KR20000025399A - Monomer for polyester copolymerization and copolyester copolymerized therewith - Google Patents
Monomer for polyester copolymerization and copolyester copolymerized therewith Download PDFInfo
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- KR20000025399A KR20000025399A KR1019980042472A KR19980042472A KR20000025399A KR 20000025399 A KR20000025399 A KR 20000025399A KR 1019980042472 A KR1019980042472 A KR 1019980042472A KR 19980042472 A KR19980042472 A KR 19980042472A KR 20000025399 A KR20000025399 A KR 20000025399A
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- Prior art keywords
- polyester
- monomer
- copolyester
- reaction
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- 229920000728 polyester Polymers 0.000 title claims abstract description 35
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 26
- 239000000178 monomer Substances 0.000 title claims abstract description 25
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 19
- 239000002184 metal Substances 0.000 abstract description 19
- 239000000835 fiber Substances 0.000 abstract description 18
- 229920000642 polymer Polymers 0.000 abstract description 12
- 239000003513 alkali Substances 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 8
- 125000002091 cationic group Chemical group 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 4
- 238000009987 spinning Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- 238000010828 elution Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- MBWVCEZZJUXUHB-UHFFFAOYSA-I zinc antimony(3+) pentaacetate Chemical compound [Sb+3].C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] MBWVCEZZJUXUHB-UHFFFAOYSA-I 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/04—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body
- H01L27/08—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including only semiconductor components of a single kind
- H01L27/085—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including only semiconductor components of a single kind including field-effect components only
- H01L27/088—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including only semiconductor components of a single kind including field-effect components only the components being field-effect transistors with insulated gate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/06—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions
- H01L29/10—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by their shape; characterised by the shapes, relative sizes, or dispositions of the semiconductor regions ; characterised by the concentration or distribution of impurities within semiconductor regions with semiconductor regions connected to an electrode not carrying current to be rectified, amplified or switched and such electrode being part of a semiconductor device which comprises three or more electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Ceramic Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
본 발명은 폴리에스테르 공중합용 단량체 및 이들이 공중합된 코폴리에스테르에 관한 것이다.The present invention relates to monomers for polyester copolymerization and copolyesters in which they are copolymerized.
일반적으로 폴리에스테르는 디메틸테레프탈레이트(이하 "DMT"라고 한다)와 에틸렌글리콜(이하 "EG"라고 한다)을 에스테르 교환반응과 중축합 반응시켜 제조한다.Generally, polyesters are prepared by transesterification and polycondensation of dimethyl terephthalate (hereinafter referred to as "DMT") and ethylene glycol (hereinafter referred to as "EG").
종래 폴리에스테르 제조반응에서는 에스테르 교환반응 단계와 중축합 반응단계에 각각 금속촉매를 일정량 투입해 반응속도를 향상시킴으로서 반응의 경제성을 높이고 있으며, 중축합 반응단계에서는 부가적으로 반응부산물인 에틸렌글리콜을 강제로 계외로 유출시킴으로서 중합반응을 보다 유리하게 수행시키고 있다. 이러한 촉매류로는 먼저 에스테르 교환반응에서는 금속초산염들이 일반적으로 사용되며, 중합촉매로는 산화안티몬, 초산안티몬 또는 금속 알콕시드(Alkoxide)류 등이 널리 사용되어 있다. 금속 알콕시드류의 금속은 티타늄, 틴 등이다. 그러나 폴리에스테르 중합반응 자체는 평형반응이므로 투입된 상기 촉매들은 정반응뿐만 아니라 역반응 및 부반응 또한 가속화시키는 문제점이 있다. 투입 사용되는 촉매들로 인하여 중축합 반응초기에는 정반응쪽으로 유리하게 작용하나, 중축합 반응 말기에는 오히려 역반응과 부반응이 보다 활성화됨으로서 생성되는 폴리에스테르의 물성저하가 우려된다. 구체적으로 폴리머의 색상이 저하되고 폴리머 내에 디에틸렌글리콜(DEG), 카르복실말단, 이중결합 및 겔 등의 부생성물들이 증가하여 최종제품의 색상 및 기계적 물성이 저하하게 된다. 특히 섬유 제조공정시 절사가 증가하거나 방사구금 주변에 이물이 축적되어 조업성이 나빠지는 문제가 있다. 따라서 일반적인 중합 반응에서는 투입된 금속촉매를 봉쇄(Capturing)하기 위해서 인(P)계 내열제를 일정량 투입한다. 투입된 내열제들은 금속촉매들과 컴플렉스(Complex)를 형성하여 효율적으로 촉매 활성을 봉쇄하게 된다. 일반적으로 인(P)계 내열제로는 인산, 트리메틸포스페이트 또는 트리알킬포스페이트 등이 사용되고 있다. 그러나 이러한 내열제를 사용할 경우 반응이 끝난 후 내열제와 금속촉매와의 컴플렉스(Complex)가 최종 폴리에스테르 고분자 내에 내부입자 형태로 존재하여 폴리머중의 새로운 이물로 작용하게 된다. 그 결과 후공정성이나 제품의 품질이 저하하게 되는 문제가 있다. 즉, 섬유로 제조하기 위한 후공정 흐름중에서 상기 내열제와 금속촉매의 컴플렉스(Complex)들이 고분자상외로 유리, 유출되면서 이물을 걸러주는 방사팩 필터에 걸리게 된다. 그 결과 방사팩 필터의 압력이 상승하여 섬유 물성이 불균일하게 되거나 저하된다. 또한 상기 컴플렉스(Complex)들이 구금하부에 부착되어 절사, 곡사를 일으키기도 한다. 또한 방사팩 필터의 교체 및 청소주기가 짧아져 섬유 제조비용이 증가하고 생산성도 저하된다.In the conventional polyester production reaction, a certain amount of metal catalyst is added to each of the transesterification step and the polycondensation reaction step to improve the reaction rate, and the polycondensation reaction step additionally forcibly applies the reaction byproduct ethylene glycol. The polymerization reaction is carried out more advantageously by flowing out of the furnace. As such catalysts, metal acetates are generally used in the transesterification reaction, and antimony oxide, antimony acetate or metal alkoxides are widely used as polymerization catalysts. Metals of the metal alkoxides are titanium, tin and the like. However, since the polyester polymerization itself is an equilibrium reaction, the added catalysts have a problem of accelerating not only forward reaction but also reverse reaction and side reaction. Due to the catalysts used, the reaction is advantageously directed toward the forward reaction at the beginning of the polycondensation reaction, but at the end of the polycondensation reaction, there is a concern that the physical properties of the resulting polyester are lowered due to more active reactions of the reverse reaction and side reactions. Specifically, the color of the polymer is lowered and by-products such as diethylene glycol (DEG), carboxyl terminal, double bond, and gel are increased in the polymer, thereby decreasing the color and mechanical properties of the final product. In particular, there is a problem that the cutting operation during the fiber manufacturing process increases or foreign matter accumulates around the spinneret, worsening the operability. Therefore, in a general polymerization reaction, a certain amount of phosphorus (P) -based heat resistant agent is added in order to block the metal catalyst introduced. The added heat resistant agents form complexes with the metal catalysts to effectively block the catalytic activity. Generally, phosphoric acid, trimethyl phosphate, trialkyl phosphate, or the like is used as the phosphorus (P) -based heat resistant agent. However, in the case of using such a heat-resistant agent, after completion of the reaction, the complex of the heat-resistant agent and the metal catalyst is present in the form of internal particles in the final polyester polymer to act as a new foreign material in the polymer. As a result, there is a problem that post-processability and product quality are deteriorated. In other words, the complex of the heat-resistant agent and the metal catalyst is released into the polymer phase out of the polymer phase in the post-process flow for manufacturing the fiber, and caught by the spin pack filter that filters foreign matter. As a result, the pressure of the spin pack filter rises, resulting in uneven or deteriorated fiber properties. In addition, the complexes are attached to the lower part of the prison to cause cutting and bending. In addition, the replacement and cleaning cycles of spin pack filters are shortened, which increases fiber manufacturing costs and reduces productivity.
본 발명은 이와 같은 종래 기술의 문제점들을 해결할 수 있도록 금속촉매의 봉쇄(Capturing)시 새로운 이물이 발생되지 않아 제사 공정성을 향상시키는 새로운 폴리에스테르 공중합용 단량체 및 이들이 공중합되어 품질이 우수한 코폴리에스테르를 제공하고자 한다.The present invention provides a new polyester copolymerizing monomer for copolymerization and new copolyester which is excellent in quality because no foreign matter is generated during capturing of the metal catalyst so as to solve the problems of the related art. I would like to.
본 발명은 폴리에스테르 중합공정 중에 종래 인(P)계 내열제와 같이 금속촉매등과 컴플렉스(Complex)를 형성하여 금속촉매의 활성을 봉쇄하면서도, 폴리머 내에 새로운 이물질을 발생시키지 않아 제사 공정성 및 섬유물성을 향상시키고, 방사팩 교체 및 청소주기를 연장시킬 수 있는 새로운 폴리에스테르 공중합용 단량체를 제공하고자 한다. 또한 본 발명은 상기 폴리에스테르 공중합 단량체가 공중합되어 수축성, 알칼리 용출성 및 양이온 염색성이 향상된 코폴리에스테르를 제공하고자 한다.The present invention forms a complex with a metal catalyst such as a phosphorus (P) -based heat-resistant agent during the polyester polymerization process to block the activity of the metal catalyst, and does not generate new foreign substances in the polymer. To improve the performance, and to provide a new monomer for copolymerizing polyester that can extend the spin pack replacement and cleaning cycle. In another aspect, the present invention is to provide a copolyester with copolymerization of the polyester copolymer monomer is improved shrinkage, alkali dissolution and cation dyeing.
본 발명은 폴리에스테르 공중합용 단량체 및 이들이 공중합된 코폴리에스테르에 관한 것이다. 더욱 구체적으로 본 발명은 아래 일반식(I)의 구조를 갖는 폴리에스테르 공중합용 단량체에 관한 것이다.The present invention relates to monomers for polyester copolymerization and copolyesters in which they are copolymerized. More specifically, the present invention relates to a monomer for polyester copolymer having a structure of formula (I) below.
(I) (I)
일반식(I)에서 R1및 R2는 알킬 그룹이다.R 1 and R 2 in formula (I) are alkyl groups.
또한 본 발명은 상기 폴리에스테르 공중합용 단량체가 폴리에스테르 내의 산성분 중량대비 0.2∼15중량% 공중합된 코폴리에스테르에 관한 것이다.The present invention also relates to a copolyester in which the polyester copolymer monomer is copolymerized 0.2 to 15% by weight based on the weight of the acid component in the polyester.
이하 본 발명을 더욱 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 종래 폴리에스테르 중합반응시 금속촉매 활성을 봉쇄하기 위해 사용해온 인(P)계 내열제와 알카리 용출성 및 수축성 등의 특수 물성부여를 위해 사용해온 디메틸 이소프탈릭 술포네이트 등과 같은 공중합물의 특성을 동시에 구비한 단량체를 제공한다.The present invention is characterized in that copolymers such as dimethyl isophthalic sulfonate and the like have been used for imparting special properties such as phosphorus (P) heat-resistant agents used to block metal catalyst activity during polyester polymerization and alkali dissolution and shrinkage properties. It provides a monomer having at the same time.
본 발명의 폴리에스테르 공중합용 단량체는 아래 일반식(I)의 구조를 갖는다.The monomer for copolymerizing polyester of this invention has a structure of the following general formula (I).
(I) (I)
상기식(I)에서 R1및 R2는 알킬 그룹이다.In formula (I), R 1 and R 2 are alkyl groups.
일반식(I)의 폴리에스테르 공중합용 단량체는 이소프탈릭 액시드와 HPO2Cl2또는 POCl3화합물을 140℃ 이상에서 반응시킨 후 수세 증류 및 정제하여 제조할 수 있다.The monomer for polyester copolymerization of general formula (I) may be prepared by reacting isophthalic acid with HPO 2 Cl 2 or POCl 3 at 140 ° C. or more, followed by distillation and purification with water.
구체적인 제조방법 중 하나를 반응식으로 살펴보면 아래와 같다.Looking at one of the specific manufacturing method as a reaction scheme as follows.
이하 일반식(I)의 폴리에스테르 공중합용 단량체로 상기 반응식에 의해 제조된 디알킬 이소프탈릭 포스포네이트(이하 "DMIP"라고 한다.)를 사용하는 경우를 중심으로 본 발명을 설명하고자 한다. 그러나 일반식(I)의 단량체가 DMIP에 국한되는 것은 아니다.Hereinafter, the present invention will be mainly described using a dialkyl isophthalic phosphonate (hereinafter referred to as "DMIP") prepared by the above reaction formula as a monomer for polyester copolymerization of general formula (I). However, the monomer of general formula (I) is not limited to DMIP.
폴리에스테르 중합공정에서 상기 DMIP를 일정량 공중합시키면 DMIP는 코폴리에스테르의 주사슬 내에 존재하게 된다. DMIP 분자 내의 인(P)은 내열성 향상에 기여함과 동시에 중축합 반응 말기에 금속촉매들과 접촉하면서 이들과 컴플렉스(Complex)를 형성하여 금속촉매의 활성을 봉쇄하게 된다. 이와같이 형성된 컴플렉스(Complex)들은 코폴리에스테르의 주사슬 내에 존재하기 때문에 후공정에서 폴리머상외로 빠져나오기 어렵게 되어 종래와 같이 폴리머내 이물로 작용하지 않게 된다. 그 결과 절사등이 감소하고 제사성 및 섬유물성이 향상된다. 또한 방사 팩의 교체 및 청소주기도 길어져 생산성이 향상되고 제조원가도 절감된다.When the DMIP is copolymerized in a predetermined amount in the polyester polymerization process, the DMIP is present in the main chain of the copolyester. Phosphorus (P) in the DMIP molecule contributes to improved heat resistance and forms a complex with these metal catalysts at the end of the polycondensation reaction, thereby blocking the activity of the metal catalyst. The complexes thus formed are present in the main chain of the copolyester, so that they are difficult to escape out of the polymer phase in the post-process, and thus do not act as foreign substances in the polymer. As a result, cutting and the like are reduced, and sandability and fiber properties are improved. In addition, replacement cycles and cleaning cycles for spin packs are extended, resulting in increased productivity and reduced manufacturing costs.
또한 공중합된 DMIP는 킨크(Kink) 구조를 갖고 있어서 코폴리에스테르 주사슬의 정렬성(Regularity)을 저하시킨다. 그 결과 코폴리에스테르 내에 비정영역이 늘어나 섬유의 수축성, 알카리 용출성이 증가하게 된다. 또한 DMIP분자 내의 인계 그룹이 음성물이기 때문에 양이온 염색성이 향상되기도 한다.In addition, the copolymerized DMIP has a kink structure, thereby reducing the regularity of the copolyester main chain. As a result, the amorphous region increases in the copolyester, which increases the shrinkage of the fiber and alkali dissolution. In addition, since the phosphorus group in the DMIP molecule is a negative substance, the cation dyeability may be improved.
본 발명은 폴리에스테르 중합공정 중에 상기 일반식(I)의 단량체를 투입, 공중합시켜 코폴리에스테르를 제조한다. 이때 일반식(I)의 단량체 함량을 코폴리에스테르 내의 산성분 중량대비 0.2∼15중량%, 더욱 좋기로는 0.2∼8중량%로 조절하는 것이 바람직 하다. 일반식(I)의 단량체 함량이 상기 범위보다 낮을 경우에는 내열성 및 금속촉매의 활성을 봉쇄하는 효과가 낮고 섬유의 수축성, 알카리 용출성 및 양이온 염색성이 저하된다. 한편 단량체 함량이 상기 범위를 초과하는 경우에는 섬유의 기계적 물성이 저하된다.In the present invention, a copolyester is prepared by adding and copolymerizing a monomer of the general formula (I) in a polyester polymerization step. At this time, the monomer content of the general formula (I) is preferably adjusted to 0.2 to 15% by weight, more preferably 0.2 to 8% by weight relative to the weight of the acid component in the copolyester. When the monomer content of Formula (I) is lower than the above range, the effect of blocking the heat resistance and activity of the metal catalyst is low, and the shrinkage of the fiber, alkali dissolution property and cation dyeing property are lowered. On the other hand, when the monomer content exceeds the above range, the mechanical properties of the fiber are lowered.
이하 실시예 및 비교실시예를 통해 본 발명을 더욱 구체적으로 살펴본다. 그러나 본 발명은 하기 실시예에만 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.
실시예 1Example 1
·디메틸 이소프탈릭 포스포네이트(DMIP) 제조Dimethyl isophthalic phosphonate (DMIP)
이소프탈릭 액시드(IPA) 500kg과 HPO2Cl2400kg을 반응기에 투입한 후 150℃에서 반응시키고, 이들을 수세한다. 수세된 반응물을 메탄올 액에 침지시킨 후 증류한 후 생성물을 정제하여 디메틸 이소프탈릭 포스포네이트(DMIP)를 제조한다.500 kg of isophthalic acid (IPA) and 400 kg of HPO 2 Cl 2 were added to the reactor and reacted at 150 ° C., and these were washed with water. The washed reactant is immersed in methanol and then distilled to purify the product to produce dimethyl isophthalic phosphonate (DMIP).
·코폴리에스테르의 제조Preparation of Copolyester
디메틸테레프탈레이트(DMT) 1500kg, 디메틸 이소프탈릭 포스포네이트(DMIP) 15kg, 에틸렌글리콜(EG) 700kg 및 초산아연 200ppm을 에스테르 교환반응기에 넣고 150℃로 승온하여 교반을 실시하고, 메탄올을 반응기외로 유출시키면서 2시간 후 온도가 230℃까지 올라가도록 가열하여 에스테르 교환반응을 시킨 다음 에틸렌글리콜을 유출시킨다. 여기에 안티몬 트리옥사이드 350ppm을 투입한 후, 반응기 온도를 280℃까지 가열하면서 압력을 상압에서 1토르(Torr) 이하의 고진공으로 감압하여 폴리에스테르를 공중합 한다. 공중합된 폴리에스테르를 통상의 방법으로 방사하여 코폴리에스테르 섬유를 제조한다. 이때 반응시간, 제사조업성, 팩 교체주기와 코폴리에스테르 섬유의 수축성, 알카리 용출성 및 양이온 염색성을 측정한 결과는 표2와 같다.1500 kg of dimethyl terephthalate (DMT), 15 kg of dimethyl isophthalic phosphonate (DMIP), 700 kg of ethylene glycol (EG), and 200 ppm of zinc acetate were placed in a transesterification reactor, heated to 150 ° C., stirred, and methanol was taken out of the reactor. After 2 hours, the temperature was raised to 230 ° C., followed by a transesterification reaction, and ethylene glycol was distilled off. 350 ppm of antimony trioxide was added thereto, followed by heating the reactor temperature to 280 ° C. to reduce the pressure to a high vacuum of 1 Torr or less at normal pressure to copolymerize the polyester. Copolyester fibers are produced by spinning the copolymerized polyester in a conventional manner. At this time, the reaction time, manufacturing performance, pack replacement cycle and shrinkage of the copolyester fiber, alkali elution and cationic dyeability measurement results are shown in Table 2.
실시예 2∼실시예 7Example 2-Example 7
코폴리에스테르 공중합시 DMIP의 사용량, 촉매의 종류 및 사용량을 표1과 같이 변경한 것을 제외하고는 실시예 1과 동일한 공정 및 조건으로 코폴리에스테르 섬유를 제조한다. 이때 반응시간, 제사조업성, 팩 교체주기와 코폴리에스테르 섬유의 수축성, 알카리 용출성 및 양이온 염색성을 측정한 결과는 표2와 같다.Copolyester fibers are manufactured by the same process and conditions as in Example 1 except that the amount of DMIP used, the type of catalyst, and the amount used of the copolymer are changed as shown in Table 1. At this time, the reaction time, manufacturing performance, pack replacement cycle and shrinkage of the copolyester fiber, alkali elution and cationic dyeability measurement results are shown in Table 2.
비교실시예 1∼비교실시예 2Comparative Example 1 to Comparative Example 2
코폴리에스테르 공중합시 DMIP 대신에 디메틸 이소프탈릭 술포네이트(이하 "DMIS" 라고한다.)를 표1과 같이 사용하고 촉매의 종류 및 사용량을 표1과 같이 변경한 것을 제외하고는 실시예 1과 동일한 공정 및 조건으로 코폴리에스테르 섬유를 제조한다. 이때 반응시간, 제사조업성, 팩 교체주기와 코폴리에스테르 섬유의 수축성, 알카리 용출성 및 양이온 염색성을 측정한 결과는 표2와 같다.Same as Example 1 except for using dimethyl isophthalic sulfonate (hereinafter referred to as "DMIS") instead of DMIP as shown in Table 1 and changing the type and amount of catalyst used as shown in Table 1. Processes and conditions produce copolyester fibers. At this time, the reaction time, manufacturing performance, pack replacement cycle and shrinkage of the copolyester fiber, alkali elution and cationic dyeability measurement results are shown in Table 2.
비교실시예 3Comparative Example 3
폴리에스테르 중합시 DMIP를 사용하지 않고, 촉매의 종류 및 사용량을 표1과 같이 변경한 것을 제외하고는 실시예 1과 동일한 공정 및 조건으로 폴리에스테르, 섬유를 제조한다. 이때 반응시간, 제사조업성, 팩 교체주기와 코폴리에스테르 섬유의 수축성, 알카리 용출성 및 양이온 염색성을 측정한 결과는 표2와 같다.A polyester and a fiber are manufactured in the same process and conditions as in Example 1, except that DMIP is not used in the polyester polymerization, and the type and amount of the catalyst are changed as shown in Table 1. At this time, the reaction time, manufacturing performance, pack replacement cycle and shrinkage of the copolyester fiber, alkali elution and cationic dyeability measurement results are shown in Table 2.
<표1> 제조조건<Table 1> Manufacturing Conditions
<표2> 조업성 및 섬유물성 평가 결과<Table 2> Operational and Textile Property Evaluation Results
본 발명에 있어서 각종 물성은 다음과 같이 측정한다.Various physical properties in the present invention are measured as follows.
·반응시간Reaction time
중축합 반응 시작부터 펠렛팅까지 소요시간을 측정한다.The time required from the start of the polycondensation reaction to the pelleting is measured.
·조업성(%)Operability (%)
총원사 드럼 중 풀원사 드럼 수를 백분율로 표시한다.Number of full yarn drums in total yarn drums in percentage.
조업성=
·방사팩 청소주기(일)· Radiation Pack Cleaning Cycle (Days)
초압에 관계없이 시작에서 부터 2800포아즈에 도달하는데 소요되는 기일을 측정한다.Measure the time it takes to reach 2800 poise from the start, regardless of pressure.
·수축성·contractility
100℃ 열수에서 15분간 처리 후 수축성을 관능 평가한다.Sensory evaluation of shrinkage after 15 minutes treatment at 100 ℃ hot water.
·알카리 용출성(%)Alkaline dissolution rate (%)
95℃인 1노르말 가성 소오다에서 30분간 처리 후 처리전 후의 무게를 다음식에 대입하여 구한다.After treatment for 30 minutes in 1-Normal caustic soda at 95 ° C, the weight before and after treatment is obtained by the following equation.
알카리 용출성(%)=
·양이온 염색성Cationic Dyeing
1% owf 염욕에서 98℃에서 30분간 염색 후 관능 평가한다.Sensory evaluation was performed after dyeing at 98 ° C. for 30 minutes in a 1% owf salt bath.
본 발명의 폴리에스테르 공중합용 단량체는 폴리에스테르 중합반응 중에 금속촉매들과 컴플렉스(Complex)를 형성하여 금속촉매의 활성을 봉쇄함과 동시에 폴리머 내에 새로운 이물을 발생시키지 않는다. 그 결과 제사시 절사 등이 감소하여 제사공정성 및 섬유물성이 향상되며, 방사 팩 교체 및 청소주기가 연장되어 생산성이 향상되고 제조원가가 절감된다.The monomer for polyester copolymerization of the present invention forms a complex with the metal catalysts during the polyester polymerization reaction to block the activity of the metal catalyst and does not generate new foreign substances in the polymer. As a result, weaving is reduced, and thus weaving processability and fiber properties are improved, and the spinning pack replacement and cleaning cycle are extended to improve productivity and reduce manufacturing costs.
또한 본 발명의 코폴리에스테르는 품질이 향상됨과 동시에 수축성, 알칼리 용출성 및 양이온 염색성이 우수하다.In addition, the copolyester of the present invention is excellent in shrinkage, alkali dissolution property and cation dyeing property while improving quality.
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019980042472A KR20000025399A (en) | 1998-10-12 | 1998-10-12 | Monomer for polyester copolymerization and copolyester copolymerized therewith |
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| KR1019980042472A KR20000025399A (en) | 1998-10-12 | 1998-10-12 | Monomer for polyester copolymerization and copolyester copolymerized therewith |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5151494A (en) * | 1991-01-04 | 1992-09-29 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
| US5180793A (en) * | 1991-12-31 | 1993-01-19 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
| JPH05117502A (en) * | 1991-10-24 | 1993-05-14 | Sekisui Chem Co Ltd | Copolyester composition |
| JPH05117381A (en) * | 1991-10-25 | 1993-05-14 | Sekisui Chem Co Ltd | Production of polyester copolymer |
-
1998
- 1998-10-12 KR KR1019980042472A patent/KR20000025399A/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5151494A (en) * | 1991-01-04 | 1992-09-29 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
| JPH05117502A (en) * | 1991-10-24 | 1993-05-14 | Sekisui Chem Co Ltd | Copolyester composition |
| JPH05117381A (en) * | 1991-10-25 | 1993-05-14 | Sekisui Chem Co Ltd | Production of polyester copolymer |
| US5180793A (en) * | 1991-12-31 | 1993-01-19 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
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| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application |