A JP 3168287A JP 3168287 A JP3168287 A JP 3168287A JP S63199222 A JPS63199222 A JP S63199222A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- glycol
- group
- catalyst
- aromatic dicarboxylic
- 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 21
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 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 12
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- JHHJZXAFNAJSCA-UHFFFAOYSA-N methyl(oxo)tin Chemical compound C[Sn]=O JHHJZXAFNAJSCA-UHFFFAOYSA-N 0.000 claims abstract description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 9
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical group CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 8
- SMQNORGDIFWNEP-UHFFFAOYSA-N dichloromethyl(dichloromethylstannylmethyl)stannane Chemical compound ClC(Cl)[SnH2]C[SnH2]C(Cl)Cl SMQNORGDIFWNEP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003606 tin compounds Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- -1 terephthalic acid Chemical compound 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 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
- 150000002334 glycols Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 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 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 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
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- JAKYSQPCKJGHDB-UHFFFAOYSA-N ethyl(oxo)tin Chemical compound CC[Sn]=O JAKYSQPCKJGHDB-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- LVLWGUYOLWOCNN-UHFFFAOYSA-N oxo(phenyl)tin Chemical compound O=[Sn]C1=CC=CC=C1 LVLWGUYOLWOCNN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- UCWABCCLELENRN-UHFFFAOYSA-N trimethyl(trimethylstannylmethyl)stannane Chemical compound C[Sn](C)(C)C[Sn](C)(C)C UCWABCCLELENRN-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はポリエステルの製造方法に関するもので、特に
新規かつ効果の優れた反応触媒を用いて高重合度ポリエ
ステルを短時間で製造する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, and in particular to a method for producing polyester with a high degree of polymerization in a short time using a novel and highly effective reaction catalyst. It is.
（従来の技術）
今日、工業的に製造されているポリエステルの内で、最
も重要なものはポリエチレンテレフタレートであり、繊
維、フィルム、その他の成形物に広く利用されている。(Prior Art) Among polyesters produced industrially today, the most important one is polyethylene terephthalate, which is widely used in fibers, films, and other molded products.
ポリエチレンテレフタレートは通常二段階の反応により
得られる。第一段階はジメチルテレフタレートとエチレ
ングリコールとを触媒の存在下１５０〜２４０℃に加熱
して生成するメタノールを除去しつつエステル交換反応
を行なわせるか、またはテレフタル酸をエチレングリコ
ールによって直接エステル化反応を行なうものであり、
第二段の反応はこれを重縮合反応させるものである。こ
の場合、重縮合は２６０℃以上のポリエチレンテレフタ
レートの融点以上の温度において減圧下に行なわれるか
、あるいは初期重合物を一旦冷却固化せしめ、適当な大
きさの粉末または、細片に粉砕した後ポリエチレンテレ
フタレートの融点以下の温度において減圧下または不活
性気流中で固相重合する。これらの反応を円滑に進める
ためには一般に触媒が利用されており、使用される触媒
の種類によって反応速度のみならずポリエステルの色調
や熱安定性が大きく左右されることが知られている。Polyethylene terephthalate is usually obtained by a two-step reaction. The first step is to heat dimethyl terephthalate and ethylene glycol to 150-240°C in the presence of a catalyst to perform a transesterification reaction while removing the methanol produced, or to directly esterify terephthalic acid with ethylene glycol. It is something that is done;
The second stage reaction involves a polycondensation reaction. In this case, the polycondensation is carried out under reduced pressure at a temperature of 260°C or higher, which is higher than the melting point of polyethylene terephthalate, or the initial polymer is once cooled and solidified, pulverized into an appropriately sized powder or fine pieces, and then polyethylene Solid state polymerization is carried out at a temperature below the melting point of terephthalate under reduced pressure or in an inert gas flow. Catalysts are generally used to facilitate these reactions, and it is known that not only the reaction rate but also the color tone and thermal stability of the polyester are greatly influenced by the type of catalyst used.
従って、適切なる性能、すなわち速い反応速度で良好な
色調を有し、かつ優れた熱安定性を示すポリエステルを
与えるごとき触媒を提供することは、極めて重要であり
、そのために従来、高重合度ポリエステルの製造に適す
る幾多の重縮合触媒が提案されている。Therefore, it is extremely important to provide a catalyst that provides suitable performance, ie, a polyester with a fast reaction rate, good color tone, and excellent thermal stability. A number of polycondensation catalysts suitable for the production of have been proposed.
例えば、アンチモン化合物としては二酸化アンチモンが
最も良く知られ、安価であり、これを触媒として製造し
たポリエステルは優れた耐熱性と加工性を有しているが
、反面、反応中にアンチモン触媒が還元されて金属アン
チモンが析出し、得られたポリマーが灰色の（すんだも
のとなる欠点を有している。For example, antimony dioxide is the most well-known and inexpensive antimony compound, and polyester produced using it as a catalyst has excellent heat resistance and processability, but on the other hand, the antimony catalyst is reduced during the reaction. The disadvantage is that metallic antimony precipitates and the resulting polymer becomes gray.
錫化合物は比較的活性の高い重合触媒であり、特に米国
特許第２７２０５０７号明細書に記載されているジアル
キル錫オキシドやそれから誘導されるアルコラード、カ
ルボキシレートまたは塩化物などの有機スズ化合物は反
応系にも溶は易く透明性の高いポリマーが得られる。ま
た特開昭５２−８２９９５号公報に記載されているモノ
アルキルスズ化合物も同様である。Tin compounds are relatively active polymerization catalysts, and in particular organotin compounds such as dialkyltin oxides and the alcoholades, carboxylates, or chlorides derived therefrom described in U.S. Pat. No. 2,720,507 are useful in the reaction system. It is also easy to dissolve and a highly transparent polymer can be obtained. The same also applies to the monoalkyltin compounds described in JP-A-52-82995.
（発明が解決しようとする問題点）
しかしながら、従来の錫触媒を用いてポリエステルを製
造する場合、得られるポリマーの色調や反応促進効果な
どの面で必ずしも満足し得るものではない。(Problems to be Solved by the Invention) However, when polyester is produced using conventional tin catalysts, the resulting polymer is not always satisfactory in terms of color tone, reaction acceleration effect, etc.
本発者等は種々の触媒を検討した結果、ポリマーの着色
は触媒の金属種と重縮合反応時間に強（依存しており、
同一金属種であっても触媒活性を改善できれば着色を抑
制できることを見出し、また、触媒分子内の近接位置に
複数の活性部位を有するように触媒を設計することが効
果的であるという知見を見出し、鋭意研究を重ねた結果
、本発明を完成した。As a result of examining various catalysts, the present inventors found that the coloration of polymers strongly (depends) on the metal species of the catalyst and the polycondensation reaction time.
We discovered that coloring can be suppressed by improving catalyst activity even when the metal species is the same, and we also discovered that it is effective to design catalysts to have multiple active sites in close proximity within the catalyst molecule. As a result of extensive research, the present invention was completed.
本発明の目的は、色相良好なる高重合度ポリエステルを
極めて迅速に製造する方法を提供することにある。An object of the present invention is to provide a method for extremely rapidly producing a highly polymerized polyester having a good hue.
（問題を解決するための手段）
本発明方法は、芳香族ジカルボン酸を主成分とする二官
能性カルボン酸またはそのエステル形成性誘導体とグリ
コールとからポリエステルを製造するに際し、触媒とし
て下記一般式（１）及び／又は（２）で示される有機錫
化合物を使用して重縮合せしめることを特徴とする。(Means for solving the problem) The method of the present invention uses the following general formula ( It is characterized by polycondensation using the organic tin compounds shown in 1) and/or (2).
本発明で用いられる一般式（１）または（２）で示され
る化合物を例示すると、メチレンビス（メチル錫オキシ
ド）、ジメチルメチレンビス（メチル錫オキシド）、ト
リメチレンビス（エチル錫オキシド）、メチレンビス（
ｎ−ブチル錫オキシド）、メチレンビス（フェニル錫オ
キシド）やこれらの有機錫の有機カルボキシレートまた
はアルコラードおよびビス（ジクロロメチルスタニル）
メタンなどが挙げられる。Examples of compounds represented by formula (1) or (2) used in the present invention include methylenebis(methyltin oxide), dimethylmethylenebis(methyltin oxide), trimethylenebis(ethyltin oxide), methylenebis(methyltin oxide),
n-butyltin oxide), methylenebis(phenyltin oxide) and organic carboxylates of these organotins or alcoholades and bis(dichloromethylstannyl)
Examples include methane.
本発明における触媒は、ジャーナル参オブ・オルガノメ
タリック・ケミストリー、第１１７巻、第８２９頁（１
９７６年）及び／又はオルガノメタリックス、第２巻、
第１０６頁（１９８８年）記載の方法を参考にして合成
することができる。The catalyst used in the present invention is described in Journal Reference of Organometallic Chemistry, Volume 117, Page 829 (1
976) and/or Organometallics, Volume 2,
It can be synthesized by referring to the method described on page 106 (1988).
例えば、メチレンビス（メチルスズオキシド）は、ビス
（トリメチルスタニル）メタン、次いで、ビス（ジクロ
ロメチルスタニル）メタンを上記の文献に従って合成し
た後、このビス（ジクロロメチルスタニル）メタンのエ
タノール溶液を希アンモニア水で処理し、得られた沈澱
を水洗、乾燥して得られる。重合反応条件は通常のもの
でよく、反応温度は２７０〜２９０℃が好ましい。For example, methylene bis(methyltin oxide) is synthesized by synthesizing bis(trimethylstannyl)methane, then bis(dichloromethylstannyl)methane according to the above literature, and then converting the ethanol solution of this bis(dichloromethylstannyl)methane into It is obtained by treating with dilute ammonia water, washing the resulting precipitate with water, and drying it. The polymerization reaction conditions may be normal ones, and the reaction temperature is preferably 270 to 290°C.
本発明の触媒の使用量は、反応条件により異なるが、一
般に最終的に得られるポリエステルポリマーに対し、通
常錫原子として０．０００５〜０．５モル％、好ましく
は０．００１〜０．２モル％である。The amount of the catalyst of the present invention to be used varies depending on the reaction conditions, but is generally 0.0005 to 0.5 mol%, preferably 0.001 to 0.2 mol% as tin atoms, based on the polyester polymer finally obtained. %.
また本発明の触媒は、通常のエステル交換またはエステ
ル化反応後、或いは重縮合の途中に添加されるのが好ま
しいが、それより前に添加しても差し支えない。Further, the catalyst of the present invention is preferably added after a normal transesterification or esterification reaction or during polycondensation, but it may be added before that.
更に本発明方法は、リン化合物のような公知の安定剤と
共存させてもよく、また酸化チタンなどの顔料や帯電防
止剤と併用しても構わない。Furthermore, in the method of the present invention, a known stabilizer such as a phosphorus compound may be used together, or a pigment such as titanium oxide or an antistatic agent may be used in combination.
本発明は、テレフタル酸とグリコールとからなるポリエ
ステルを製造する場合に、有効に適用されるが、この場
合の代表的なグリコールは、エチレングリコールおよび
、１．４−ブタンジオールである。又、テレフタル酸と
これらのグリコール以外の少なくとも一種の第三成分を
含有する共重合ポリエステルの製造にも適用される。こ
の場合、第三成分とは、イソフタル酸、ｐ−β−オキシ
エトキシ安息香酸、ジフェニルスルホンジカルボン酸、
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、アジピン酸、セパチン酸、５−ナトリウ
ムスルホイソフタル酸、プロピレングリコール、トリエ
チレングリコール、ネオペンチルグリコール、ｌ、４−
シクロヘキサンジオール、１．４−シクロヘキサンジメ
タツール、１．４−ビスオキシエトキシベンゼン、ビス
フェノールＡ１ポリエチレングリコール等、ポリエステ
ルの改質に使用される公知の化合物を指す口（発明の効
果）
本発明方法は従来の方法に比べ、ポリエステルの重縮合
反応時間が著しく短縮され、しかも、得られるポリエス
テルは色相良好である。また本発明により得られたポリ
エステルはフィラメント。The present invention is effectively applied to the production of polyester made of terephthalic acid and glycol, and typical glycols in this case are ethylene glycol and 1,4-butanediol. It is also applied to the production of a copolyester containing terephthalic acid and at least one third component other than these glycols. In this case, the third component is isophthalic acid, p-β-oxyethoxybenzoic acid, diphenylsulfonedicarboxylic acid,
Diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid, adipic acid, sepatic acid, 5-sodium sulfoisophthalic acid, propylene glycol, triethylene glycol, neopentyl glycol, l, 4-
Cyclohexanediol, 1,4-cyclohexane dimetatool, 1,4-bisoxyethoxybenzene, bisphenol A1 polyethylene glycol, and other known compounds used for modifying polyester (effects of the invention) The method of the present invention Compared to conventional methods, the polyester polycondensation reaction time is significantly shortened, and the resulting polyester has good color. Moreover, the polyester obtained by the present invention is a filament.
フィルム及び成形物等に好適に使用される。Suitable for use in films, molded products, etc.
（実施例）
次に本発明の実施例をあげて説明するが、本発明はこれ
らの実施例によって限定されるものではない。尚、実施
例中「部」とあるのは重量部、極限粘度はフェノール：
テトラクロルエタン（６０：４０）を溶媒として２０°
Ｃで測定した値である。(Examples) Next, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. In the examples, "parts" refers to parts by weight, and the intrinsic viscosity refers to phenol:
20° using tetrachloroethane (60:40) as a solvent
This is the value measured at C.
実施例１
テレフタル酸１００部、エチレングリコール４５部を精
留塔、かきまぜ機付の反応器に入れ、窒素ガスで２ｋｇ
／ｃｍ２Ｑに加圧し、十分かきまぜなから２５０°Ｃに
約２時間で昇温した。同温度に維持しながら、副生成物
の水を遂次系外へ精留塔を通して抜き出し、その留出水
が２０部になった時点で第１段の反応を終了した。Example 1 100 parts of terephthalic acid and 45 parts of ethylene glycol were placed in a rectification column and a reactor equipped with a stirrer, and 2 kg of nitrogen gas was added.
/cm2Q, stirred thoroughly, and heated to 250°C in about 2 hours. While maintaining the same temperature, by-product water was successively extracted from the system through a rectification column, and when the distilled water amounted to 20 parts, the first stage reaction was completed.
次に、この反応生成物を重縮合用反応器にうつし、触媒
としてメチレンビス（メチル錫オキシド）を、ポリエス
テルポリマーに対し、錫原子としてｌＸ１０ モル％と
なるように加え、２８０°Ｃの浴中で８０分かけて１τ
ｎｍＨｇ以下に減圧した。更に１時間反応せしめて得ら
れた重合体は極限粘度〔η〕が０．６８５であり、色調
は透明で良好であった。Next, this reaction product was transferred to a polycondensation reactor, and methylene bis (methyl tin oxide) was added as a catalyst to the polyester polymer so that the amount of tin atoms was lx10 mol%, and the mixture was placed in a bath at 280°C. 1τ over 80 minutes
The pressure was reduced to below nmHg. The polymer obtained by further reacting for 1 hour had an intrinsic viscosity [η] of 0.685 and a good transparent color tone.
実施例２
実施例１において触媒をポリエステルポリマーに対して
錫原子として４ Ｘ １０−２モル％用い、２８０”Ｃ
の浴中で８０分かけて１ ｍｍＨｇ以下に減圧し、更に
、８０分反応せしめた。Example 2 In Example 1, the catalyst was 4 x 10-2 mol% of tin atoms relative to the polyester polymer, and 280"C
The pressure was reduced to 1 mmHg or less over 80 minutes in a water bath, and the reaction was continued for an additional 80 minutes.
得られた重合体は極限粘度〔η〕が０．６９１で、色調
は透明で良好であった。The obtained polymer had an intrinsic viscosity [η] of 0.691 and a good transparent color tone.
比較例１
実施例１において、触媒としてメチレンビス（メチル錫
オキシド）の代わりにジ−ｎ−ブチル錫オキシドを用い
た。得られた重合体は極限粘度〔η〕が０．５１６であ
り、色調は透明であるが、やや黄色に着色していた。Comparative Example 1 In Example 1, di-n-butyltin oxide was used instead of methylenebis(methyltin oxide) as a catalyst. The obtained polymer had an intrinsic viscosity [η] of 0.516 and was transparent in color, but slightly yellow in color.
比較例２
実施例２において、触媒としてメチレンビス（メチル錫
オキシド）の代わりに二酸化アンチモンを４ Ｘ １０
”２モル％用いたところ、極限粘度〔η〕は０．８９２
と低く、色調もわずかに灰白色に着色していた。Comparative Example 2 In Example 2, antimony dioxide was used as a catalyst instead of methylenebis(methyltin oxide) at 4×10
``When using 2 mol%, the intrinsic viscosity [η] was 0.892.
The color was low, and the color tone was slightly grayish-white.
Claims (5)
ボン酸またはそのエステル形成性誘導体とグリコールと
からポリエステルを製造するに際し、触媒として下記一
般式（１）及び／又は（２）で示される有機錫化合物を
使用して重縮合せしめることを特徴とするポリエステル
の製造方法。 ▲数式、化学式、表等があります▼………………（１） ▲数式、化学式、表等があります▼………………（２） （式中Ｒ＾１、Ｒ＾３はアルキル基、アリール基、Ｒ＾
２はアルキレン基、Ｘ＾１、Ｘ＾２、Ｘ＾３、Ｘ＾４は
ＯＨ基、ＯＲ基、ＯＣＯＲ基、Ｃｌ、Ｂｒ またはＩであり、ここに含まれるＲはア ルキル基またはアリール基である。）(1) When producing a polyester from a difunctional carboxylic acid whose main component is an aromatic dicarboxylic acid or an ester-forming derivative thereof and glycol, a catalyst represented by the following general formula (1) and/or (2) is used. A method for producing polyester, characterized by polycondensation using an organic tin compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼………………(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼……………………(2) (In the formula, R^1 and R^3 are alkyl group, aryl group, R^
2 is an alkylene group; X^1, X^2, X^3, and X^4 are an OH group, an OR group, an OCOR group, Cl, Br, or I; be. )
求の範囲第１項に記載の方法。(2) The method according to claim 1, wherein the aromatic dicarboxylic acid is terephthalic acid.
の範囲第１項に記載の方法。(3) The method according to claim 1, wherein the glycol is ethylene glycol.
数１〜４のアルキレン基である特許請求の範囲第１項に
記載の方法。(4) The method according to claim 1, wherein R^2 in general formulas (1) and (2) is an alkylene group having 1 to 4 carbon atoms.
ス（ジクロロメチルスタニル）メタンである特許請求の
範囲第１項記載の方法。(5) The method according to claim 1, wherein the catalyst is methylenebis(methyltin oxide) or bis(dichloromethylstannyl)methane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62031682A JP2531584B2 (en) | 1987-02-13 | 1987-02-13 | Method for producing polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62031682A JP2531584B2 (en) | 1987-02-13 | 1987-02-13 | Method for producing polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63199222A true JPS63199222A (en) | 1988-08-17 |
| JP2531584B2 JP2531584B2 (en) | 1996-09-04 |
Family
ID=12337866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62031682A Expired - Lifetime JP2531584B2 (en) | 1987-02-13 | 1987-02-13 | Method for producing polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2531584B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0266958A (en) * | 1988-09-01 | 1990-03-07 | Fujitsu Ltd | Semiconductor integrated circuit device |
-
1987
- 1987-02-13 JP JP62031682A patent/JP2531584B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0266958A (en) * | 1988-09-01 | 1990-03-07 | Fujitsu Ltd | Semiconductor integrated circuit device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2531584B2 (en) | 1996-09-04 |
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