WO2016163765A1 - Decrosslinked polyolefin resin and resin composition containing same - Google Patents

Decrosslinked polyolefin resin and resin composition containing same 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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polyolefin resin
decrosslinked
resin
weight
resin composition
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PCT/KR2016/003634
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French (fr)
Korean (ko)
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신지욱
남기준
홍순만
구종민
백범기
라윤호
황승상
백경열
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엘에스전선 주식회사
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Publication of WO2016163765A1 publication Critical patent/WO2016163765A1/en

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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.

Abstract

The present invention relates to a decrosslinked polyolefin resin that is recycled after crosslinking, a method for preparing same, and a resin composition containing same. Specifically, the present invention relates to a recycled decrosslinked polyolefin resin, a method for preparing same, and a resin composition containing same, the recycled decrosslinked polyolefin resin exhibiting more excellent processability, flame retardant properties, mechanical properties, etc. compared to an uncrosslinked new polyolefin resin.

Description

탈가교 폴리올레핀 수지 및 이를 포함하는 수지 조성물Decrosslinked Polyolefin Resin and Resin Composition Comprising the Same
본 발명은 가교후 재활용된 탈가교 폴리올레핀 수지 및 이를 포함하는 수지 조성물에 관한 것이다. 구체적으로, 본 발명은 가교되지 않은 신재 폴리올레핀 수지에 비해 오히려 가공성, 난연성, 기계적 물성 등이 우수한 재활용된 탈가교 폴리올레핀 수지 및 이를 포함하는 수지 조성물에 관한 것이다.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.
자원보호, 환경오염 방지 차원에서 최근 혼합 폐플라스틱의 재활용을 위한 기술개발이 중요한 사회적 문제로 대두되고 있다. 일반 가정에서 사용되고 있는 폐 포장 필름류 등에 대해서는 「생산자 책임 재활용 제도」의 시행으로 재활용 효율성이 점차 향상되고 있다.Recently, technology development for recycling mixed waste plastics has emerged as an important social issue in terms of resource protection and environmental pollution prevention. Recycling efficiency has been gradually improved due to the implementation of the "Responsibility for Recycling of Producers" for waste packaging films used in homes.
그러나, 폴리에틸렌계 수지 등의 폴리올레핀계 수지는 저렴한 가격에 비하여 우수한 물성을 가짐에 따라 범용 플라스틱 중에서 가장 많이 사용되고 있지만, 가교되는 경우 가교된 고분자 사슬의 불용성(insoluble) 및 불융성(infusible)으로 인해 아직까지 적절한 처리나 재생방법이 제대로 개발되어 있지 않다.However, 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.
따라서, 현재 가교 폴리올레핀계 수지는 대부분 소각되거나 매립될 뿐, 효과적인 재활용이 이루어지지 않고 있으며, 이는 환경적으로 많은 문제점들을 야기하고 있다.Therefore, at present, crosslinked polyolefin resins are mostly incinerated or buried, and effective recycling is not achieved, which causes many environmental problems.
이러한 폐 가교 폴리올레핀계 수지를 재활용하기 위해서는 탈가교 반응을 통해 가교 폴리올레핀계 수지의 가교 구조를 제거함으로써 탈가교화시키고, 탈가교된 반응 생성물을 유/무기화시키는 복합적인 시스템을 필요로 한다.In order to recycle such waste crosslinked polyolefin-based resins, there is a need for a complex system of decrosslinking by removing the crosslinked structure of the crosslinked polyolefin-based resin through a decrosslinking reaction and organic / inorganicizing the decrosslinked reaction product.
종래 폐 고밀도 폴리에틸렌, 폐 저밀도 폴리에틸렌 등을 재활용하는 기술이 공지되어 있으나, 종래의 재활용 방법은 고가의 설비를 요하거나 대량생산이 용이하지 않는 등 재활용된 수지의 상용화가 곤란하거나, 종래의 재활용 방법에 의해 재활용된 폴리올레핀 수지는 가교되지 않은 신재 수지에 비해 가공성, 필러로딩성, 기계적 물성 등이 저하되는 문제를 갖고 있다.Conventionally, technologies for recycling waste high density polyethylene, waste low density polyethylene, and the like are known. However, the conventional recycling method is difficult to commercialize recycled resin, such as requiring expensive equipment or not easy to mass production, or to conventional recycling methods. The polyolefin resin recycled by this method has a problem in that workability, filler loading property, mechanical properties, etc. are lowered compared to new resin which is not crosslinked.
따라서, 가교되지 않은 신재 폴리올레핀 수지에 비해 저하되지 않은 가공성, 필러로딩성, 기계적 특성 등을 나타내고 제조비용이 저렴한 재활용된 탈가교 폴리올레핀 수지 및 이의 제조방법이 절실히 요구되고 있는 실정이다.Accordingly, there is an urgent need for a recycled decrosslinked polyolefin resin and a method for producing the same, which show less workability, filler loading property, mechanical properties, and the like, compared to new non-crosslinked new polyolefin resin.
본 발명은 가공성, 필러로딩성, 기계적 특성 등이 신재 폴리올레핀 수지에 비해 저하되지 않는 재활용된 탈가교 폴리올레핀 수지를 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a recycled decrosslinked polyolefin resin in which processability, filler loading properties, mechanical properties and the like are not lowered compared to new polyolefin resins.
또한, 본 발명은 신재 폴리올레핀 수지에 비해 난연성이 우수한 재활용된 탈가교 폴리올레핀 수지를 제공하는 것을 목적으로 한다.It is also an object of the present invention to provide a recycled decrosslinked polyolefin resin having excellent flame retardancy compared to new polyolefin resin.
상기 과제를 해결하기 위해, 본 발명은,In order to solve the above problems, the present invention,
가교 후 재활용을 위해 탈가교된 폴리올레핀 수지로서, 중량평균분자량(Mw)이 70,000 이상이고, 다분산성(PDI)이 10 이상이며, 겔분율이 0.2 내지 20%인, 탈가교 폴리올레핀 수지를 제공한다.A crosslinked polyolefin resin for recycling after crosslinking, the crosslinked polyolefin resin 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%.
여기서, 상기 가교가 실린가교이고, 상기 수지의 총 중량을 기준으로, 규소(Si)의 함량이 0.05 내지 2 중량%인 것을 특징으로 하는, 탈가교 폴리올레핀 수지를 제공한다.Here, 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.
또한, 상기 폴리올레핀 수지는 폴리에틸렌 수지를 포함하는 것을 특징으로 하는, 탈가교 폴리올레핀 수지를 제공한다.In addition, the polyolefin resin provides a decrosslinked polyolefin resin, characterized in that it comprises a polyethylene resin.
그리고, 가교 폴리올레핀 수지가 300 내지 400℃의 반응온도 및 8 내지 30 MPa의 반응압력 하에서 반응용매인 초임계 유체에 의해 탈가교됨으로써 제조되는 것을 특징으로 하는, 탈가교 폴리올레핀 수지를 제공한다.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.
한편, 상기 탈가교 폴리올레핀 수지 및 가교되지 않은 신재 폴리올레핀 수지를 10:90 내지 70:30의 배합비로 포함하는, 폴리올레핀 수지 조성물을 제공한다.On the other hand, it provides a 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.
여기서, 중량평균분자량(Mw)이 100,000 이상이고, 다분산성(PDI)이 5.5 이상인 것을 특징으로 하는, 폴리올레핀 수지 조성물을 제공한다.Here, 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.
또한, 상용화제, 난연제, 산화방지제 및 활제를 추가로 포함하고, 수지와 상용화제의 혼합물 100 중량부를 기준으로, 상기 난연제의 함량은 50 내지 200 중량부인 것을 특징으로 하는, 폴리올레핀 수지 조성물을 제공한다.In addition, further comprising a compatibilizer, a flame retardant, an antioxidant and a lubricant, based on 100 parts by weight of the mixture of the resin and the compatibilizer, characterized in that the content of the flame retardant is 50 to 200 parts by weight, to provide a polyolefin resin composition. .
그리고, 상기 난연제는 수산화알루미늄, 수산화마그네슘, 수산화칼슘, 훈타이드(huntite)(Mg3Ca(CO3)4) 및 하이드로마그네시아트(hydromagnesite)(Mg5(CO3)4(OH)2)로 이루어진 그룹으로부터 선택된 1종 이상의 무기 난연제를 포함하는 것을 특징으로 하는, 폴리올레핀 수지 조성물을 제공한다.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.
본 발명에 따른 탈가교 폴리올레핀 수지는 정밀하게 제어된 분자량과 분자량 분포, 그리고 이에 따라 정밀하게 제어된 점도와 겔분율을 통해 오히려 신재 폴리올레핀에 비해 우수한 가공성, 필러로딩성, 기계적 특성을 나타내는 우수한 효과를 나타낸다.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.
또한, 본 발명에 따른 탈가교 폴리올레핀 수지는 가교 잔기 함량의 정밀한 제어를 통해 우수한 난연성을 나타내는 우수한 효과를 나타낸다.In addition, 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.
도 1은 실시예 1 내지 4 및 비교예 1 내지 4 각각에 따른 폴리에틸렌 수지 조성물의 점도를 측정한 결과를 나타낸 것이다.1 shows the results of measuring the viscosity of the polyethylene resin composition according to Examples 1 to 4 and Comparative Examples 1 to 4, respectively.
도 2는 실시예 4 및 비교예 4 각각에 따른 폴리에틸렌 수지 조성물로부터 제조된 시편의 인장강도를 측정한 결과를 나타낸 것이다.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.
도 3은 실시예 1 내지 4 및 비교예 1 내지 4 각각에 다른 폴리에틸렌 수지 조성물의 산소지수(LOI)를 측정한 결과를 나타낸 것이다.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.
이하, 본 발명의 바람직한 실시예들을 상세히 설명하기로 한다. 그러나, 본 발명은 여기서 설명된 실시예들에 한정되지 않고 다른 형태로 구체화될 수도 있다. 오히려, 여기서 소개되는 실시예들은 개시된 내용이 철저하고 완전해질 수 있도록, 그리고 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 제공되어지는 것이다.Hereinafter, preferred embodiments of the present invention will be described in detail. However, the invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosure may be made thorough and complete, and to fully convey the spirit of the present invention to those skilled in the art.
본 발명은 가교 후 재활용을 위해 탈가교된 폴리올레핀 수지에 관한 것이다. 여기서, 상기 가교는 유기 과산화물 등의 가교제에 의한 화학가교, 실란계 가교제에 의한 실란가교(또는 수가교) 등의 가교를 포함한다.The present invention relates to a polyolefin resin decrosslinked for recycling after crosslinking. Here, 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.
본 발명에 따른 탈가교 폴리올레핀 수지는 가교 폴리올레핀 수지의 재활용을 위한 탈가교 반응에 의해 상기 가교 폴리올레핀 수지가 탈가교됨으로써 제조될 수 있다. 상기 탈가교 반응은 예를 들어 특정 온도와 압력 조건 하에서 반응용매로서 초임계 유체를 이용하여 수행될 수 있다.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.
본 발명에 따른 탈가교 폴리올레핀 수지는 중량평균분자량(Mw)이 70,000 이상, 바람직하게는 100,000 이상이고, 특히 분자량 분포를 나타내는 다분산성(Polydispersity; PDI)(Mw/Mn)이 10 이상일 수 있다.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.
여기서, 상기 탈가교 폴리올레핀 수지는 중량평균분자량(Mw)이 70,000 이상이므로 기계적 특성이 충분한 동시에, 가교되지 않은 신재 저밀도 폴리에틸렌의 다분산성(PDI)인 4.4에 비해 2배 이상 증가한 다분산성(PDI)을 가지므로 압출 성형성 등의 가공성 및 난연제 등의 필러 로딩성(filler loading property)이 크게 향상된다.Here, 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.
또한, 본 발명에 따른 탈가교 폴리올레핀 수지는 잔존하는 가교 부분을 나타내는 겔분율이 0.2 내지 20%일 수 있다. 상기 탈가교 폴리올레핀 수지의 겔분율이 0.2% 미만인 경우 불필요하게 가교 부분이 제거된 것인 반면 상기 겔분율이 20% 초과인 경우 가교 부분이 과도하게 잔존하여 상기 탈가교 폴리올레핀 수지의 점도가 상승하는 등의 이유로 압출 성형성 등의 가공성이 저하될 수 있다.In addition, the decrosslinked polyolefin resin according to the present invention may have a gel fraction representing the remaining crosslinked portion of 0.2 to 20%. When 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.
그리고, 본 발명에 따른 탈가교 폴리올레핀 수지는 실란가교 후 탈가교된 경우 상기 탈가교 폴리올레핀 수지의 고분자 사슬에 잔존하는 실란 잔기가 상기 탈가교 폴리올레핀 수지의 난연성을 추가로 향상시킬 수 있다. 여기서, 상기 실란 잔기의 화학 구조는 -SiOCH3, -SiOH, -Si-O-Si- 등일 수 있다.In addition, in the decrosslinked polyolefin resin according to the present invention, when decrosslinked after silane crosslinking, silane residues remaining in the polymer chain of the decrosslinked polyolefin resin may further improve flame retardancy of the decrosslinked polyolefin resin. Here, the chemical structure of the silane residue may be -SiOCH 3 , -SiOH, -Si-O-Si- and the like.
또한, 상기 실란 잔기의 규소(Si)의 함량은 상기 수지의 총 중량을 기준으로 0.05 내지 2 중량%일 수 있다. 상기 규소(Si)의 함량이 0.05 중량% 미만인 경우 난연성이 향상되는 정도가 극히 미미할 수 있는 반면, 2 중량%를 초과하는 경우 상기 탈가교 폴리올레핀 수지의 점도가 상승하는 등의 이유로 압출 성형성 등의 가공성 및 필러 로딩성이 저하될 수 있고, 오히려 난연성이 저하될 수 있다.In addition, 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. When 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.
본 발명에 따른 탈가교 폴리올레핀 수지에 있어서, 상기 폴리올레핀 수지는 폴리에틸렌, 폴리프로필렌 등의 올레핀계 단독 중합체, 또는 2종 이상의 올레핀 단량체의 중합체 의한 올레핀계 랜덤 또는 블록 공중합체를 포함할 수 있고, 바람직하게는 폴리에틸렌일 수 있다. 상기 폴리에틸렌은 초저밀도 폴리에틸렌(ULDPE), 저밀도 폴리에틸렌(LDPE), 선형 저밀도 폴리에틸렌(LLDPE), 중밀도 폴리에틸렌(MDPE), 고밀도 폴리에틸렌(HDPE), 또는 이들의 조합일 수 있다.In the decrosslinked polyolefin resin according to the present invention, 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.
본 발명에 따른 탈가교 폴리올레핀 수지는 가교 폴리올레핀 수지가 예를 들어 일축 압축기 내부에서 300 내지 400℃의 반응온도 및 8 내지 30 MPa의 반응압력 하에서 반응용매인 초임계 유체에 의해 탈가교됨으로써 연속적으로 제조될 수 있다.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.
상기 반응용매로서 사용된 초임계 유체는 일반적인 액체나 기체 상태의 물질이 임계점이라 불리는 고온, 고압의 한계를 넘으면서 기체와 액체를 구별할 수 없는 임계 상태에 이른 물질을 지칭한다. 초임계 유체의 분자의 밀도는 액체에 가깝지만 점도는 낮아 기체에 가깝고, 확산이 빨라 열전도성이 물만큼이나 높다.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.
따라서, 초임계 유체를 탈가교 반응의 반응용매로 사용하면 녹아있는 분자, 즉, 용질 주변의 용매 농도가 극히 높아져 탈가교 반응이 일어나게 된다. 상기 초임계 유체로서 증류수, 메탄올, 에탄올 등의 알코올류, 또는 이들의 혼합물이 사용될 수 있다.Therefore, when the supercritical fluid is used as the reaction solvent in the decrosslinking reaction, the concentration of the dissolved molecule, that is, the solvent around the solute is extremely high, resulting in the decrosslinking reaction. As the supercritical fluid, alcohols such as distilled water, methanol, ethanol, or a mixture thereof may be used.
본 발명은 상기 탈가교 폴리올레핀 수지를 포함하는 폴리올레핀 수지 조성물에 관한 것이다.The present invention relates to a polyolefin resin composition comprising the decrosslinked polyolefin resin.
본 발명에 따른 폴리올레핀 수지 조성물은 상기 탈가교 폴리올레핀 수지와 가교되지 않은 신재 폴리올레핀 수지를 포함할 수 있다. 여기서, 상기 탈가교 폴리올레핀 수지와 상기 신재 폴리올레핀 수지의 배합비는 약 10:90 내지 70:30, 바람직하게는 약 10:90 내지 50:50일 수 있다.The polyolefin resin composition according to the present invention may include a new polyolefin resin not crosslinked with the decrosslinked polyolefin resin. Here, 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.
본 발명에 따른 폴리올레핀 수지 조성물은 중량평균분자량(Mw)이 100,000 이상, 바람직하게는 155,000 이상, 그리고 다분산성(PDI)이 5.5 이상일 수 있다. 이로써, 상기 폴리올레핀 수지 조성물은 우수한 기계적 특성 및 가공성을 동시에 구현할 수 있다.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. As a result, the polyolefin resin composition may simultaneously realize excellent mechanical properties and processability.
또한, 본 발명에 따른 폴리올레핀 수지 조성물은 난연제 등의 첨가제의 필러 로딩성을 추가로 향상시키기 위해 에틸렌비닐아세테이트(Ethylene vinyl acetate; EVA) 수지를 추가로 포함할 수 있다. 여기서, 상기 에틸렌비닐아세테이트(EVA) 수지의 함량은 수지와 상용화제의 혼합물 100 중량부를 기준으로 25 내지 50 중량부일 수 있다. 상기 에틸렌비닐아세테이트(EVA) 수지의 함량이 25 중량부 미만인 경우 필러 로딩성이 향상되는 수준이 미미한 반면, 50 중량부 초과인 경우 상기 폴리올레핀 수지 조성물의 기계적·전기적 특성이 저하될 수 있다.In addition, 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. Here, 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. When the content of the ethylene vinyl acetate (EVA) resin is less than 25 parts by weight, 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.
본 발명에 따른 폴리올레핀 수지 조성물은 난연제, 산화방지제, 활제 등의 첨가제를 포함할 수 있다. 상기 난연제는 수산화알루미늄, 수산화마그네슘, 수산화칼슘, 훈타이드(huntite)(Mg3Ca(CO3)4) 및 하이드로마그네시아트(hydromagnesite)(Mg5(CO3)4(OH)2)로 이루어진 그룹으로부터 선택된 1종 이상의 무기 난연제를 포함할 수 있다.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.
상기 난연제로서 사용되는 수산화마그네슘(Mg(OH)2) 등의 무기입자는 고표면 에너지를 갖는 친수성인 반면, 폴리올레핀 등의 수지는 저표면 에너지를 갖는 소수성이기 때문에, 상기 무기입자는 상기 수지에 대한 분산성이 좋지 않고, 기계적·전기적 특성에도 악영향을 미칠 수 있다. 따라서, 이러한 문제점을 해결하기 위하여 수산화마그네슘 등의 무기입자는 비닐실란, 스테아린산, 올레인산, 아미노폴리실록산, 티타네이트계 커플링제 등으로 표면 처리될 수 있다.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.
상기 무기입자가 비닐실란 등에 의해 표면 처리되는 경우, 비닐실란 등의 가수분해기가 축합반응에 의해 수산화마그네슘 등의 무기입자 표면에 화학 결합을 함으로써 부착되고, 실란기가 상기 수지와 반응하여 우수한 분산성을 확보할 수 있게 된다. 또한, 상기 실란기는 상기 폴리올레핀 수지 조성물의 난연성을 추가로 향상시킬 수 있다.When the inorganic particles are surface treated with vinyl silane or the like, hydrolysers such as vinyl silane are attached by chemical bonding to the surface of inorganic particles such as magnesium hydroxide by a condensation reaction, and the silane groups react with the resin to provide excellent dispersibility. It can be secured. In addition, the silane group may further improve the flame retardancy of the polyolefin resin composition.
상기 난연제의 함량은 상기 수지와 상용화제의 혼합물 100 중량부를 기준으로 50 내지 200 중량부일 수 있다. 상기 난연제의 함량이 50 중량부 미만인 경우 충분한 난연성을 구현할 수 없는 반면, 200 중량부 초과인 경우 상기 폴리올레핀 수지 조성물의 압출 성형성 등의 가공성이 크게 저하될 수 있다. 한편, 상기 산화방지제, 활제 등의 기타 첨가제는 상기 수지와 상용화제의 혼합물 100 중량부를 기준으로 1 내지 10 중량부로 포함될 수 있다.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.
[실시예]EXAMPLE
1. 제조예1. Preparation
아래 표 1에 나타난 바와 같은 구성성분 및 함량으로 실시예 및 비교예 각각에 따른 폴리에틸렌 수지 조성물을 제조했다. 아래 표 1에 기재된 함량의 단위는 중량부이다.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.
비교예1Comparative Example 1 실시예1Example 1 비교예2Comparative Example 2 실시예2Example 2 비교예3Comparative Example 3 실시예3Example 3 비교예4Comparative Example 4 실시예4Example 4
수지1 Resin 1 6565 4040 6565 4040
수지2 Resin 2 6565 4040 6565 4040
수지3Resin 3 2525 2525 5050 5050 2525 2525 5050 5050
상용화제 Compatibilizer 1010 1010 1010 1010 1010 1010 1010 1010
난연제Flame retardant 100100 100100 100100 100100 150150 150150 150150 150150
산화방지제Antioxidant 1One 1One 1One 1One 1One 1One 1One 1One
활제Lubricant 1One 1One 1One 1One 1One 1One 1One 1One
- 수지1 : 신재 폴리에틸렌 수지Resin 1: New Polyethylene Resin
- 수지2 : 수가교 후 탈가교된 폴리에틸렌 수지(규소 함량 : 1.5 중량%) 30 중량% + 신재 폴리에틸렌 수지 70 중량%-Resin 2: 30% by weight of cross-linked polyethylene resin (silicon content: 1.5% by weight) + 70% by weight of new polyethylene resin
- 수지3 : 에틸렌비닐아세테이트 수지Resin 3: Ethylene vinyl acetate resin
- 난연제 : 수산화알루미늄Flame Retardant: Aluminum Hydroxide
- 산화방지제 : Irganox 1010Antioxidant: Irganox 1010
- 활제 : LC 왁스Lubricant: LC wax
2. 물성 평가2. Property evaluation
1) 가공성 평가1) Machinability Evaluation
실시예 1 내지 4 및 비교예 1 내지 4 각각에 따른 폴리에틸렌 수지 조성물의 점도를 측정했고, 그 결과는 도 1에 나타난 바와 같다.The viscosity of the polyethylene resin composition according to each of Examples 1 to 4 and Comparative Examples 1 to 4 was measured, and the results are shown in FIG. 1.
도 1에 도시된 바와 같이, 본 발명에 따른 실시예 1 내지 4의 수지 조성물은 본 발명에 따른 탈가교 폴리에틸렌 수지가 포함되어 신재 폴리에틸렌 수지만이 포함된 비교예 1 내지 4의 수지 조성물에 비해 점도가 낮아 압출 성형성 등의 가공성이 우수한 것으로 확인되었다.As shown in Figure 1, 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.
2) 기계적 특성 평가2) Mechanical property evaluation
실시예 4 및 비교예 4 각각에 따른 폴리에틸렌 수지 조성물로부터 제조된 시편의 인장강도를 100℃의 열화 조건에서 7일(168시간), 14일(336시간) 및 21일(504시간) 후 측정했고, 그 결과는 도 2에 나타난 바와 같다.Tensile strength of the specimens prepared from the polyethylene resin compositions according to Example 4 and Comparative Example 4, respectively, was measured after 7 days (168 hours), 14 days (336 hours) and 21 days (504 hours) at 100 ° C deterioration conditions. The results are as shown in FIG.
도 2에 도시된 바와 같이, 본 발명에 따른 실시예 4의 수지 조성물에 의해 형성된 시편은 비교예 4의 수지 조성물에 의해 형성된 시편에 비해 열화 시간이 늘어감에 따라 인장강도가 오히려 우수한 것으로 확인되었다.As shown in FIG. 2, 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. .
3) 난연성 평가3) Flame retardancy evaluation
실시예 1 내지 4 및 비교예 1 내지 4 각각에 다른 폴리에틸렌 수지 조성물의 산소지수(LOI)를 측정했고, 그 결과는 도 3에 나타난 바와 같다.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.
도 3에 도시된 바와 같이, 본 발명에 따른 실시예 1 내지 4의 수지 조성물은 비교예 1 내지 4의 수지 조성물에 비해 산소지수가 높아 난연성이 12 내지 20% 정도 향상된 것으로 확인되었다. 이는 실시예 1 내지 4의 수지 조성물은 탈가교 폴리에틸렌 수지의 고분자 사슬에 잔존하는 규소(Si)에 의해 난연성이 추가로 향상된 것으로 예측된다. As 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.
본 명세서는 본 발명의 바람직한 실시예를 참조하여 설명하였지만, 해당 기술분야의 당업자는 이하에서 서술하는 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경 실시할 수 있을 것이다. 그러므로 변형된 실시가 기본적으로 본 발명의 특허청구범위의 구성요소를 포함한다면 모두 본 발명의 기술적 범주에 포함된다고 보아야 한다.Although the present specification has been described with reference to preferred embodiments of the invention, those skilled in the art may variously modify and change the invention without departing from the spirit and scope of the invention as set forth in the claims set forth below. Could be done. Therefore, it should be seen that all modifications included in the technical scope of the present invention are basically included in the scope of the claims of the present invention.

Claims (8)

  1. 가교 후 재활용을 위해 탈가교된 폴리올레핀 수지로서,Decrosslinked polyolefin resin for recycling after crosslinking,
    중량평균분자량(Mw)이 70,000 이상이고,The weight average molecular weight (Mw) is 70,000 or more,
    다분산성(PDI)이 10 이상이며,Polydispersity (PDI) of 10 or greater,
    겔분율이 0.2 내지 20%인, 탈가교 폴리올레핀 수지.Decrosslinked polyolefin resin having a gel fraction of 0.2 to 20%.
  2. 제1항에 있어서,The method of claim 1,
    상기 가교가 실린가교이고,The crosslinking is silinic crosslinking,
    상기 수지의 총 중량을 기준으로, 규소(Si)의 함량이 0.05 내지 2 중량%인 것을 특징으로 하는, 탈가교 폴리올레핀 수지.Decrosslinked polyolefin resin, characterized in that the content of silicon (Si) is 0.05 to 2% by weight based on the total weight of the resin.
  3. 제1항 또는 제2항에 있어서,The method according to claim 1 or 2,
    상기 폴리올레핀 수지는 폴리에틸렌 수지를 포함하는 것을 특징으로 하는, 탈가교 폴리올레핀 수지.The polyolefin resin, characterized in that it comprises a polyethylene resin, decrosslinked polyolefin resin.
  4. 제1항 또는 제2항에 있어서,The method according to claim 1 or 2,
    가교 폴리올레핀 수지가 300 내지 400℃의 반응온도 및 8 내지 30 MPa의 반응압력 하에서 반응용매인 초임계 유체에 의해 탈가교됨으로써 제조되는 것을 특징으로 하는, 탈가교 폴리올레핀 수지.The crosslinked polyolefin resin is produced 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.
  5. 제1항 또는 제2항의 탈가교 폴리올레핀 수지 및 가교되지 않은 신재 폴리올레핀 수지를 10:90 내지 70:30의 배합비로 포함하는, 폴리올레핀 수지 조성물.A polyolefin resin composition comprising the decrosslinked polyolefin resin of claim 1 or 2 and a new non-crosslinked polyolefin resin in a blending ratio of 10:90 to 70:30.
  6. 제5항에 있어서,The method of claim 5,
    중량평균분자량(Mw)이 100,000 이상이고, 다분산성(PDI)이 5.5 이상인 것을 특징으로 하는, 폴리올레핀 수지 조성물.The weight average molecular weight (Mw) is 100,000 or more, and polydispersity (PDI) is 5.5 or more, The polyolefin resin composition characterized by the above-mentioned.
  7. 제5항에 있어서,The method of claim 5,
    상용화제, 난연제, 산화방지제 및 활제를 추가로 포함하고,Further comprises compatibilizers, flame retardants, antioxidants, and lubricants,
    수지와 상용화제의 혼합물 100 중량부를 기준으로, 상기 난연제의 함량은 50 내지 200 중량부인 것을 특징으로 하는, 폴리올레핀 수지 조성물.Based on 100 parts by weight of the mixture of the resin and the compatibilizer, the content of the flame retardant is 50 to 200 parts by weight, polyolefin resin composition.
  8. 제7항에 있어서,The method of claim 7, wherein
    상기 난연제는 수산화알루미늄, 수산화마그네슘, 수산화칼슘, 훈타이드(huntite)(Mg3Ca(CO3)4) 및 하이드로마그네시아트(hydromagnesite)(Mg5(CO3)4(OH)2)로 이루어진 그룹으로부터 선택된 1종 이상의 무기 난연제를 포함하는 것을 특징으로 하는, 폴리올레핀 수지 조성물.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 ) A polyolefin resin composition comprising at least one inorganic flame retardant selected.
PCT/KR2016/003634 2015-04-09 2016-04-07 Decrosslinked polyolefin resin and resin composition containing same WO2016163765A1 (en)

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