KR970065588A - Process for producing polyester resin excellent in biodegradability - Google Patents

Process for producing polyester resin excellent in biodegradability Download PDF

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Publication number
KR970065588A
KR970065588A KR1019960005473A KR19960005473A KR970065588A KR 970065588 A KR970065588 A KR 970065588A KR 1019960005473 A KR1019960005473 A KR 1019960005473A KR 19960005473 A KR19960005473 A KR 19960005473A KR 970065588 A KR970065588 A KR 970065588A
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South Korea
Prior art keywords
acid
component
aliphatic polyester
diol component
mol
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KR1019960005473A
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Korean (ko)
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KR0181673B1 (en
Inventor
임대우
김순식
김대진
이영춘
이명섭
이창수
정성구
Original Assignee
박홍기
제일합섬 주식회사
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Priority to KR1019960005473A priority Critical patent/KR0181673B1/en
Publication of KR970065588A publication Critical patent/KR970065588A/en
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Publication of KR0181673B1 publication Critical patent/KR0181673B1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

본 발명은 기계적 강신도가 우수하고 생분해성이 우수한 고분자량의 지방족 폴리에스테르를 얻음을 목적으로 하며, 지방족 폴리에스테르는 특성상 완전분해가 가능하나, 결정성 고분자는 분자량과 유리전이온도는 높으나, 딱딱하고 용해도가 낮아 주로 의료용에 이용되어져 왔으나, 본 발명은 지방족 폴리에스테르 및 개질된 지방족 폴리에스테르를 혼합하여 생분해성 및 기계적 물성이 뛰어난 분해성 사출품, 필름을 얻기 위한 신규한 제조방법에 관한 것으로 그 기술구성은 산성분과 지방족 디올성분의 단량체를 에스테르화 교환반응시킨 다음, 티탄계 또는 주석계통의 축중합 촉매의 존재하에서 약간의 열안정제, 윤활제 및 UV 안정제를 첨가하여 축중합 반응을 얻어지는 지방족 폴리에스테르의 제조방법에 있어서, 산성분으로 숙신산 또는 그 에스테르화합물과 아디프산 또는 그 에스테르 화합물을 사용하고 디올성분으로 1,4 - 부탄티올 또는 에틸렌글리콜과의 조합에 의해 합성된 지방족 폴리에스테르(Ⅰ)과 산성분으로 테레프탈산 또는 세바식산을 사용하고, 디올성분으로 에틸렌글리콜 또는 1,4 - 부탄디올등돠의 조합에 의해 지방족 폴리에스테르(Ⅱ)를 일정비율로 혼합하여 불로잉필름 성형에 의해 140∼180℃의 온도에서 용융 압출시킴을 특징으로 하는 생분해성이 우수한 폴리에스테르 수지의 제조방법.The objective of the present invention is to obtain a high molecular weight aliphatic polyester excellent in mechanical strength and biodegradability. Although the aliphatic polyester is completely decomposable by its nature, the crystalline polymer has a high molecular weight and a high glass transition temperature, The present invention relates to a novel production method for obtaining a degradable article and film having excellent biodegradability and mechanical properties by mixing an aliphatic polyester and a modified aliphatic polyester, A process for producing an aliphatic polyester in which a monomer of an acid component and an aliphatic diol component is subjected to ester exchange reaction and then a condensation polymerization reaction is obtained by adding a little heat stabilizer, a lubricant and a UV stabilizer in the presence of a titanium- or tin- In the method, succinic acid or its esters An aliphatic polyester (I) synthesized by using a leucine compound and an adipic acid or an ester compound thereof and a diol component in combination with 1,4-butanethiol or ethylene glycol, and terephthalic acid or sebacic acid as an acid component, (II) by a combination of ethylene glycol or 1,4-butanediol as a diol component, and melt-extruding the mixture at a temperature of 140 to 180 DEG C by blowing film molding A method for producing a polyester resin having excellent properties.

Description

생분해성이 우수한 폴리에스테르 수지의 제조방법Process for producing polyester resin excellent in biodegradability

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음Since this is a trivial issue, I did not include the contents of the text.

Claims (4)

산성분과 지방족 디올성분의 단량체를 에스테르화 교환반응시킨 다음, 디탄계 또는 주석계통의 축중합 촉매의 존재하에서 약간의 열안정제, 및 UV 안정제를 첨가하여 축중합 반응으로 얻어지는 지방족 폴리에스테르의 제조방법에 있어서, 산성분으로 숙신산 또는 그 에스테르화합물과 아디프산 또는 그 에스테르 화합물을 사용하고 디올성분으로 1,4 - 부탄티올 또는 에틸렌글리콜과의 조합에 의해 합성된 지방족 폴리에스테르(Ⅰ)과 산성분으로 테레프탈산 또는 세바식산을 사용하고, 디올성분으로 에틸렌글리콜 또는 1,4 - 부탄디올등과의 조합에 의해 지방족 폴리에스테르(Ⅱ)를 일정비율로 혼합하여 불로잉필름 성형에 의해 140∼180℃의 온도에서 용융 압출시킴을 특징으로 하는 생분해성이 우수한 폴리에스테르 수지의 제조방법.There is provided a process for producing an aliphatic polyester obtained by subjecting a monomer of an acid component and an aliphatic diol component to an esterification exchange reaction and then adding a little heat stabilizer and a UV stabilizer in the presence of a di- or tin- (I) synthesized by using succinic acid or its ester compound and adipic acid or its ester compound as an acid component and combining with 1,4-butanethiol or ethylene glycol as a diol component and an acidic component Terephthalic acid or sebacic acid as a diol component and aliphatic polyester (II) in combination with ethylene glycol or 1,4-butanediol as a diol component at a certain ratio and melt at a temperature of 140 to 180 DEG C by blowing film molding Wherein the biodegradable polyester resin is a polyester resin. 제1항에 있어서, 지방족 폴리에스테르(Ⅰ)은 산성분으로는 숙신산 또는 그 에스테르 화합물이 40 내지 90몰%, 아디프산 또는 그 에스테르 화합물이 10 내지 60몰%로 구성되고, 디올성분으로는 1,4 - 부탄디올 또는 에틸렌글리콜이 단독 혹은 두성분이 혼합 구성되고, 3관능 이상의 다관능성을 갖는 화합물잔기가 0.01 내지 1몰%의 비율로 구성된 것으로, 여기서 3관능 이상의 다관능성을 갖는 화합물이 산잔기인 경우에는 산성분을 기준으로 나타내고 알콜잔기인 경우에는 디올성분을 기준으로 나타낸 것음을 특징으로 하는 생분해성 폴리에스테르 수지의 제조방법.[Claim 2] The method according to claim 1, wherein the aliphatic polyester (I) has an acid component comprising 40 to 90 mol% of succinic acid or its ester compound and 10 to 60 mol% of adipic acid or an ester compound thereof, 1,4-butanediol or ethylene glycol is used alone or in combination of two components, and the compound residue having three or more functionalities is composed of 0.01 to 1 mol%, wherein the trifunctional or more polyfunctional compound is an acid Wherein the diol component is expressed on the basis of an acid component in the case of a residue and in the case of an alcohol residue on the basis of a diol component. 제1항에 있어서, 지방족 폴리에스테르(Ⅱ)는 산성분으로서는 테레프탈산, 잇프탈산, 디메틸레레프탈레이트, 디메틸이소프탈레이트 중에 단독 또는 2종이상으로 구성된 페닐렌 잔기가 30 내지 70몰%, 석신산, 아디프산, 세바식산, 아젤라익산 또는 이들 산의 에스테르 화합물 중 단독 또는 2종 이상으로 구성된 지방족 디카르복시산 잔기가 30 내지 70몰%로 구성되고, 디올성분으로는 에틸렌글리콜, 1,2 - 프로판디올, 1,3 - 프로판디올 - 1,4 - 부탄디올, 1,6 - 헥산디올중 단독 또는 2종 이상으로 구성되고, 3관능 이상의 다관능성을 갖는 화합물 잔기가 0.1 내지 3몰%의 비율로 구성된 것으로 여기서 3관능 이상의 다관능성을 갖는 산잔기인 경우에는 산성분으르 기준으로 나타낸 것이고, 3관능 이상의 다관능성을 갖는 알콜잔기인 경우에는 디올성분을 기준으로 나타낸 것임을 특지으로 하는 생분해성 폴리에스테르 수지의 제조방법.2. The polyester resin composition according to claim 1, wherein the aliphatic polyester (II) is at least one selected from the group consisting of terephthalic acid, phthalic acid, dimethylterephthalate and dimethyl isophthalate in an amount of 30 to 70 mol% Dicarboxylic acid, dibasic acid, sebacic acid, sebacic acid, azelaic acid, or an ester compound of these acids in an amount of 30 to 70 mol%, and examples of the diol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol-1,4-butanediol, and 1,6-hexanediol, wherein the compound residue having three or more functionalities is composed of 0.1 to 3 mol% In the case of an acid residue having three or more functionalities, it is shown on the basis of an acid component, and in the case of an alcohol residue having three or more functionalities, it is based on the diol component Process for producing a biodegradable polyester resin that as Bounty. 제1항에 있어서, 지방족 폴리에스테르(Ⅰ)의 함량은 10∼90중량부이고, 폴리에스테르(Ⅱ)의 함량은 90∼10중량부가 되게 혼합시킴을 특징으로 하는 생분해성 폴리에스테르 수지의 제조방법.The method for producing a biodegradable polyester resin according to claim 1, wherein the content of the aliphatic polyester (I) is 10 to 90 parts by weight, and the content of the polyester (II) is 90 to 10 parts by weight . ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: It is disclosed by the contents of the first application.
KR1019960005473A 1996-03-02 1996-03-02 Process for preparing polyester resin having excellent biodegradable property KR0181673B1 (en)

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KR1019960005473A KR0181673B1 (en) 1996-03-02 1996-03-02 Process for preparing polyester resin having excellent biodegradable property

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990015024A (en) * 1997-08-01 1999-03-05 조민호 Manufacturing Method of Biodegradable Packaging Film for Phone Card

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101460314B1 (en) * 2012-12-07 2014-11-13 도레이케미칼 주식회사 Polymer for bio plastics, Composition of the same and Preparing method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990015024A (en) * 1997-08-01 1999-03-05 조민호 Manufacturing Method of Biodegradable Packaging Film for Phone Card

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