WO2019240417A1 - Composition de plastifiant et composition de résine la comprenant - Google Patents

Composition de plastifiant et composition de résine la comprenant Download PDF

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Publication number
WO2019240417A1
WO2019240417A1 PCT/KR2019/006637 KR2019006637W WO2019240417A1 WO 2019240417 A1 WO2019240417 A1 WO 2019240417A1 KR 2019006637 W KR2019006637 W KR 2019006637W WO 2019240417 A1 WO2019240417 A1 WO 2019240417A1
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WO
WIPO (PCT)
Prior art keywords
group
formula
composition
plasticizer composition
carbon atoms
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/KR2019/006637
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English (en)
Korean (ko)
Inventor
김현규
문정주
정석호
조윤기
김주호
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.)
LG Chem Ltd
Original Assignee
LG Chem 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
Priority claimed from KR1020190063854A external-priority patent/KR102260896B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP19819107.4A priority Critical patent/EP3805302B1/fr
Priority to US17/040,784 priority patent/US11746079B2/en
Priority to ES19819107T priority patent/ES2956465T3/es
Priority to CN201980018806.4A priority patent/CN111868157A/zh
Publication of WO2019240417A1 publication Critical patent/WO2019240417A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings

Definitions

  • plasticizers react with alcohols to polycarboxylic acids such as phthalic acid and adipic acid to form the corresponding esters.
  • polycarboxylic acids such as phthalic acid and adipic acid
  • plasticizer compositions that can replace phthalate-based plasticizers such as terephthalate-based, adipate-based, and other polymer-based plastics is being continued.
  • the present invention is derived to solve the problems of the prior art, and when used as a plasticizer of the resin composition, a plasticizer composition which can improve the physical properties such as plasticization efficiency, heating loss, light resistance, thermal stability and transferability to an excellent level; It is to provide a resin composition comprising the same.
  • the present invention is a cyclohexane-1,4-diester-based material represented by the formula (1); Epoxidized alkyl ester composition comprising at least one compound represented by the formula (2); And it provides a plasticizer composition comprising a citrate-based material represented by the formula (3):
  • R 4 to R 7 are each independently an alkyl group having 4 to 10 carbon atoms.
  • the plasticizer composition according to an embodiment of the present invention may be used in a resin composition to provide a plasticizer composition capable of improving physical properties such as plasticization efficiency, heating loss, light resistance, and heat resistance to excellent levels.
  • the compound name used herein may be a conventionally used name and is named according to a substituent that is characteristically bonded to each compound, even if the compound name does not correspond to a conventional name, and is named according to a substituent represented in the structure of a chemical formula. Can be understood.
  • Iodine number in the present invention can be measured based on ASTM D5768-02.
  • the oxirane content rate in the present invention can be measured based on ASTM D1652-04.
  • the term “straight vinyl chloride polymer” refers to one of the types of vinyl chloride polymers, which may be polymerized through suspension polymerization or bulk polymerization. A large amount of pores having a size of tens to hundreds of micrometers may be used. It refers to a polymer having the form of distributed porous particles and having no cohesiveness and excellent flowability.
  • the term “paste vinyl chloride polymer” refers to one of the types of vinyl chloride polymers, which may be polymerized through microsuspension polymerization, microseed polymerization, or emulsion polymerization, and may have a size of several tens to thousands of nanometers. It refers to a polymer having fine and dense pores with no cohesiveness and poor flowability.
  • Plasticizer composition is 1) cyclohexane-1,4-diester-based material represented by the formula (1); 2) an epoxidized alkyl ester composition comprising at least one compound represented by formula (2); And 3) a citrate-based material represented by Formula 3:
  • R 1 and R 2 are each independently an alkyl group having 8 carbon atoms
  • R 3 is an alkyl group having 8 to 20 carbon atoms including one or more epoxy groups
  • R 4 to R 7 are each independently an alkyl group having 4 to 10 carbon atoms.
  • the cyclohexane-1,4-diester-based material may be dioctyl cyclohexane-1,4-dicarboxylate or di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate.
  • the cyclohexane-1,4-diester-based material may be included in 10 to 90% by weight, 20 to 90% by weight or 30 to 80% by weight, based on the total weight of the plasticizer composition, of which 30 to 80% by weight It is preferably included in%.
  • a resin composition having good mechanical properties such as plasticization efficiency, heating loss, light resistance and tensile strength, elongation and the like can be provided.
  • the derivative of cyclohexane-1,4-dicarboxylic acid may be at least one selected from the group consisting of anhydrides of cyclohexane-1,4-dicarboxylic acid and alkyl esters of cyclohexane-1,4-dicarboxylic acid.
  • the alkyl ester may be an alkyl ester having 1 to 6 carbon atoms.
  • the alcohol is an alkyl alcohol having 8 carbon atoms.
  • the alcohol is 2 to 1 mole of the cyclohexane-1,4-dicarboxylic acid or derivative thereof. It may be used in 10 to 10 moles, 2 to 8 moles, 2 to 6 moles or 2 to 5 moles, preferably 2 to 5 moles.
  • the direct esterification reaction may be carried out in the presence of a catalyst, and the catalyst may be at least one selected from the group consisting of inorganic acids, organic acids and Lewis acids.
  • the inorganic acid may be at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid.
  • the Lewis acid is an aluminum derivative (aluminum oxide, aluminum hydroxide), tin derivative (C 3 to C 12 fatty acid tin, tin oxide, tin hydroxide), titanium derivative (C 3 to C 8 tetraalkyl titanate, titanium oxide, hydroxide Titanium), lead derivatives (lead oxide, lead hydroxide) and zinc derivatives (zinc oxide, zinc hydroxide).
  • the catalyst when it is a heterogeneous catalyst, it may be used in an amount of 5 to 200 parts by weight or 5 to 100 parts by weight, based on 100 parts by weight of cyclohexane-1,4-dicarboxylic acid or a derivative thereof and alcohol. It is preferably used in parts by weight.
  • the direct esterification reaction may be performed at 100 to 280 ° C., 130 to 250 ° C. or 150 to 230 ° C., and preferably at 150 to 230 ° C.
  • the direct esterification reaction may be performed for 3 to 30 hours or 3 to 25 hours, preferably 3 to 25 hours.
  • the alcohol may be used in 2 to 10 moles, 2 to 8 moles, 2 to 6 moles or 2 to 5 moles with respect to 1 mole of the derivative of cyclohexane-1,4-dicarboxylic acid, of which 2 to 5 moles are used. It is preferred to be used.
  • the transesterification reaction may be carried out in the presence of a catalyst, in which case the reaction time may be shortened.
  • the catalyst may be at least one selected from the group consisting of Lewis acids and alkali metals.
  • the transesterification reaction may be carried out for 0.5 to 10 hours or 0.5 to 8 hours, preferably 0.5 to 8 hours.
  • the direct esterification reaction or trans esterification reaction further comprises at least one member selected from the group consisting of benzene, toluene, xylene and cyclohexane in order to promote the outflow of lower alcohols such as water or methanol produced by the reaction.
  • Nitrogen or the like which can be used commercially for the same purpose, may be used as the entrainment.
  • the cyclohexane-1,4-diester-based material prepared by the direct esterification or trans esterification reaction may be purified by performing a separate post treatment.
  • the post treatment may be at least one selected from the group consisting of deactivation treatment (neutralization treatment, base treatment), water washing treatment, distillation (pressure reduction or dehydration treatment) and adsorption purification treatment of the catalyst.
  • a manufacturing method including converting a dialkyl terephthalate-based material into a cyclohexane-1,4-diester-based material by hydrogenation in the presence of a metal catalyst may be applied.
  • R 4 is a butyl group (butyl, abbreviation B), isobutyl group (isobutyl, abbreviation iB), pentyl group (pentyl, abbreviation P), isopentyl group (isopentyl, abbreviation iP), hexyl group (hexyl , Abbreviation Hx), isohexyl group (isohexyl, abbreviation iHx), heptyl group (heptyl, abbreviation Hp), isoheptyl group (isoHptyl, abbreviation iHp), octyl group (octyl, abbreviation nO), isooctyl group (isooctyl, abbreviation iO), 2-ethylhexyl (2-ethylhexyl, abbreviated EH or O), nonyl (nonyl, abbre
  • R 8 is an alkyl group having 8 to 20 carbon atoms
  • the epoxidized oil may be, for example, one or more of epoxidized oils represented by the following Chemical Formulas 5 to 11.
  • R 5 to R 7 be an alkyl group having 4 to 8 carbon atoms, and more preferably an alkyl group having 4 to 6 carbon atoms.
  • R 5 to R 7 be an alkyl group having 5 to 10 carbon atoms, and an alkyl group having 8 to 10 carbon atoms. It is more preferable.
  • the citrate-based material may be included in 5 to 70% by weight, 5 to 60% by weight or 10 to 50% by weight, based on the total weight of the plasticizer composition, it is preferably included in 10 to 50% by weight. .
  • the derivative of citric acid may be one or more selected from the group consisting of anhydrides of citric acid and alkyl esters of citric acid.
  • the alkyl ester may be an alkyl ester having 1 to 6 carbon atoms.
  • the resin in which the plasticizer composition is used may be produced as a resin product through melt processing or plastisol processing, and the melt processed resin and plastisol processed resin may be produced differently according to each polymerization method.
  • the resin composition may further include a filler.
  • the filler may be 0 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 200 parts by weight based on 100 parts by weight of the resin.
  • 1,4-DBCH Dibutyl cyclohexane-1,4-dicarboxylate (LG Chemical Co., Ltd.)
  • 1,4-DIDCH Diisodecyl cyclohexane-1,4-dicarboxylate (LG Chemical Co., Ltd.)
  • TPC tripentyl citrate (LG Chemical Co., Ltd.)
  • ATBC acetyltributyl citrate (LG Chemical Co., Ltd.)
  • Examples 6 to 9 the less the average carbon number of R 5 to R 7 It can be confirmed that the superior plasticization efficiency, heating loss, elongation, absorption rate.
  • Examples 4 and 5 show a different aspect than Examples 6-9, which is due to the properties of tributylcitrate.
  • Examples 11 to 14 it was confirmed that as the content of cyclohexane-1,4-diester-based material is reduced, the transition loss, heating loss, elongation and absorption rate is improved.

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  • 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 qui comprend un matériau cyclohexane-1,4-diester, une composition d'ester alkylique époxydé, et un matériau citrate, la composition de plastifiant étant respectueuse de l'environnement tout en ayant une excellente stabilité et des propriétés physiques de base.
PCT/KR2019/006637 2018-06-11 2019-06-03 Composition de plastifiant et composition de résine la comprenant Ceased WO2019240417A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP19819107.4A EP3805302B1 (fr) 2018-06-11 2019-06-03 Composition de plastifiant et composition de résine la comprenant
US17/040,784 US11746079B2 (en) 2018-06-11 2019-06-03 Plasticizer composition and resin composition including the same
ES19819107T ES2956465T3 (es) 2018-06-11 2019-06-03 Composición plastificante y composición de resina que incluye la misma
CN201980018806.4A CN111868157A (zh) 2018-06-11 2019-06-03 增塑剂组合物和包含该增塑剂组合物的树脂组合物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20180067038 2018-06-11
KR10-2018-0067038 2018-06-11
KR1020190063854A KR102260896B1 (ko) 2018-06-11 2019-05-30 가소제 조성물 및 이를 포함하는 수지 조성물
KR10-2019-0063854 2019-05-30

Publications (1)

Publication Number Publication Date
WO2019240417A1 true WO2019240417A1 (fr) 2019-12-19

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PCT/KR2019/006637 Ceased WO2019240417A1 (fr) 2018-06-11 2019-06-03 Composition de plastifiant et composition de résine la comprenant

Country Status (2)

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ES (1) ES2956465T3 (fr)
WO (1) WO2019240417A1 (fr)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140116371A (ko) * 2011-10-14 2014-10-02 갈라타 케미컬스, 엘엘씨 재생가능한 원료로부터 유도된 가소제
KR20150131016A (ko) * 2013-03-15 2015-11-24 다우 글로벌 테크놀로지스 엘엘씨 천연 오일 비누 스톡으로부터의 에폭시화 지방산 알킬 에스테르 가소제 및 이러한 에폭시화 지방산 알킬 에스테르 가소제의 제조 방법
JP2016022708A (ja) * 2014-07-24 2016-02-08 平岡織染株式会社 産業用ターポリン及びテント構造物用膜材
KR20160047221A (ko) * 2014-10-22 2016-05-02 한화케미칼 주식회사 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트 및 시트레이트계 화합물을 포함하는 가소제 조성물, 및 이를 포함하는 염화비닐 수지 조성물
KR20170121059A (ko) * 2016-04-22 2017-11-01 주식회사 엘지화학 가소제 조성물 및 이를 포함하는 수지 조성물
KR20170141599A (ko) * 2016-06-15 2017-12-26 주식회사 엘지화학 가소제 조성물, 수지 조성물 및 이들의 제조 방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140116371A (ko) * 2011-10-14 2014-10-02 갈라타 케미컬스, 엘엘씨 재생가능한 원료로부터 유도된 가소제
KR20150131016A (ko) * 2013-03-15 2015-11-24 다우 글로벌 테크놀로지스 엘엘씨 천연 오일 비누 스톡으로부터의 에폭시화 지방산 알킬 에스테르 가소제 및 이러한 에폭시화 지방산 알킬 에스테르 가소제의 제조 방법
JP2016022708A (ja) * 2014-07-24 2016-02-08 平岡織染株式会社 産業用ターポリン及びテント構造物用膜材
KR20160047221A (ko) * 2014-10-22 2016-05-02 한화케미칼 주식회사 디(2-에틸헥실)사이클로헥산-1,4-디카르복실레이트 및 시트레이트계 화합물을 포함하는 가소제 조성물, 및 이를 포함하는 염화비닐 수지 조성물
KR20170121059A (ko) * 2016-04-22 2017-11-01 주식회사 엘지화학 가소제 조성물 및 이를 포함하는 수지 조성물
KR20170141599A (ko) * 2016-06-15 2017-12-26 주식회사 엘지화학 가소제 조성물, 수지 조성물 및 이들의 제조 방법

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ES2956465T3 (es) 2023-12-21

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