WO2016163765A1 - Résine de polyoléfine déréticulée et composition de résine la contenant - Google Patents

Résine de polyoléfine déréticulée et composition de résine la contenant Download PDF

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Publication number
WO2016163765A1
WO2016163765A1 PCT/KR2016/003634 KR2016003634W WO2016163765A1 WO 2016163765 A1 WO2016163765 A1 WO 2016163765A1 KR 2016003634 W KR2016003634 W KR 2016003634W WO 2016163765 A1 WO2016163765 A1 WO 2016163765A1
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WO
WIPO (PCT)
Prior art keywords
polyolefin resin
decrosslinked
resin
weight
resin composition
Prior art date
Application number
PCT/KR2016/003634
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English (en)
Korean (ko)
Inventor
신지욱
남기준
홍순만
구종민
백범기
라윤호
황승상
백경열
Original Assignee
엘에스전선 주식회사
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Publication of WO2016163765A1 publication Critical patent/WO2016163765A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/50—Partial depolymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a decrosslinked polyolefin resin recycled after crosslinking and a resin composition comprising the same. Specifically, the present invention relates to a recycled decrosslinked polyolefin resin having excellent processability, flame retardancy, mechanical properties, and the like, and a resin composition including the same, as compared to new non-crosslinked new polyolefin resin.
  • polyolefin resins such as polyethylene resins are most commonly used among general-purpose plastics because they have excellent physical properties compared to low prices, but when crosslinked, they are still due to the insoluble and infusible crosslinked polymer chains. Proper treatment or regeneration is not well developed.
  • crosslinked polyolefin resins are mostly incinerated or buried, and effective recycling is not achieved, which causes many environmental problems.
  • a crosslinked polyolefin resin for recycling after crosslinking having a weight average molecular weight (Mw) of 70,000 or more, a polydispersity (PDI) of 10 or more, and a gel fraction of 0.2 to 20%.
  • Mw weight average molecular weight
  • PDI polydispersity
  • the crosslinking is silinic crosslinking, and based on the total weight of the resin, the content of silicon (Si) is characterized in that 0.05 to 2% by weight, to provide a decrosslinked polyolefin resin.
  • the polyolefin resin provides a decrosslinked polyolefin resin, characterized in that it comprises a polyethylene resin.
  • the crosslinked polyolefin resin is prepared by decrosslinking with a supercritical fluid which is a reaction solvent under a reaction temperature of 300 to 400 ° C. and a reaction pressure of 8 to 30 MPa.
  • polyolefin resin composition comprising the decrosslinked polyolefin resin and a new non-crosslinked polyolefin resin in a blending ratio of 10:90 to 70:30.
  • the polyolefin resin composition is characterized by having a weight average molecular weight (Mw) of 100,000 or more and polydispersity (PDI) of 5.5 or more.
  • the flame retardant is made of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, huntite (Mg 3 Ca (CO 3 ) 4 ) and hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 ) It provides a polyolefin resin composition, characterized in that it comprises at least one inorganic flame retardant selected from the group.
  • the decrosslinked polyolefin resin according to the present invention has an excellent effect of showing excellent processability, filler loading property and mechanical properties compared to new polyolefins through precisely controlled molecular weight and molecular weight distribution, and thus precisely controlled viscosity and gel fraction. Indicates.
  • the decrosslinked polyolefin resin according to the present invention exhibits an excellent effect of showing excellent flame retardancy through precise control of the crosslinking residue content.
  • Figure 2 shows the results of measuring the tensile strength of the specimen prepared from the polyethylene resin composition according to Example 4 and Comparative Example 4.
  • Figure 3 shows the results of measuring the oxygen index (LOI) of the polyethylene resin composition according to Examples 1 to 4 and Comparative Examples 1 to 4, respectively.
  • the present invention relates to a polyolefin resin decrosslinked for recycling after crosslinking.
  • the crosslinking includes crosslinking such as chemical crosslinking by a crosslinking agent such as an organic peroxide, and silane crosslinking (or water crosslinking) by a silane crosslinking agent.
  • the decrosslinked polyolefin resin according to the present invention may be prepared by decrosslinking the crosslinked polyolefin resin by a decrosslinking reaction for recycling the crosslinked polyolefin resin.
  • the decrosslinking reaction can be carried out, for example, using a supercritical fluid as a reaction solvent under specific temperature and pressure conditions.
  • the decrosslinked polyolefin resin according to the present invention may have a weight average molecular weight (Mw) of 70,000 or more, preferably 100,000 or more, and in particular, polydispersity (PDI) (Mw / Mn) having a molecular weight distribution of 10 or more.
  • Mw weight average molecular weight
  • PDI polydispersity
  • the decrosslinked polyolefin resin has a weight average molecular weight (Mw) of 70,000 or more, so that the mechanical properties are sufficient, and polydispersity (PDI), which is more than two times higher than the polydispersity (PDI) of the new low-density polyethylene, which is not crosslinked, is increased by more than twice. Therefore, workability such as extrusion property and filler loading property such as flame retardant are greatly improved.
  • the decrosslinked polyolefin resin according to the present invention may have a gel fraction representing the remaining crosslinked portion of 0.2 to 20%.
  • the gel fraction of the decrosslinked polyolefin resin is less than 0.2%, the crosslinked portion is unnecessarily removed, whereas when the gel fraction is more than 20%, the crosslinked portion is excessively left to increase the viscosity of the decrosslinked polyolefin resin. For this reason, workability such as extrusion moldability may be lowered.
  • silane residues remaining in the polymer chain of the decrosslinked polyolefin resin may further improve flame retardancy of the decrosslinked polyolefin resin.
  • the chemical structure of the silane residue may be -SiOCH 3 , -SiOH, -Si-O-Si- and the like.
  • the content of silicon (Si) of the silane residue may be 0.05 to 2% by weight based on the total weight of the resin.
  • the content of silicon (Si) is less than 0.05% by weight, the degree of improvement of flame retardancy may be extremely small, whereas when it exceeds 2% by weight, such as extrusion moldability, the viscosity of the decrosslinked polyolefin resin may be increased. Processability and filler loading property may be lowered, but flame retardancy may be lowered.
  • the polyolefin resin may include an olefin homopolymer such as polyethylene or polypropylene, or an olefin random or block copolymer made of a polymer of two or more olefin monomers. May be polyethylene.
  • the polyethylene may be ultra low density polyethylene (ULDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), or a combination thereof.
  • the decrosslinked polyolefin resin according to the present invention is continuously produced by crosslinking the polyolefin resin, for example, by decrosslinking with a supercritical fluid which is a reaction solvent under a reaction temperature of 300 to 400 ° C. and a reaction pressure of 8 to 30 MPa in a single screw compressor. Can be.
  • a supercritical fluid which is a reaction solvent under a reaction temperature of 300 to 400 ° C. and a reaction pressure of 8 to 30 MPa in a single screw compressor. Can be.
  • the supercritical fluid used as the reaction solvent refers to a substance in which a general liquid or gaseous substance has reached a critical state where gas and liquid cannot be distinguished while exceeding a high temperature and high pressure limit called a critical point.
  • the density of the molecules in the supercritical fluid is close to liquid, but the viscosity is low, close to gas, and the diffusion is so fast that the thermal conductivity is as high as water.
  • the concentration of the dissolved molecule, that is, the solvent around the solute is extremely high, resulting in the decrosslinking reaction.
  • alcohols such as distilled water, methanol, ethanol, or a mixture thereof may be used.
  • the present invention relates to a polyolefin resin composition comprising the decrosslinked polyolefin resin.
  • the polyolefin resin composition according to the present invention may include a new polyolefin resin not crosslinked with the decrosslinked polyolefin resin.
  • the mixing ratio of the decrosslinked polyolefin resin and the new polyolefin resin may be about 10:90 to 70:30, preferably about 10:90 to 50:50.
  • the polyolefin resin composition according to the present invention may have a weight average molecular weight (Mw) of 100,000 or more, preferably 155,000 or more, and polydispersity (PDI) of 5.5 or more.
  • Mw weight average molecular weight
  • PDI polydispersity
  • the polyolefin resin composition according to the present invention may further include an ethylene vinyl acetate (Ethylene vinyl acetate; EVA) resin to further improve the filler loading of additives such as flame retardants.
  • EVA ethylene vinyl acetate
  • the content of the ethylene vinyl acetate (EVA) resin may be 25 to 50 parts by weight based on 100 parts by weight of the mixture of the resin and the compatibilizer.
  • the filler loading is improved, whereas when the content is more than 50 parts by weight, the mechanical and electrical properties of the polyolefin resin composition may be reduced.
  • the polyolefin resin composition according to the present invention may include additives such as a flame retardant, an antioxidant, a lubricant.
  • the flame retardant is from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, huntite (Mg 3 Ca (CO 3 ) 4 ) and hydromagnesite (Mg 5 (CO 3 ) 4 (OH) 2 ) It may include one or more inorganic flame retardants selected.
  • Inorganic particles such as magnesium hydroxide (Mg (OH) 2 ) used as the flame retardant are hydrophilic having a high surface energy, whereas resins such as polyolefins are hydrophobic having a low surface energy, and thus the inorganic particles Dispersibility is not good and may adversely affect mechanical and electrical properties. Therefore, in order to solve this problem, inorganic particles such as magnesium hydroxide may be surface treated with vinylsilane, stearic acid, oleic acid, aminopolysiloxane, titanate coupling agent, and the like.
  • the silane groups react with the resin to provide excellent dispersibility. It can be secured.
  • the silane group may further improve the flame retardancy of the polyolefin resin composition.
  • the content of the flame retardant may be 50 to 200 parts by weight based on 100 parts by weight of the mixture of the resin and the compatibilizer. If the content of the flame retardant is less than 50 parts by weight can not implement sufficient flame retardancy, if it is more than 200 parts by weight can be greatly reduced the processability, such as the extrusion moldability of the polyolefin resin composition. On the other hand, other additives such as antioxidants, lubricants, etc. may be included in 1 to 10 parts by weight based on 100 parts by weight of the mixture of the resin and the compatibilizer.
  • the polyethylene resin composition according to each of Examples and Comparative Examples was prepared with the components and contents as shown in Table 1 below. Units of the content described in Table 1 below are parts by weight.
  • Resin 1 New Polyethylene Resin
  • Resin 3 Ethylene vinyl acetate resin
  • Antioxidant Irganox 1010
  • Lubricant LC wax
  • the resin composition of Examples 1 to 4 according to the present invention is a viscosity compared to the resin composition of Comparative Examples 1 to 4 containing only a new polyethylene resin containing a cross-linked polyethylene resin according to the present invention It was confirmed that it was low and was excellent in workability, such as extrusion moldability.
  • the specimen formed by the resin composition of Example 4 according to the present invention was found to have superior tensile strength as the deterioration time increased compared to the specimen formed by the resin composition of Comparative Example 4. .
  • Oxygen index (LOI) of the polyethylene resin composition of each of Examples 1 to 4 and Comparative Examples 1 to 4 was measured, and the results are shown in FIG. 3.
  • the resin compositions of Examples 1 to 4 according to the present invention have a high oxygen index compared to the resin compositions of Comparative Examples 1 to 4 and have been found to have improved flame retardancy by about 12 to 20%. It is expected that the resin compositions of Examples 1 to 4 further improved flame retardancy by silicon (Si) remaining in the polymer chain of the decrosslinked polyethylene resin.

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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)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une résine de polyoléfine déréticulée qui est recyclée après réticulation, un procédé pour sa préparation, et une composition de résine contenant cette dernière. Plus précisément, la présente invention concerne une résine de polyoléfine déréticulée recyclée, un procédé pour sa préparation, et une composition de résine contenant cette dernière, la résine de polyoléfine déréticulée recyclée présentant une meilleur aptitude au traitement, de meilleures propriétés ignifuges, propriétés mécaniques, etc. par rapport à une nouvelle résine de polyoléfine non réticulée.
PCT/KR2016/003634 2015-04-09 2016-04-07 Résine de polyoléfine déréticulée et composition de résine la contenant WO2016163765A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020150050292A KR101721512B1 (ko) 2015-04-09 2015-04-09 탈가교 폴리올레핀 수지 및 이를 포함하는 수지 조성물
KR10-2015-0050292 2015-04-09

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WO2016163765A1 true WO2016163765A1 (fr) 2016-10-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4053169A4 (fr) * 2019-10-28 2023-11-15 LS Cable & System Ltd. Résine de polyoléfine déréticulée et composition de résine la contenant

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102151360B1 (ko) * 2019-10-28 2020-09-02 엘에스전선 주식회사 케이블 개재용 탈가교 폴리올레핀 수지 및 이를 포함하는 수지 조성물
KR20220121397A (ko) * 2021-02-25 2022-09-01 엘에스전선 주식회사 가교 수지를 포함하는 분말형 첨가제 및 이를 포함하는 수지 조성물

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JP2002128961A (ja) * 2000-10-24 2002-05-09 Nof Corp エチレン系ポリマー組成物、架橋物およびその脱架橋物
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KR20110026035A (ko) * 2009-09-07 2011-03-15 한국과학기술연구원 폐 가교 고밀도 폴리에틸렌계 파이프의 재생방법
KR20130001566A (ko) * 2011-06-27 2013-01-04 한국과학기술연구원 초임계 탈가교 반응으로부터 수득되는 폐가교 폴리올레핀수지를 이용한 발포 성형물 제조 방법 및 발포 성형물
KR20140021498A (ko) * 2013-12-30 2014-02-20 한국과학기술연구원 초임계 탈가교 반응으로부터 수득되는 폐가교 폴리올레핀수지를 이용한 발포 성형물 제조 방법 및 발포 성형물

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JP2002256102A (ja) 2001-03-01 2002-09-11 Chubu Electric Power Co Inc 架橋ポリオレフィンの再生方法
JP2002256103A (ja) 2001-03-01 2002-09-11 Chubu Electric Power Co Inc 架橋ポリオレフィンの再生方法

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Publication number Priority date Publication date Assignee Title
JP2002128961A (ja) * 2000-10-24 2002-05-09 Nof Corp エチレン系ポリマー組成物、架橋物およびその脱架橋物
KR20070063436A (ko) * 2005-12-14 2007-06-19 신에쓰 가가꾸 고교 가부시끼가이샤 비할로겐 난연 수지 조성물
KR20100045282A (ko) * 2008-10-23 2010-05-03 한국과학기술연구원 폐 저밀도 폴리에틸렌계 발포체의 재생방법
KR20110026035A (ko) * 2009-09-07 2011-03-15 한국과학기술연구원 폐 가교 고밀도 폴리에틸렌계 파이프의 재생방법
KR20130001566A (ko) * 2011-06-27 2013-01-04 한국과학기술연구원 초임계 탈가교 반응으로부터 수득되는 폐가교 폴리올레핀수지를 이용한 발포 성형물 제조 방법 및 발포 성형물
KR20140021498A (ko) * 2013-12-30 2014-02-20 한국과학기술연구원 초임계 탈가교 반응으로부터 수득되는 폐가교 폴리올레핀수지를 이용한 발포 성형물 제조 방법 및 발포 성형물

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4053169A4 (fr) * 2019-10-28 2023-11-15 LS Cable & System Ltd. Résine de polyoléfine déréticulée et composition de résine la contenant

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KR20160121658A (ko) 2016-10-20

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