[go: up one dir, main page]

WO2018056666A1 - Composition de plastifiant composite, son procédé de préparation et composition de résine polymère l'utilisant - Google Patents

Composition de plastifiant composite, son procédé de préparation et composition de résine polymère l'utilisant Download PDF

Info

Publication number
WO2018056666A1
WO2018056666A1 PCT/KR2017/010238 KR2017010238W WO2018056666A1 WO 2018056666 A1 WO2018056666 A1 WO 2018056666A1 KR 2017010238 W KR2017010238 W KR 2017010238W WO 2018056666 A1 WO2018056666 A1 WO 2018056666A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
weight
compound
polymer resin
phthalate
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.)
Ceased
Application number
PCT/KR2017/010238
Other languages
English (en)
Korean (ko)
Inventor
이종화
이정무
김영관
정종환
위성유
김장수
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AEKYUNGPETROCHEMICAL Co Ltd
Original Assignee
AEKYUNGPETROCHEMICAL Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by AEKYUNGPETROCHEMICAL Co Ltd filed Critical AEKYUNGPETROCHEMICAL Co Ltd
Publication of WO2018056666A1 publication Critical patent/WO2018056666A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a composite plasticizer composition, a preparation method thereof, and a polymer resin composition using the same.
  • Polymer resins are used in various fields such as household goods, home appliances, clothing, automobiles, construction materials, packaging materials, etc. To date, polyethylene (PE), polypropylene (PP), polystyrene (PP), polyurethane (PU), polyvinyl chloride (PVC), and the like are widely used.
  • PE polyethylene
  • PP polypropylene
  • PP polystyrene
  • PU polyurethane
  • PVC polyvinyl chloride
  • PVC resin is hard, soft properties, and can be molded in a variety of ways and excellent price competitiveness has a universal utility has been applied to various applications from household goods to industrial materials.
  • PVC resins can not be used alone, and added to the plasticizer to implement a variety of physical properties.
  • Plasticizers serve to impart flexibility to the PVC resin and to improve processability and compatibility. However, as the industry develops, plasticizers are not only flexible, but also diverse according to the characteristics required for their application fields such as aging resistance, cold resistance, oil resistance, water resistance, transition resistance, and heat resistance.
  • plasticizers suitable for aging resistance and compatibility are selected and used according to application fields.
  • the plasticizer that satisfies the environmental regulation is excellent in room temperature and aging properties, but there is a problem that the workability is lowered.
  • DIDP diisodecyl phthalate
  • the present invention provides an environment-friendly plasticizer that is harmless to the human body, and provides a polymer resin composition having excellent physical properties such as tensile strength, elongation rate, 100% modulus, elongation residual rate, volatilization loss, etc. by mixing it with a polymer resin. It aims to do it.
  • the present invention for achieving the above object is 1 to 20% by weight of the compound of Formula 1, 1 to 30% by weight of the compound of Formula 2, 1 to 50% by weight of the compound of Formula 3, 1 to 30 of the compound of Formula 4
  • a terephthalate derivative mixture comprising 1 wt% to 70 wt% of the compound of Formula 5, and 1 wt% to 80 wt% of the compound of Formula 6;
  • Another one aspect of this invention relates to the polymeric resin composition containing the said composite plasticizer composition.
  • Another one aspect of this invention relates to the molded article containing the said polymeric resin composition.
  • a) a reaction solution comprising 2-ethyl-1-hexanol, isononyl alcohol, 2-propyl-1-heptyl alcohol and terephthalic acid is reacted to synthesize a terephthalate derivative mixture. step; And b) mixing the synthesized terephthalate derivative mixture with a phthalate compound of formula (7).
  • the composite plasticizer composition according to the present invention is an environmentally friendly plasticizer that is harmless to the human body, and has excellent compatibility and can provide a polymer resin composition having improved physical properties such as processability, heating loss, heat resistance, aging resistance, and weather resistance when mixed with a polymer resin. have.
  • the inventors of the present invention have high environmental hazards and high imports, although diisodecyl phthalate (DIDP), which has been conventionally used as a plasticizer for polymer resins such as polyvinyl chloride resin, can impart very excellent properties to polymer resins.
  • DIDP diisodecyl phthalate
  • the mixed plasticizer composition mixed with different kinds of terephthalate derivatives and di (2-propylheptyl) phthalate is an environmentally friendly plasticizer that is harmless to the human body and is inferior to DIDP. It has been found that the present invention provides the physical properties without which the present invention has been completed.
  • the present invention relates to a composite plasticizer composition
  • a composite plasticizer composition comprising a terephthalate derivative mixture, and di (2-propylheptyl) phthalate, and by using the same, provides an environmentally friendly plasticizer that is harmless to the human body, and mixes it with a polymer resin to increase tensile strength and elongation. It provides a polymer resin composition having excellent physical properties, such as 100% modulus, elongation residual ratio, volatilization loss.
  • the composite plasticizer composition according to an embodiment of the present invention is 1 to 20% by weight of the compound of Formula 1, 1 to 30% by weight of the compound of Formula 2, 1 to 50% by weight of the compound of Formula 3, Formula 4 Terephthalate derivative mixture comprising 1 to 30% by weight of the compound, 1 to 70% by weight of the compound of Formula 5, and 1 to 80% by weight of the compound of Formula 6; And a phthalate compound represented by Formula 7, wherein the weight ratio of the terephthalate derivative mixture: phthalate compound may be 5 to 95: 95 to 5.
  • the composite plasticizer composition in which terephthalate derivative mixtures of different types and di (2-propylheptyl) phthalate are mixed in a specific ratio is an environmentally friendly plasticizer that is harmless to humans, and has excellent compatibility and processability and heating when mixed with a polymer resin.
  • a polymer resin composition having improved physical properties such as weight loss, heat resistance, aging resistance, and weather resistance can be provided.
  • physical properties such as heat resistance, aging resistance, etc. may be poor, and when out of the weight% range, tensile strength, elongation, 100% modulus, elongation residual rate Or physical properties such as volatilization loss may be lowered.
  • the composite plasticizer composition according to an embodiment of the present invention is 1 to 10% by weight of the compound of Formula 1, 5 to 15% by weight of the compound of Formula 2, 10 to 40% by weight of the compound of Formula 3, Compound 5 of Formula 4 Terephthalate derivative mixture comprising 15 wt%, 10-30 wt% of compound of Formula 5, and 10-40 wt% of compound of Formula 6; And a phthalate compound represented by Chemical Formula 7, wherein the weight ratio of the terephthalate derivative mixture: phthalate compound may be 20 to 40:80 to 60.
  • the polymer resin when mixed and used in the polymer resin, it is possible to give the polymer resin a similar or better mechanical and aging properties than the commercial plasticizer DIDP. Specifically, excellent tensile strength of 1.5 to 2.0 kfg / mm 2, elongation of 360 to 380%, 100% modulus of 0.58 to 0.65 kfg / mm 2, elongation of 78 to 90%, and volatilization loss of 0 to 7% by weight. It may have physical properties, and the bleeding phenomenon may not occur. In this case, each physical property may be measured according to a measuring method to be described later.
  • the method for producing a composite plasticizer composition includes a) synthesizing a terephthalate derivative mixture by reacting a reaction solution containing 2-ethyl-1-hexanol, isononyl alcohol, 2-propyl-1-heptyl alcohol and terephthalic acid. step; And b) mixing the synthesized terephthalate derivative mixture with a phthalate compound represented by Formula 7 below.
  • step a) with respect to 1 mol (mol) of terephthalic acid, 0.2-0.5 mol of 2-ethyl-1-hexanol, 0.4-0.8 mol of isononyl alcohol, 2-propyl-1 -Heptyl alcohol may be reacted with 0.8 ⁇ 1.2 moles.
  • 1 to 20% by weight of the compound of Formula 1, 1 to 30% by weight of the compound of Formula 2, 1 to 50% by weight of the compound of Formula 3, 1 to 30% by weight of the compound of Formula 4, 1 to 70% by weight of the compound of Formula 5, and 1 to 80% by weight of the compound of Formula 6 may be synthesized.
  • step a) may be carried out for 10 to 20 hours at 230 ⁇ 250 °C.
  • the esterification reaction may be effectively performed, and the compound of Formula 1 to the compound of Formula 6 may be synthesized in the above ranges.
  • step b) is a step of mixing the synthesized terephthalate derivative mixture with a phthalate compound of formula (7), that is, di (2-propylheptyl) phthalate, the weight ratio of the terephthalate derivative mixture: phthalate compound is 5 to 95: may be 95 to 5. It is possible to provide a polymer resin composition having excellent compatibility in such a range, and improved physical properties such as workability, heating loss, heat resistance, aging resistance, and weather resistance when mixed with a polymer resin.
  • the weight ratio of terephthalate derivative mixture: phthalate compound may be 20-40: 80-60.
  • tensile strength 1.5 to 2.0 kfg / mm 2, elongation of 360 to 380%, 100% modulus of 0.58 to 0.65 kfg / mm 2, elongation of 78 to 90%, loss of volatilization of 0 to 7% by weight, etc. It may have excellent physical properties of, and the bleeding phenomenon may not occur.
  • the composite plasticizer composition according to the present invention may be applied to a polymer resin. That is, the present invention can provide a polymer resin composition containing a composite plasticizer composition.
  • the polymer resin is not necessarily limited thereto, but may include polyvinyl chloride resin, olefin resin, ABS resin, acrylic resin, polyester resin, and the like, preferably polyvinyl chloride (PVC). ) May be a resin.
  • PVC polyvinyl chloride
  • the composite plasticizer composition may be added in an amount of 20 to 120 parts by weight, more preferably 30 to 100 parts by weight, and more preferably 40 to 90 parts by weight, based on 100 parts by weight of the polymer resin. .
  • physical properties such as tensile strength, elongation rate, 100% modulus, elongation residual rate, and volatilization loss can be improved.
  • polyvinyl chloride resin when used as the polymer resin and satisfies the above range, 1.5 to 2.0 kfg / It has excellent physical properties such as tensile strength of 2 mm2, elongation rate of 360 to 380%, 100% modulus of 0.58 to 0.65 kfg / mm2, elongation residual ratio of 78 to 90%, and volatilization loss of 0 to 7% by weight. This may not occur.
  • the polymer resin composition may further include any one or two or more additives selected from secondary plasticizers, stabilizers, fillers, lubricants, flame retardants, viscosity regulators, foaming agents, enhancers and pigments.
  • the additive is not particularly limited, but may be added in an amount of 0.1 to 10 parts by weight, and more preferably 1 to 5 parts by weight, based on 100 parts by weight of the polymer resin. Each additive in the above range can achieve the desired effect.
  • the present invention can provide a molded article prepared from the polymer resin composition described above.
  • the molded article may be silver wallpaper, compound, wire compound, sheet, film, tarpaulin, hose, shoes, sealant, office supplies, gloves, caps, mats, gaskets, food packaging materials, medical supplies, automotive products, toys, baby products, Floor materials, electromechanical parts, etc. can be used in various ways.
  • Elongation Residual Rate (%): After leaving the test piece in aging conditions at 113 ° C. and 168 hours in a Geer Oven, the test piece was calculated as (test piece elongation strength after aging / test piece elongation before aging) ⁇ 100. The closer this value is to 100%, the similar mechanical properties as before aging. This property means the durability to the extent that the wire compound can maintain and use the initial properties for how long. Elongation strength of the test piece was conducted according to KS M 3156.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de plastifiant composite comprenant un mélange de dérivés de téréphtalate et un composé à base de dialkylphtalate, son procédé de préparation et une composition de résine polymère en comprenant. La présente invention concerne une composition de résine polymère présentant d'excellentes propriétés physiques, par exemple en termes de résistance à la traction, d'allongement, de module à 100 %, de rétention d'allongement et de perte par volatilisation, etc., utilisant une composition de plastifiant composite selon les présentes.
PCT/KR2017/010238 2016-09-20 2017-09-19 Composition de plastifiant composite, son procédé de préparation et composition de résine polymère l'utilisant Ceased WO2018056666A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2016-0119912 2016-09-20
KR1020160119912A KR101731366B1 (ko) 2016-09-20 2016-09-20 복합 가소제 조성물, 이의 제조방법, 및 이를 이용한 고분자 수지 조성물

Publications (1)

Publication Number Publication Date
WO2018056666A1 true WO2018056666A1 (fr) 2018-03-29

Family

ID=58701894

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/010238 Ceased WO2018056666A1 (fr) 2016-09-20 2017-09-19 Composition de plastifiant composite, son procédé de préparation et composition de résine polymère l'utilisant

Country Status (2)

Country Link
KR (1) KR101731366B1 (fr)
WO (1) WO2018056666A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101731366B1 (ko) * 2016-09-20 2017-04-28 애경유화주식회사 복합 가소제 조성물, 이의 제조방법, 및 이를 이용한 고분자 수지 조성물
KR102108875B1 (ko) * 2017-08-25 2020-05-20 애경유화주식회사 복합 가소제 조성물, 이의 제조방법 및 이를 이용한 고분자 수지 조성물
WO2019039879A2 (fr) * 2017-08-25 2019-02-28 애경유화 주식회사 Composition de plastifiant composite, procédé de préparation associé et composition de résine polymère l'utilisant
KR102354744B1 (ko) * 2018-03-21 2022-01-25 애경케미칼주식회사 복합 가소제 조성물, 이의 제조방법 및 이를 이용한 고분자 수지 조성물
US12122895B2 (en) 2018-08-27 2024-10-22 Lg Chem, Ltd. Plasticizer composition and resin composition including the same
KR102520601B1 (ko) 2021-05-03 2023-04-12 (주)네오 신규 디사이클로헥실 에스테르 조성물 및 이의 제조방법
KR102531143B1 (ko) 2021-05-03 2023-05-11 (주)네오 신규 사이클로헥산계 에스테르 조성물 및 이의 제조방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070075341A (ko) * 2006-01-12 2007-07-18 옥세노 올레핀케미 게엠베하 디알킬 테레프탈레이트 및 그의 용도
KR20140052838A (ko) * 2012-10-25 2014-05-07 애경유화주식회사 에폭시계 에스테르 화합물을 포함한 복합 가소제 조성물 및 이를 이용한 고분자 수지 조성물
JP2015083690A (ja) * 2006-08-30 2015-04-30 イーストマン ケミカル カンパニー 酢酸ビニルポリマー組成物中の可塑剤としてのテレフタレート
KR101569560B1 (ko) * 2012-10-10 2015-11-16 주식회사 엘지화학 가소제 조성물, 제조 방법 및 내열 수지 조성물
WO2016005357A1 (fr) * 2014-07-08 2016-01-14 Basf Se Composition de plastifiant contenant des esters d'acide dicarboxylique aliphatiques et des dialkylesters d'acide téréphtalique
KR101731366B1 (ko) * 2016-09-20 2017-04-28 애경유화주식회사 복합 가소제 조성물, 이의 제조방법, 및 이를 이용한 고분자 수지 조성물

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070075341A (ko) * 2006-01-12 2007-07-18 옥세노 올레핀케미 게엠베하 디알킬 테레프탈레이트 및 그의 용도
JP2015083690A (ja) * 2006-08-30 2015-04-30 イーストマン ケミカル カンパニー 酢酸ビニルポリマー組成物中の可塑剤としてのテレフタレート
KR101569560B1 (ko) * 2012-10-10 2015-11-16 주식회사 엘지화학 가소제 조성물, 제조 방법 및 내열 수지 조성물
KR20140052838A (ko) * 2012-10-25 2014-05-07 애경유화주식회사 에폭시계 에스테르 화합물을 포함한 복합 가소제 조성물 및 이를 이용한 고분자 수지 조성물
WO2016005357A1 (fr) * 2014-07-08 2016-01-14 Basf Se Composition de plastifiant contenant des esters d'acide dicarboxylique aliphatiques et des dialkylesters d'acide téréphtalique
KR101731366B1 (ko) * 2016-09-20 2017-04-28 애경유화주식회사 복합 가소제 조성물, 이의 제조방법, 및 이를 이용한 고분자 수지 조성물

Also Published As

Publication number Publication date
KR101731366B1 (ko) 2017-04-28

Similar Documents

Publication Publication Date Title
WO2018056666A1 (fr) Composition de plastifiant composite, son procédé de préparation et composition de résine polymère l'utilisant
KR101720381B1 (ko) 압출 또는 사출용 염화비닐계 수지 조성물
WO2018048169A1 (fr) Composition de plastifiant et composition de résine comprenant ladite composition de plastifiant
WO2018008914A1 (fr) Composition plastifiante, composition de résine et procédé pour les produire
EP2345630A2 (fr) Plastifiant et résine de polychlorure de vinyle (pvc) contenant ce dernier
WO2020246743A1 (fr) Composition de plastifiant et composition de résine de chlorure de vinyle la comprenant
US8546604B2 (en) Polyvinyl chloride resin plasticiser
WO2016098496A1 (fr) Plastifiant pour résine à base d'halogène
KR102710486B1 (ko) 가소제 조성물 및 이를 이용한 수지 조성물
WO2018110922A1 (fr) Composition de plastifiant et composition de résine la contenant
WO2017074056A1 (fr) Composition de plastifiant, composition de résine et leurs procédés de préparation
WO2017074057A1 (fr) Composition de plastifiant, composition de résine, et procédés pour les préparer
KR101940219B1 (ko) 가소제 조성물, 수지 조성물 및 이들의 제조 방법
WO2017018841A1 (fr) Composition plastifiante, composition de résine, et leurs procédés de préparation
WO2019112293A1 (fr) Composition de plastifiant et composition de résine la comprenant
WO2022005130A1 (fr) Composition de plastifiant et composition de résine de chlorure de vinyle la comprenant
WO2021194245A1 (fr) Composition de plastifiant composite et composition de résine polymère l'utilisant
KR102108875B1 (ko) 복합 가소제 조성물, 이의 제조방법 및 이를 이용한 고분자 수지 조성물
WO2022270910A1 (fr) Composition de plastifiant à base d'isophtalate et composition de résine la comprenant
WO2022270911A1 (fr) Composition de plastifiant à base de triester et composition de résine comprenant ladite composition de plastifiant
WO2019039879A2 (fr) Composition de plastifiant composite, procédé de préparation associé et composition de résine polymère l'utilisant
KR102354744B1 (ko) 복합 가소제 조성물, 이의 제조방법 및 이를 이용한 고분자 수지 조성물
KR20240047582A (ko) 트리멜리테이트계 가소제 및 이를 포함하는 고분자 수지 조성물
WO2021194246A1 (fr) Plastifiant, et composition de résine polymère le comprenant
KR100768744B1 (ko) 2,2,4-트리메틸-1,3-펜탄디올 디에스테르계 가소제 조성물및 이를 포함하는 ｐｖｃ계 고분자 수지 조성물

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17853380

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17853380

Country of ref document: EP

Kind code of ref document: A1