JPH03152137A - Polyester porous material, production thereof and solid phase polymerization of polyester - Google Patents
Polyester porous material, production thereof and solid phase polymerization of polyesterInfo
- Publication number
- JPH03152137A JPH03152137A JP28869189A JP28869189A JPH03152137A JP H03152137 A JPH03152137 A JP H03152137A JP 28869189 A JP28869189 A JP 28869189A JP 28869189 A JP28869189 A JP 28869189A JP H03152137 A JPH03152137 A JP H03152137A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- solvent
- phase polymerization
- prepolymer
- 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.)
- Pending
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 70
- 239000007790 solid phase Substances 0.000 title claims abstract description 34
- 229920000728 polyester Polymers 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011148 porous material Substances 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 8
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 abstract description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012965 benzophenone Substances 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- 239000012071 phase Substances 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- -1 alkylene terephthalate Chemical compound 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids 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
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 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
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-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
- 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 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000001000 micrograph Methods 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- IBBQVGDGTMTZRA-UHFFFAOYSA-N sodium;2-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O IBBQVGDGTMTZRA-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- 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、比表面積0.1nf/g以上のポリエステル
多孔体及びその製造法及びそのポリエステル多孔体を用
いる、ポリエステルの固相重合法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyester porous material having a specific surface area of 0.1 nf/g or more, a method for producing the same, and a solid phase polymerization method for polyester using the polyester porous material.
更に詳しくは、本発明は、比表面積の著しく拡大された
ポリエステル多孔体を利用することにより、繊維、フィ
ルム、その他の成形物に有用な高品質のポリエステルを
、面相重合で迅速に製造する方法に関する。More specifically, the present invention relates to a method for rapidly producing high-quality polyester useful for fibers, films, and other molded products by surface phase polymerization by utilizing a porous polyester material with a significantly expanded specific surface area. .
(従来の技術)
ポリエステルの重合度を増大させる方法としてポリエス
テル粒子を減圧下または不活性気体流通下に、融点以下
の温度で反応させる、いわゆる固相重合法はよく知られ
ている。(Prior Art) As a method for increasing the degree of polymerization of polyester, a so-called solid phase polymerization method in which polyester particles are reacted under reduced pressure or under an inert gas flow at a temperature below their melting point is well known.
しかしながら、通常用いられるチップと称される円柱状
、角柱状体等(粒径3〜5−相当)では、反応副生成物
の拡散が遅い等の理由により固相重合速度が非常に遅く
、充分な経済性が得られない。However, in the case of commonly used cylindrical or prismatic bodies (equivalent to particle size 3 to 5) called chips, the solid phase polymerization rate is very slow due to slow diffusion of reaction by-products, etc. economical efficiency cannot be achieved.
また、チップ表面の方が内部よりも反応副生成物の拡散
が速く、即ち重合速度が速いために、固相重合後のチッ
プ内外に重合度のばらつきが生じ、これを利用した成形
品の品質は粗悪なものになるという欠点を有す。In addition, because reaction byproducts diffuse faster on the chip surface than inside the chip, in other words, the polymerization rate is faster, variations in the degree of polymerization occur inside and outside the chip after solid-phase polymerization, and this can lead to quality problems in molded products. has the disadvantage of being inferior.
これらの低固相重合速度や、チップ内の広い重合度分布
を解消するための抜本的な方法として、チップの小粒子
化が試みられているが、ポリエステルポリマーの強靭さ
の故に、粉砕コストが多大にかかり、また、固相重合装
置内で融着が生じやすくなり、さらには移送時の取扱が
面倒である等プロセス上の問題も多い、また、粉砕した
場合に、粒度分布が必ず生じ、これを固相重合すると粒
径の違いにより固相重合速度が異なって来るため、粉砕
物の固相重合後の分子量分布は極めて広いものとなる。As a drastic method to solve these low solid phase polymerization rates and wide polymerization degree distribution within chips, attempts have been made to make chips smaller, but due to the toughness of polyester polymers, the crushing cost is high. It takes a lot of time, and there are many process problems such as fusion easily occurring in the solid phase polymerization equipment and troublesome handling during transportation.Furthermore, when pulverized, particle size distribution inevitably occurs. When this is subjected to solid phase polymerization, the solid phase polymerization rate varies depending on the particle size, so the molecular weight distribution of the pulverized product after solid phase polymerization becomes extremely wide.
これらのことより、小粒化による方法の実用化は困難で
ある。For these reasons, it is difficult to put the method of particle size reduction into practical use.
(発明が解決しようとする諜ll!l)本発明は、これ
まで製造することが困難であった速い面相重合速度と粒
子内の狭い重合度分布を得るのに要するポリエステル多
孔体、その製造法及びそれを用いたポリエステルの固相
重合法を提供するものである。(Intelligence to be solved by the invention!l) The present invention provides a polyester porous material necessary for obtaining a high surface phase polymerization rate and a narrow polymerization degree distribution within the particles, which have been difficult to produce up to now, and a method for producing the same. The present invention also provides a method for solid phase polymerization of polyester using the same.
(課題を解決するための手段)
本発明者らは、ポリエステルの固相重合に関する諸因子
と重合速度等との関係に着目し、ポリマーの多孔化によ
る比表面積の拡大方法に着眼し種々検討した結果、ポリ
マーに溶媒を加えて加熱溶解後冷却した場合に、該溶液
が固化する溶媒を選び、固化した状態から溶媒を脱離す
ることによって、多孔化が可能となることを見出した。(Means for Solving the Problems) The present inventors focused on the relationship between various factors related to the solid phase polymerization of polyester and the polymerization rate, etc., and conducted various studies focusing on a method for increasing the specific surface area by making the polymer porous. As a result, it was discovered that when a solvent is added to a polymer, heated and dissolved, and then cooled, a solvent that solidifies the solution is selected, and by removing the solvent from the solidified state, it is possible to create porosity.
さらに、この多孔化状態は、面相重合温度でも保持され
ており、このポリエステル多孔体をプレポリマーとして
面相重合すれば、速い重合速度が得られ、かつ重合度分
布の狭い生成物が得られることを見出した。そして、こ
れらの知見に基づき本発明を完成するに到った。Furthermore, this porous state is maintained even at the face-phase polymerization temperature, indicating that if this porous polyester material is subjected to face-phase polymerization as a prepolymer, a high polymerization rate and a product with a narrow degree of polymerization distribution can be obtained. I found it. Based on these findings, we have completed the present invention.
即ち、本発明は;
■ 比表面積が0.1m2/g以上で、極限粘度が0.
2以上のポリアルキレンテレフタレートプレポリマー多
孔体であり、また、
■ ポリアルキレンテレフタレートプレポリマー1部に
対して溶剤を0.1〜100部加え、加熱溶解した後、
冷却固化してから溶剤を除去する、比表面積が0.In
f/g以上で、極限粘度が0.2以上のポリアルキレン
テレフタレートプレポリマーの製造法であり、また、
■ ポリアルキレンテレフタレートの固相重合において
、前記■記載のプレポリマーを用いる、ポリエステルの
面相重合法である。That is, the present invention has; (1) a specific surface area of 0.1 m2/g or more and an intrinsic viscosity of 0.1 m2/g or more;
2 or more polyalkylene terephthalate prepolymer porous body;
The solvent is removed after cooling and solidifying, and the specific surface area is 0. In
A method for producing a polyalkylene terephthalate prepolymer having a polyalkylene terephthalate of f/g or more and an intrinsic viscosity of 0.2 or more; It's legal.
さらに、本発明を具体的に説明する。Furthermore, the present invention will be specifically explained.
本発明において、部とは特に断らない限り重量部を表す
。In the present invention, parts refer to parts by weight unless otherwise specified.
本発明の(多孔性)ポリエステルプレポリマー多孔体は
、比表面積が0.1rrf/g以上であることが必要で
ある。The (porous) polyester prepolymer porous body of the present invention needs to have a specific surface area of 0.1 rrf/g or more.
ポリエステルの固相重合においては、反応副生成物の拡
散を促すために、ポリマーの比表面積を拡大することが
必要であり、本発明の比表面積の拡大された多孔性ポリ
エステルプレポリマーを用いることにより面相重合速度
を高めることが出来る。比表面積がO,1rrf/g未
満では固相重合速度が改善されない、好ましい比表面積
は0.5m/g以上で、さらに好ましくは、lnf/g
以上である。In solid phase polymerization of polyester, it is necessary to expand the specific surface area of the polymer in order to promote the diffusion of reaction byproducts, and by using the porous polyester prepolymer with an expanded specific surface area of the present invention, The surface phase polymerization rate can be increased. If the specific surface area is less than O.1rrf/g, the solid phase polymerization rate will not be improved.The specific surface area is preferably 0.5m/g or more, more preferably lnf/g.
That's all.
本発明のポリエステルプレポリマーは多孔性であり、非
多孔性プレポリマーと比べて、ポリマー内部と外層の副
生成物の拡散速度に大きな差が生まれることがない、従
って、面相重合後のポリマーの重合度分布の幅を、非多
孔性プレポリマーを用いる場合に比べ、狭めることが出
来る。The polyester prepolymers of the present invention are porous, and compared to non-porous prepolymers, there is no significant difference in the diffusion rate of by-products inside the polymer and in the outer layer; therefore, the polymerization of the polymer after face-phase polymerization The width of the degree distribution can be narrowed compared to when a non-porous prepolymer is used.
本発明でいう多孔性とは、例えば第1図の走査電子S微
鏡写真に示されるようなもので、第2図ニ示されるよう
な単に粉砕したプレポリマーの表面とは全く異なるもの
である。The porosity referred to in the present invention is, for example, as shown in the scanning electron S micrograph of FIG. 1, and is completely different from the surface of a simply pulverized prepolymer as shown in FIG. 2D. .
本発明のプレポリマーの極限粘度は、0.2以上である
ことが必要である。極限粘度が0.2未満では、多孔化
後のプレポリマーが脆くてくずれやすいので、固相重合
中、及びその前後のプロセスで取り扱いが非常に面倒に
なる。The intrinsic viscosity of the prepolymer of the present invention needs to be 0.2 or more. When the intrinsic viscosity is less than 0.2, the porous prepolymer is brittle and easily crumbles, making it very difficult to handle it during solid phase polymerization and in the processes before and after the solid phase polymerization.
ここで言う極限粘度は、オルソクロロフェノールに溶解
し35°Cで測定したものである。The intrinsic viscosity referred to here is the value measured at 35°C after dissolving in orthochlorophenol.
本発明でいうポリエステルとは、アルキレンテレフタレ
ートを主たる繰り返し単位とするものであり、テレフタ
ル酸を主な酸成分とし、炭素数2〜6のアルキレングリ
コール、即ちエチレングリコール、トリメチレングリコ
ール、テトラメチレングリコール、ペンタメチレングリ
コール、ヘキサメチレングリコールから、特に好ましく
はエチレングリコール、テトラメチレングリコールから
選ばれた少なくとも一種のグリコールを主なグリコール
成分として得られるポリエステルを対象とする。The polyester used in the present invention is one that has alkylene terephthalate as the main repeating unit, and has terephthalic acid as the main acid component, and alkylene glycols having 2 to 6 carbon atoms, such as ethylene glycol, trimethylene glycol, tetramethylene glycol, The object is a polyester obtained as a main glycol component of at least one glycol selected from pentamethylene glycol and hexamethylene glycol, particularly preferably ethylene glycol and tetramethylene glycol.
また、テレフタル酸成分の一部を他の二官能性カルボン
酸成分で置換えたポリエステルであってもよく、グリコ
ール成分の一部を主成分以外の上記グリコール、若しく
は他のジオール成分で置換えたポリエステルであっても
よい。It may also be a polyester in which part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, or a polyester in which part of the glycol component is replaced with the above glycol other than the main component or another diol component. There may be.
ここで使用されるテレフタル酸以外の二官能性カルボン
酸としては、例えばイソフタル酸、ナフタリンジカルボ
ン酸、ジフェニルカルボン酸、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息香族、P−オキ
シ安息香酸、5−ナトリウムスルホイソフタル酸、アジ
ピン酸、セバシン酸、1.4−シクロヘキサンジカルボ
ン酸の如き芳香族、脂肪族、脂環族の二官能性カルボン
酸を挙げることができる。Examples of difunctional carboxylic acids other than terephthalic acid used here include isophthalic acid, naphthalene dicarboxylic acid, diphenylcarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, P-oxybenzoic acid, 5- Mention may be made of aromatic, aliphatic, and alicyclic difunctional carboxylic acids such as sodium sulfoisophthalic acid, adipic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid.
また、上記グリコール以外のジオール化合物としては、
例えばシクロヘキサン−1,4−ジメタツール、ネオペ
ンチルグリコール、ビスフェノールA1ビスフエノール
Sの如き脂肪族、脂環族、芳香族のジオール化合物およ
びポリオキシアルキレングリコール、ユニオールDAを
挙げることができる。In addition, as diol compounds other than the above glycols,
For example, aliphatic, alicyclic and aromatic diol compounds such as cyclohexane-1,4-dimetatool, neopentyl glycol, bisphenol A1 bisphenol S, polyoxyalkylene glycol and Uniol DA can be mentioned.
また、本発明のポリエステルは、トリメチロールプロパ
ン、ペンタエリスリトール、グリセリン、トリメシン酸
などの多官能性架橋剤や、モノメトキシポリエチレング
リコール、ナフトエ酸などの一官能性末端停止剤や、酸
化防止剤、紫外線吸収剤、艶消し剤としての酸化チタン
などの添加物を含んでいてもよい。In addition, the polyester of the present invention may contain polyfunctional crosslinking agents such as trimethylolpropane, pentaerythritol, glycerin, and trimesic acid, monofunctional terminal terminators such as monomethoxypolyethylene glycol and naphthoic acid, antioxidants, and ultraviolet rays. It may contain additives such as titanium oxide as an absorbent and a matting agent.
本発明の多孔性ポリエステルプレポリマーは、以下の方
法で製造することが出来る。即ち、ポリエステルポリマ
ー1部に対して溶剤を0.1〜100部を加えて、加熱
熔解した後、冷却固化した後で溶剤を除去することによ
り製造することが出来る。The porous polyester prepolymer of the present invention can be produced by the following method. That is, it can be produced by adding 0.1 to 100 parts of a solvent to 1 part of the polyester polymer, heating and melting it, cooling it to solidify it, and then removing the solvent.
ここで使用される溶剤としては、ポリエステルを溶解出
来るものならば何でもよく、炭化水素類、ハロゲン化炭
化水素類、エーテル類、ケトン類、アルコール類、フェ
ノール類、ハロゲン化フェノール類、アミン類、ニトロ
化合物類、ニトリル類、アミド類、チオール類、チオエ
ーテル類、スルホン類、スルホキシド類等が挙げられる
。特に好ましいものは、ベンゾフェノン、ジベンゾフラ
ン、ジフェニルエーテル等である。また、溶剤は単独で
用いてもよ(又2種類以上のものを混合して用いてもよ
い。The solvent used here may be any solvent as long as it can dissolve the polyester, including hydrocarbons, halogenated hydrocarbons, ethers, ketones, alcohols, phenols, halogenated phenols, amines, nitro Examples include compounds, nitriles, amides, thiols, thioethers, sulfones, sulfoxides, and the like. Particularly preferred are benzophenone, dibenzofuran, diphenyl ether and the like. Further, the solvent may be used alone (or two or more types may be used in combination).
溶剤の混合比率は、ポリエステルポリマー1部に対して
0.1〜100部であることが必要である。0.1部よ
り少ないと目的の比表面積を持つ多孔体が得られない、
また、100部より多いと多孔体が非常に脆く、粉末化
しやす(、プロセス上の取り扱いが面倒になる。好まし
い溶削量は、ポリマー1部に対し0.3〜30部である
。The mixing ratio of the solvent needs to be 0.1 to 100 parts to 1 part of the polyester polymer. If it is less than 0.1 part, a porous body with the desired specific surface area cannot be obtained.
On the other hand, if the amount is more than 100 parts, the porous body becomes very brittle and easily powdered (and handling in the process becomes troublesome).The preferable amount to be melted is 0.3 to 30 parts per part of the polymer.
原料ポリエステルの溶剤への溶解方法としては、例えば
、■ 原料ポリエステルを製造して一旦チツブ化した後
、別の溶解槽で溶解する方法、■ チップをスクリュー
で再溶融させた状態に溶剤を注入し、スクリユー内で溶
解させる方法、■ 溶融重合缶から、重合後のポリマー
を取り出す際に、スクリュー、ギアポンプ等を通過させ
る時点で溶媒を注入して溶解させる方法、■ 熔融重合
後重合部に溶剤を注入し溶解する方法、或いは
■ 溶剤を重合缶に入れた状態でプレポリマーを重合す
る方法等いくつかあるが、いずれの方法でもよい。Methods for dissolving the raw polyester in a solvent include, for example: 1) manufacturing the raw polyester and once turning it into chips and then dissolving it in a separate melting tank; 2) injecting the solvent into the chip that has been remelted with a screw. , method of dissolving in a screw, ■ method of dissolving the polymer by injecting it at the time when the polymer after polymerization is passed through a screw, gear pump, etc. when taking it out from the melt polymerization can, ■ method of dissolving the polymer by injecting it into the polymerization part after melt polymerization. There are several methods, including a method of injecting and dissolving, and a method of polymerizing a prepolymer while a solvent is placed in a polymerization can, and any method may be used.
溶解に際しての熔解温度、溶解圧力は、ポリエステルが
溶ける範囲で適宜決定される。The melting temperature and melting pressure during melting are appropriately determined within the range in which the polyester can be melted.
前記ポリエステルを熔解した溶液の冷却は、溶剤量、溶
剤量に応じて適宜行われる。Cooling of the solution obtained by melting the polyester is performed as appropriate depending on the amount of the solvent.
固化した時のポリマーの形状は、ローブ状、シート状或
いはそれらを切断したチップ状等の任意形状に作られる
。細いノズルを用いることにより繊維状に固化させ、多
孔性糸状体を製造することも出来る。The shape of the polymer when solidified can be any desired shape, such as a lobe, a sheet, or a chip formed by cutting them. By using a thin nozzle, it can be solidified into a fibrous form to produce a porous filament.
次に、この固化された溶剤の含んだ状態のポリマーから
溶剤を除去するには、溶剤による抽出、常圧下或いは減
圧下に溶剤を蒸発させる方法等いくつかあるが、いずれ
の方法でもよい。Next, there are several methods for removing the solvent from the solidified polymer containing the solvent, such as extraction with a solvent, evaporation of the solvent under normal pressure or reduced pressure, and any method may be used.
また、多孔化後のプレポリマーを、触媒、安定剤、抗酸
化剤、帯電防止剤等の添加物の含んだ液体又は、気体で
処理することにより、これらの添加物をプレポリマー内
に配合してもよい、また、これらの添加物を、多孔化の
際の抽出溶媒にあらかじめ入れておくことにより、多孔
性が得られるのと同時に、該プレポリマー内に添加物を
配合せしめることも出来る。In addition, by treating the porous prepolymer with a liquid or gas containing additives such as catalysts, stabilizers, antioxidants, and antistatic agents, these additives can be blended into the prepolymer. Alternatively, by adding these additives to the extraction solvent used for porosity formation in advance, porosity can be obtained and the additives can be blended into the prepolymer at the same time.
例えば、成形前に、チップブレンド等と称して各種の添
加物とチップを混合することも行われているが、ポリマ
ー内部にまで均一に配合するのは、均一性の点でも、時
間的にも問題がある。特に、ポリマー粒子(チップ)の
大きさが大きくなる程困難さを増す。For example, before molding, various additives and chips are mixed together in a process known as chip blending, but it is difficult to mix them evenly into the polymer, both in terms of uniformity and in terms of time. There's a problem. In particular, the difficulty increases as the size of the polymer particles (chips) increases.
しかしながら、この多孔性ポリマーを使用すると、ポリ
マー粒子(チップ)の大きさに関係なく、ポリマー内部
にまで均一にしかも迅速に配合することが出来て、これ
を利用することにより、より品質の高い多孔性成形体を
経済的に得ることが出来る。However, when this porous polymer is used, it is possible to uniformly and quickly blend it into the polymer, regardless of the size of the polymer particles (chips), and by utilizing this, higher quality pores can be created. It is possible to economically obtain a flexible molded product.
また、固相重合前に、この多孔性ポリエステルプレポリ
マーにアニーリング等の処理を施して、融点、結晶性を
高めておくことも出来る。Furthermore, before solid phase polymerization, this porous polyester prepolymer can be subjected to a treatment such as annealing to increase its melting point and crystallinity.
このようにして得られた多孔性ポリエステルプレポリマ
ーは、常法によって固相重合される。The porous polyester prepolymer thus obtained is solid-phase polymerized by a conventional method.
即ち、減圧下又は不活性気体流通下に固相重合は行われ
る。また、減圧下に少量の不活性気体を流通させる方法
も用いることが出来る。That is, solid phase polymerization is performed under reduced pressure or under inert gas flow. Furthermore, a method of flowing a small amount of inert gas under reduced pressure can also be used.
減圧下に固相重合を行う場合に、減圧度は高い程重合速
度は大きく、即ち経済的に高分子量体を得るためには1
0To r r以下、好ましくは2Torr以下、さら
に好ましくはITo r r以下の圧力にする。When performing solid phase polymerization under reduced pressure, the higher the degree of reduced pressure, the higher the polymerization rate.
The pressure is set to 0 Torr or less, preferably 2 Torr or less, and more preferably ITorr or less.
また、不活性気体を用いる場合に、不活性気体として窒
素、二酸化炭素、アルゴン等を用いることが出来る。Further, when an inert gas is used, nitrogen, carbon dioxide, argon, etc. can be used as the inert gas.
固相重合温度は、多孔性ポリエステルプレポリマーがお
互いに融着しないように、その融点以下として面相重合
を行う必要がある。固相重合中にポリエステルの融点は
アニーリングされて徐々に高くなるので、面相重合温度
を徐々に高くすることも大きな重合速度を得るためには
有効な方法である。好ましくは200〜270℃、さら
に好ましくは220〜260℃の重合温度が採用される
。The solid phase polymerization temperature must be below the melting point of the porous polyester prepolymer so that the porous polyester prepolymers do not fuse together. During solid phase polymerization, the melting point of polyester is gradually increased by annealing, so gradually increasing the surface phase polymerization temperature is also an effective method for obtaining a high polymerization rate. Preferably, a polymerization temperature of 200 to 270°C, more preferably 220 to 260°C is employed.
本発明を以下の実施例で説明するが、本発明は、これら
の実施例に限定されるものではない、各々の測定値は、
次に述べる方法で測定されたものであって、特にことわ
らない限り部とは重量部を表す。The present invention will be explained by the following Examples, but the present invention is not limited to these Examples.
It was measured by the method described below, and unless otherwise specified, parts represent parts by weight.
■還元粘度;
ポリマーをO−クロロフェノールに1g/aの濃度で溶
解し、ウベローデ型粘度針により35°Cで測定したも
のである。(2) Reduced viscosity: The polymer was dissolved in O-chlorophenol at a concentration of 1 g/a, and the viscosity was measured at 35°C using an Ubbelohde viscosity needle.
■比表面積;
島津製作断裂アキュソーブを用い、BET法によりN、
を物理吸着させ測定した。■Specific surface area: Using fracture accusorb manufactured by Shimadzu, N,
was physically adsorbed and measured.
実施例1
テレフタル酸ジメチル100部、エチレングリコール6
8部、酢酸マンガン0.05部を窒素雰囲気下140〜
220°Cに加熱し、副生ずるメタノールを2.5時間
かけて留去した。これにトリメチルフォスフェート0.
03部、酸化アンチモン0.05部を加えた後、295
°Cに昇温し、0゜5閣Hgの減圧下でエチレングリコ
ールを留去しながら2時間反応した。得られた重合物は
0.69の還元粘度であった。Example 1 100 parts of dimethyl terephthalate, 6 parts of ethylene glycol
8 parts and 0.05 part of manganese acetate under nitrogen atmosphere at 140~
The mixture was heated to 220°C, and by-produced methanol was distilled off over 2.5 hours. Add 0.0% trimethyl phosphate to this.
After adding 0.03 parts and 0.05 parts of antimony oxide, 295
The temperature was raised to 0.degree. C., and the mixture was reacted for 2 hours while ethylene glycol was distilled off under a reduced pressure of 0.5 degrees Hg. The obtained polymer had a reduced viscosity of 0.69.
このようにして得られたポリマーを、150℃の乾燥空
気を4時間流すことにより乾燥した。The polymer thus obtained was dried by flowing dry air at 150° C. for 4 hours.
この乾燥されたポリマー1部に対して2部のジフェニル
エーテルを加え、250°Cに昇温し、10分後に均一
溶液を得た。これを冷却し固化させた後、その固体を取
り出して切断し、粒径3〜5閤相当のチップにした。2 parts of diphenyl ether was added to 1 part of this dried polymer, the temperature was raised to 250°C, and a homogeneous solution was obtained after 10 minutes. After cooling and solidifying this, the solid was taken out and cut into chips with a particle size of 3 to 5 grains.
次に、この含溶剤固体1部に対して5部のアセトンを加
え、30分間攪拌し、溶剤を抽出した後に、含溶剤アセ
トンを排出した。この操作を5回繰り返し、はぼ完全に
ポリマーから溶剤を除去した。Next, 5 parts of acetone was added to 1 part of this solvent-containing solid, and the mixture was stirred for 30 minutes to extract the solvent, and then the solvent-containing acetone was discharged. This operation was repeated five times to almost completely remove the solvent from the polymer.
この多孔化されたポリマーの比表面積は114rrf/
gであった。また、還元粘度は0.69であり、該多孔
性ポリエステルの形状は(抽出前と同じであった。The specific surface area of this porous polymer is 114rrf/
It was g. Further, the reduced viscosity was 0.69, and the shape of the porous polyester was the same as before extraction.
この多孔性ポリエステルを、プレポリマーとして固相重
合機中で、0.3Torr、250℃で1時間反応させ
た。This porous polyester was reacted as a prepolymer in a solid phase polymerization machine at 0.3 Torr and 250° C. for 1 hour.
反応後の還元粘度は、1.60であった。The reduced viscosity after the reaction was 1.60.
また、チップ外表面と内部の還元粘度は、それぞれ1.
61と1.58でほとんど差がなかった。The reduced viscosity of the outer surface and inside of the chip is 1.
There was almost no difference between 61 and 1.58.
固相重合機内で、チップ同志、チップと壁面間の融着現
象は見られなかった。No fusion phenomenon was observed between the chips or between the chips and the wall inside the solid phase polymerization machine.
比較例1
実施例1と同様の方法で作られた還元粘度0゜69のポ
リエステルポリマーを多孔化せずに粒径3〜5−相当の
チップに切断し、実施例1と同様の面相重合条件で固相
重合を行った。Comparative Example 1 A polyester polymer with a reduced viscosity of 0°69 made in the same manner as in Example 1 was cut into chips with a particle size of 3 to 5 mm without making it porous, and subjected to the same face phase polymerization conditions as in Example 1. Solid phase polymerization was performed.
この固相重合後のチップの粘度は平均0.76であり、
実施例1で用いた多孔性プレポリマーと比較して、固相
重合速度が著しく劣る。The average viscosity of the chip after solid phase polymerization is 0.76,
Compared to the porous prepolymer used in Example 1, the solid state polymerization rate is significantly lower.
また、チップ外表面と内部の還元粘度はそれぞれ0.7
0と0.85で大きな開きがあった。In addition, the reduced viscosity on the outer surface and inside of the chip is each 0.7.
There was a big difference between 0 and 0.85.
実施例2〜3
ポリマーと溶剤の比率を第1表のように変更した以外は
、実施例1と同じ操作を行った。いずれも固相重合を含
む工程中、チップの形状が崩れることがなく、また融着
も生じなかった。Examples 2-3 The same operation as in Example 1 was performed except that the ratio of polymer to solvent was changed as shown in Table 1. In either case, the shape of the chip did not collapse during the process including solid phase polymerization, and no fusion occurred.
固相重合後のチップの外表面と内部の還元粘度はほぼ同
じであった。The reduced viscosity on the outer surface and inside of the chip after solid-state polymerization was almost the same.
第1表
比表面積は105rrf/gであった。固相重合後の還
元粘度は平均して1.55であり、チップの外表面と内
部の還元粘度の差はほとんどなかった。The specific surface area in Table 1 was 105rrf/g. The average reduced viscosity after solid phase polymerization was 1.55, and there was almost no difference in reduced viscosity between the outer surface and the inside of the chip.
比較例2
実施例1と同様の方法で溶融重合させた還元粘度0.6
9のポリマーを粉砕し、分級して粒径的1、 0閣で比
表面積が0.007m/gのポリエステルパウダーを得
た。これを実施例1と同様の条件で固相重合した。Comparative Example 2 Reduced viscosity 0.6 melt polymerized in the same manner as Example 1
The polymer No. 9 was crushed and classified to obtain a polyester powder having a particle size of 1.0 and a specific surface area of 0.007 m/g. This was subjected to solid phase polymerization under the same conditions as in Example 1.
固相重合後の粘度は1.15であり、本発明の多孔性ポ
リエステルチップに比べて劣り、しかも、面相重合機内
でパウダーの融着が生じ、面相重合機内の掃除等の手間
が増え、取り扱いが困難であった。The viscosity after solid phase polymerization was 1.15, which is inferior to the porous polyester chip of the present invention.Moreover, powder fusion occurs in the surface phase polymerization machine, which increases the effort of cleaning the inside of the surface phase polymerization machine, and makes handling difficult. was difficult.
実施例4
溶剤の種類をジフェニルエーテルからベンゾフェノンに
変える他は実施例1と同様の操作を行って得られたポリ
マーは、チップ形状を保持し、(発明の効果)
本発明に従って、ポリエステル多孔体を製造し、それを
用いて固相重合すると、従来には得られなかった速い面
相重合速度で重合度を増加させることが出来、しかも固
相重合で得られたポリマーの重合度分布を従来より狭く
出来、短時間に経済的に高品質の高重合度ポリエステル
を得ることが出来る。Example 4 The polymer obtained by performing the same operation as in Example 1 except that the type of solvent was changed from diphenyl ether to benzophenone retained the chip shape. (Effects of the invention) Polyester porous bodies were manufactured according to the present invention. However, when it is used for solid phase polymerization, it is possible to increase the degree of polymerization at a faster surface phase polymerization rate that could not be obtained conventionally, and the degree of polymerization distribution of the polymer obtained by solid phase polymerization can be made narrower than before. , it is possible to economically obtain high quality polyester with a high degree of polymerization in a short time.
本発明で使われた図面は、いずれも走査型電子顕微鏡で
1,000倍の倍率で撮った写真である。
第1図は、本発明の実施例1で作られたポリマー多孔体
の表面の走査型電子顕@鏡写真(1゜000倍)である
。
第2図は、比較例2で作られた還元粘度0. 69のポ
リマーを粉砕し、分級して得られた粒径約1論のポリエ
ステルパウダーの表面の走査型電子顕@鏡写真(1,0
00倍)である。
(ほか1名)The drawings used in the present invention are all photographs taken with a scanning electron microscope at a magnification of 1,000 times. FIG. 1 is a scanning electron micrograph (1°000x magnification) of the surface of the polymer porous body produced in Example 1 of the present invention. Figure 2 shows the reduced viscosity 0. Scanning electron micrograph (1,0
00 times). (1 other person)
Claims (4)
0.2以上のポリアルキレンテレフタレートプレポリマ
ー多孔体。(1) A polyalkylene terephthalate prepolymer porous body having a specific surface area of 0.1 m^2/g or more and an intrinsic viscosity of 0.2 or more.
に対して溶剤を0.1〜100部加え、加熱溶解した後
、冷却固化してから溶剤を除去することを特徴とする、
比表面積が0.1m^2/g以上で、極限粘度が0.2
以上のポリアルキレンテレフタレートプレポリマー多孔
体の製造法。(2) Adding 0.1 to 100 parts of a solvent to 1 part of polyalkylene terephthalate prepolymer, heating and dissolving, cooling and solidifying, and then removing the solvent,
Specific surface area is 0.1m^2/g or more, and intrinsic viscosity is 0.2
The method for producing the polyalkylene terephthalate prepolymer porous body described above.
て、請求項(1)記載のプレポリマー多孔体を用いるこ
とを特徴とする、ポリエステルの固相重合法。(3) A method for solid-state polymerization of polyester, characterized in that the porous prepolymer according to claim (1) is used in the solid-state polymerization of polyalkylene terephthalate.
合度が増加された、比表面積0.1m^2/g以上のポ
リアルキレンテレフタレートポリマー多孔体。(4) A polyalkylene terephthalate polymer porous body having an increased degree of polymerization and having a specific surface area of 0.1 m^2/g or more, produced by the solid phase polymerization method according to claim (3).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28869189A JPH03152137A (en) | 1989-11-08 | 1989-11-08 | Polyester porous material, production thereof and solid phase polymerization of polyester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28869189A JPH03152137A (en) | 1989-11-08 | 1989-11-08 | Polyester porous material, production thereof and solid phase polymerization of polyester |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03152137A true JPH03152137A (en) | 1991-06-28 |
Family
ID=17733446
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP28869189A Pending JPH03152137A (en) | 1989-11-08 | 1989-11-08 | Polyester porous material, production thereof and solid phase polymerization of polyester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03152137A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0850982A3 (en) * | 1996-12-31 | 2000-01-05 | Shell Internationale Researchmaatschappij B.V. | Process for recovering a solid microporous polyester polymer from a recycle stream and products made thereby |
FR2786496A1 (en) * | 1998-11-27 | 2000-06-02 | Tergal Fibres | PROCESS FOR MANUFACTURING POLYESTER |
WO2005100460A1 (en) * | 2004-04-15 | 2005-10-27 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for recycling polyesters or polyester mixtures from polyester-containing waste |
-
1989
- 1989-11-08 JP JP28869189A patent/JPH03152137A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0850982A3 (en) * | 1996-12-31 | 2000-01-05 | Shell Internationale Researchmaatschappij B.V. | Process for recovering a solid microporous polyester polymer from a recycle stream and products made thereby |
FR2786496A1 (en) * | 1998-11-27 | 2000-06-02 | Tergal Fibres | PROCESS FOR MANUFACTURING POLYESTER |
WO2000032673A1 (en) * | 1998-11-27 | 2000-06-08 | Rhodia Ster S.A. | A process for manufacturing polyester |
WO2000032674A1 (en) * | 1998-11-27 | 2000-06-08 | Tergal Fibres | Method for making polyester |
WO2005100460A1 (en) * | 2004-04-15 | 2005-10-27 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for recycling polyesters or polyester mixtures from polyester-containing waste |
US7935736B2 (en) | 2004-04-15 | 2011-05-03 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for recycling polyesters or polyester mixtures from polyester-containing waste |
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