WO2014171772A1 - Low-particle-size polyethylene, chlorinated polyethylene thereof, and pvc composition containing same - Google Patents

Low-particle-size polyethylene, chlorinated polyethylene thereof, and pvc composition containing same Download PDF

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Publication number
WO2014171772A1
WO2014171772A1 PCT/KR2014/003375 KR2014003375W WO2014171772A1 WO 2014171772 A1 WO2014171772 A1 WO 2014171772A1 KR 2014003375 W KR2014003375 W KR 2014003375W WO 2014171772 A1 WO2014171772 A1 WO 2014171772A1
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Prior art keywords
polyethylene
chlorinated polyethylene
weight
chlorinated
pvc
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PCT/KR2014/003375
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French (fr)
Korean (ko)
Inventor
유성훈
이진복
도상록
배근열
장상필
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(주) 엘지화학
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Priority claimed from KR1020140044891A external-priority patent/KR101603407B1/en
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to CN201480001129.2A priority Critical patent/CN104271616B/en
Publication of WO2014171772A1 publication Critical patent/WO2014171772A1/en

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    • 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
    • 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
    • C08F10/02—Ethene
    • 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
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene

Definitions

  • the present invention relates to a low particle size polyethylene, a chlorinated polyethylene thereof, and a PVC composition comprising the same, and more particularly, to a low particle size polyethylene having excellent chlorine distribution uniformity in polyethylene during chlorination; Chlorinated polyethylene having excellent compatibility with PVC and impact reinforcing performance and greatly shortening the Fusion Time; And it relates to a PVC composition excellent in impact strength, processability and productivity.
  • Polyethylene is a chain-like high molecular compound produced by polymerization of ethylene, and is classified into low density polyethylene (LDEP) and high density polyethylene (HDPE) according to density.
  • LDEP low density polyethylene
  • HDPE high density polyethylene
  • High density polyethylene can generally be prepared by polymerizing ethylene at about 70 ° C. and around 10 atm using a Ziegler-Natta catalyst.
  • High density polyethylene has excellent softening point, firmness, strength and electrical insulation, and is used in various containers, packaging films, fibers, pipes, packings, insulating materials and the like.
  • Chlorinated polyethylene is chlorinated polyethylene treated with chlorine.
  • Chlorinated polyethylene is generally prepared by reacting polyethylene with chlorine in suspension, or by reacting polyethylene with chlorine in aqueous HCl.
  • Chlorinated polyethylene is widely used as an impact modifier for PVC pipes and window profiles because of its excellent chemical resistance, weather resistance, flame retardancy, processability and impact strength reinforcement.
  • the present invention aims to provide a polyethylene which is excellent in uniformity of chlorine distribution in polyethylene upon chlorination.
  • the present invention aims to provide a PVC composition excellent in impact strength and workability.
  • the present substrate has an average particle size of 30 to 170 ⁇ m, or 30 to 150 ⁇ m, melt index (5.0 kg) is 0.001 to 20, or 0.01 to 100, the weight average molecular weight 10,000 to 1,000,000 polyethylene having a molecular weight distribution (MWD) of 20 or less, or 3 to 20, a melting temperature of 125 to 140 ° C., a density of 0.94 g / cm 3 or more, and used for the production of chlorinated polyethylene To provide.
  • melt index 5.0 kg
  • MWD molecular weight distribution
  • the present substrate has an average particle size of 50 to 150 ⁇ m, or 50 to 130 ⁇ m, a melt index (5.0 kg) of 0.001 to 5, or 0.1 to 10, a weight average molecular weight of 50,000 to 300,000 g / mol, and a molecular weight
  • the present disclosure also provides chlorinated polyethylene made from the polyethylene.
  • the present disclosure also provides a PVC composition comprising the chlorinated polyethylene and vinyl chloride polymer (PVC).
  • PVC chlorinated polyethylene and vinyl chloride polymer
  • a low particle size polyethylene having excellent uniformity of chlorine distribution in polyethylene during chlorination; Chlorinated polyethylene having excellent compatibility with PVC and impact reinforcing performance and greatly shortening the Fusion Time; And it is effective to provide a PVC composition excellent in impact strength, processability and productivity.
  • the polyethylene of the present disclosure has an average particle size of 30 to 150 ⁇ m, a melt index (5.0 kg) of 0.01 to 100, a weight average molecular weight of 10,000 to 1,000,000 g / mol, a molecular weight distribution (MWD) of 3 to 20, and melting
  • the temperature is 125 to 140 ° C. and the density is 0.94 g / cm 3 or more, and is used for the production of chlorinated polyethylene.
  • the polyethylene of the present disclosure has, for example, 20 to 100% by weight, 50 to 90% by weight, or 60 to 90% by weight of low particle size polyethylene having a particle size of 150 ⁇ m or less. It is excellent, and when applied as an impact modifier in PVC, the impact reinforcing performance, plasticization rate and productivity is greatly improved.
  • the polyethylene of the present disclosure has an average particle size of 50 to 150 ⁇ m, 70 to 150 ⁇ m, 90 to 130 ⁇ m, or 50 to 130 ⁇ m, and has excellent chlorine distribution uniformity in polyethylene when chlorinated within this range, When applied as an impact modifier, the impact reinforcement performance, plasticization speed and productivity are greatly improved.
  • the polyethylene of the present disclosure has a melt index (5.0 kg) of 0.1 to 10, 0.1 to 3.0, or 0.1 to 2.0, and has excellent impact reinforcing effect within this range.
  • the polyethylene of the present disclosure has a weight average molecular weight of another example of 50,000 to 300,000 g / mol, 100,000 to 250,000 g / mol, or 150,000 to 250,000 g / mol.
  • the polyethylene of the present disclosure has a molecular weight distribution (MWD) of 3.5 to 15, or 4 to 10, and has an effect of greatly improving plasticization rate and productivity when applied as an impact modifier to PVC within this range.
  • MFD molecular weight distribution
  • the polyethylene of the present disclosure has a melting temperature of 130 to 140 ° C, or 130 to 136 ° C.
  • the polyethylene of the present disclosure has a density of 0.94 to 0.960 g / cm 3 as another example.
  • the polyethylene of the present disclosure may be, for example, a comonomer free polyethylene that does not contain a comonomer.
  • the chlorinated polyethylene may be produced by, for example, an aqueous phase method or an acid phase method.
  • the CPE chloride time and the post-treatment time such as neutralization and water washing are greatly shortened.
  • the polyethylene of the present disclosure may be prepared, for example, by reacting an ethylene monomer with a catalyst under a molecular weight modifier in a continuous stirred reactor (CSTR).
  • CSTR continuous stirred reactor
  • the molecular weight modifier may be hydrogen, for example.
  • the catalyst may be, for example, a Ziegler-Natta catalyst or a Ziegler-Natta catalyst diluted in a solvent.
  • the Ziegler-Natta catalyst has an average particle size of 3 to 10 ⁇ m, or 5 to 8 ⁇ m, and can effectively obtain polyethylene having a low particle size and a constant molecular weight distribution (MWD) within this range.
  • MWD molecular weight distribution
  • the chlorinated polyethylene of the present disclosure is characterized in that it is made from the polyethylene of the present disclosure.
  • the chlorination may be carried out by an aqueous phase method or an acid phase method, for example, in this case, there is an effect of improving the elasticity (elastic) of the CPE produced by uniform chlorine distribution in the chlorinated polyethylene.
  • the aqueous phase method is, for example, a method of chlorination using an emulsifier and a dispersant together with water
  • the acidic method is, for example, a method of chlorination of an acid aqueous solution such as an aqueous hydrochloric acid (HCl) solution using an emulsifier and a dispersant.
  • the chlorinated polyethylene may for example have a chlorine content of 20 to 45% by weight, 31 to 40% by weight, or 33 to 38% by weight.
  • the chlorinated polyethylene may be, for example, random chlorinated polyethylene.
  • the chlorinated polyethylene for example, has a volume resistance of 10 13 to 10 17 ⁇ cm, 10 14 to 10 17 ⁇ cm, or 10 15 to 10 16 ⁇ cm, and is excellent in insulation effect when used for electric wires within this range.
  • the chlorinated polyethylene for example, has a thermal stability of 160 to 180 °C, or 170 to 175 °C, when used in the cross-linking reaction within this range there is an effect that the decomposition is not good.
  • the chlorinated polyethylene has an MDR crosslinking torque of 1.0 to 3.0 Nm, or 1.5 to 2.5 Nm, and has excellent crosslinking density and tensile strength within this range.
  • the chlorinated polyethylene of the present disclosure can be produced by, for example, dispersing polyethylene with water, an emulsifier and a dispersant, and then reacting with a catalyst and chlorine.
  • the emulsifier is for example polyether or polyalkylene oxide.
  • the dispersant is for example a polymer salt or an organic acid polymer salt.
  • the organic acid may be, for example, methacrylic acid, acrylic acid, or the like.
  • the catalyst is, for example, a chlorination catalyst, and in another example, a peroxide or an organic peroxide.
  • the chlorine may be used alone or in combination with an inert gas, for example.
  • the final chlorination reaction temperature is for example 60 to 150 °C, 70 to 145 °C, 90 to 140 °C, or 130 to 137 °C.
  • the chlorination reaction time is, for example, 10 minutes to 10 hours, 1 to 6 hours, or 2 to 4 hours.
  • the chlorinated polyethylene of the present disclosure may be dispersed in water by 100 parts by weight of polyethylene, 0.01 to 1.0 parts by weight or 0.05 to 0.5 parts by weight of an emulsifier, and 0.1 to 10 parts by weight or 0.5 to 5.0 parts by weight of a dispersant, and then 0.01 to 1.0 catalyst. It can manufacture by making it react by adding a weight part or 0.05-0.5 weight part and 80-200 weight part or 100-150 weight part of chlorine.
  • the chlorinated polyethylene prepared by the above reaction or chlorination process may be obtained as a powdered chlorinated polyethylene through further neutralization, washing and drying.
  • the neutralization process may be, for example, a process of neutralizing a reactant that has undergone a chlorination process with a base solution at 70 to 90 ° C. or 75 to 80 ° C. for 4 to 8 hours.
  • the PVC composition of the present disclosure is characterized by comprising the chlorinated polyethylene and vinyl chloride polymer (PVC) of the present disclosure.
  • the PVC composition may include, for example, 1 to 40% by weight of chlorinated polyethylene and 60 to 99% by weight of vinyl chloride polymer (PVC).
  • PVC vinyl chloride polymer
  • the chlorinated polyethylene may be, for example, 1 to 15% by weight, or 5 to 10% by weight.
  • the vinyl chloride polymer (PVC) may be, for example, 85 to 99% by weight, or 90 to 95% by weight.
  • the PVC composition of the present disclosure may comprise 1 to 20% by weight of chlorinated polyethylene, 70 to 90% by weight of vinyl chloride polymer (PVC), 1 to 10% by weight of TiO 2, 1 to 10% by weight of CaCO 3 , and It may comprise 1 to 10% by weight of composite stearate (Ca, Zn-stearate).
  • the PVC composition has, for example, a plasticization time of 170 seconds or less, 150 seconds or less, or 150 to 100 seconds, and an Izod impact strength of 100 kg ⁇ cm / cm or more, 125 kg ⁇ cm / cm or more, or 125 to 145 kg. * Cm / cm, there is an effect excellent in the physical properties balance and productivity within this range.
  • High-density polyethylene (CE6040X, manufactured by LG Chemical) manufactured with a Ziegler-Natta catalyst having an average particle size of 5.5 ⁇ m was used.
  • This high density polyethylene is in powder form, and the average density, MI, MWD, melting temperature and density are shown in Table 1 below.
  • the chlorinated reactant was neutralized with NaOH or Na 2 CO 3 for 4 hours, washed again with running water for 4 hours, and finally dried at 120 ° C. to prepare chlorinated polyethylene in powder form.
  • a chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that HDPE prepared using a Ziegler-Natta catalyst having an average particle size of 3.5 ⁇ m was used as the high density polyethylene in Example 1.
  • Example 1 A chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chemical CE6040K prepared using Ziegler-Natta catalyst having an average particle size of 8.5 ⁇ m as a high density polyethylene was used in Example 1.
  • a chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chemical CE6040 prepared using Ziegler-Natta catalyst having an average particle size of 12 ⁇ m as the high density polyethylene was used in Example 1.
  • the high density polyethylene used in Comparative Examples 1 to 6 is in the form of a powder, and the average density, MI, MWD, melting temperature and density are shown in Table 2 below.
  • a chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that HDPE having an average particle size of 220 ⁇ m was commercially available as high density polyethylene in Example 1.
  • a chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chem CE2080, which was prepared using Ziegler-Natta catalyst having an average particle size of 12 ⁇ m as the high density polyethylene, was used in Example 1.
  • a chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chem CE2080M prepared using a metallocene catalyst having an average particle size of 10 ⁇ m as a high density polyethylene was used in Example 1.
  • a chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chemical CE2080T1 prepared using a Ziegler-Natta catalyst having an average particle size of 12 ⁇ m was used as the high density polyethylene in Example 1.
  • a chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chem CE2030K prepared using Ziegler-Natta catalyst having an average particle size of 8.5 ⁇ m as a high density polyethylene was used in Example 1.
  • CPE chlorinated polyethylene
  • PVC composition specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were measured by the following method, and the results are shown in Tables 1 and 2 below.
  • Weight average molecular weight (g / mol): Measured by gel permeation chromatography.
  • the measuring instrument used was PL-GPC 220 from Agilent (Polymer Laboratories).
  • the sample was dissolved in TCB (Trichlorobenzene) by adding 0.2% by weight of HDPE and 125 ppm of BHT and then dissolved at 165 ° C. for 2 hours.
  • the samples were then mixed with three Mixed-B Columns manufactured by Agilent (Polymer Laboratories). Analyzed by passing through one B Guard Column.
  • Melting temperature measured at a rate of temperature increase of 10 ° C./min using DSC.
  • Low particle size content (150 ⁇ m or less): Calculated in weight percent using a sieve of 150 ⁇ m mesh.
  • a particle size analyzer corresponding to 50% of the total weight of the sample was calculated by mounting a total of nine Sieves (63 ⁇ 850 ⁇ m) in Taylor type auto shaker.
  • Density measured according to ASTM D-792.
  • Chlorine content The sample was burned at 1000 °C using Automatic Quick Furnace to collect the gas in H 2 O and Cl content analysis by IC (Ion Chromatograph) device.
  • Plasticization time Measured by the time when the PVC is melted and the plasticization is stabilized when the PVC and the chlorinated polyethylene are combined. Thermo Haake was used under conditions of temperature 170 ° C., Screw speed 60 rpm, and resin filling amount (PVC composition) 63 g.
  • the PVC composition was composed of 100 parts by weight of PVC, 8 parts by weight of chlorinated polyethylene, 4 parts by weight of TiO 2 , 5.5 parts by weight of CaCO 3 and 5.5 parts by weight of composite stearate (Ca, Zn).
  • Izod impact strength (1/4 "notched at 0 ° C., kg ⁇ cm / cm): measured in accordance with ASTM D256.
  • volume resistivity Measure the volume resistivity of CPE sheet with measuring area 19.625 cm 3 and specimen thickness 0.2 cm according to ASTM D257 method.
  • Cross-link density The cross-linking agent, cross-linking aid, lubricant and cross-linking agent together with talc and calcium carbonate in chlorinated polyethylene were roll-milled at 130 ° C. for 2 minutes and press-molded at 150 ° C. for 2 minutes to prepare a sheet. ASTM D- Based on 2080, the Scorch Time and the curing rate were measured at 165 ° C.
  • Example 2 PE Low particle content 75 85 53 Average particle size 120 95 145 MI (5 kg) 0.9 0.8 0.45 Mw 175,000 185,000 200,000 MWD 5.5 5.5 5 Melting temperature 133 133 133 density 0.952 0.953 0.952 CPE Chlorine Content 36 36 36 Volume resistivity (* 10 14 ) 170 240 130 Thermal stability 172 174 175 Bridging torque 2.0 2.1 2.3 PVC Plasticization time 140 130 150 Izod impact strength 125 130 145
  • the PVC composition comprising chlorinated polyethylene according to the present invention is a PVC composition comprising chlorinated polyethylene prepared from polyethylene having an average particle size of 180 or 220 ⁇ m ( Compared with Comparative Examples 1 to 5), it was confirmed that the plasticization time was greatly shortened (productivity improved) and the Izod impact strength was also excellent.
  • Comparative Example 6 the average particle size of polyethylene used was 145 ⁇ m but MWD was 24, which is significantly different from the range of MWD of polyethylene according to the present disclosure, and it was confirmed that Izod impact strength was significantly poor.

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Abstract

The present invention relates to a polyethylene, a chlorinated polyethylene thereof, and a PVC composition containing the same, and more specifically, to: a polyethylene having an average particle size of 30-170 μm, a melt index (5.0 kg) of 0.001-100, a weight average molecular weight of 50,000-300,000, a molecular weight distribution (MWD) of 20 or less, a melting point of 125-140 ℃ and a density of 0.94 g/cm3 or more, and is used for preparing a chlorinated polyethylene; a chlorinated polyethylene thereof; and a PVC composition containing the same. According to the present invention, there is an effect of providing: a polyethylene in which the uniformity of chlorine distribution in polyethylene is excellent during chlorination; a chlorinated polyethylene in which compatibility with PVC and impact reinforcement performance are excellent and fusion time is remarkably reduced; and a PVC composition having remarkable impact strength, processability and productivity.

Description

저입도 폴리에틸렌, 이의 염소화 폴리에틸렌 및 이를 포함하는 PVC 조성물Low particle size polyethylene, chlorinated polyethylene thereof and PVC composition comprising the same
본 기재는 저입도 폴리에틸렌, 이의 염소화 폴리에틸렌 및 이를 포함하는 PVC 조성물에 관한 것으로, 보다 상세하게는 염소화(chlorination) 시 폴리에틸렌 내의 염소 분포 균일성이 우수해지는 저입도 폴리에틸렌; PVC와의 상용성 및 충격보강 성능이 뛰어나고 가소화 시간(Fusion Time)을 크게 단축시키는 염소화 폴리에틸렌; 및 충격강도, 가공성 및 생산성이 뛰어난 PVC 조성물에 관한 것이다.The present invention relates to a low particle size polyethylene, a chlorinated polyethylene thereof, and a PVC composition comprising the same, and more particularly, to a low particle size polyethylene having excellent chlorine distribution uniformity in polyethylene during chlorination; Chlorinated polyethylene having excellent compatibility with PVC and impact reinforcing performance and greatly shortening the Fusion Time; And it relates to a PVC composition excellent in impact strength, processability and productivity.
폴리에틸렌은 에틸렌의 중합으로 생기는 사슬 모양의 고분자 화합물로, 밀도에 따라 저밀도 폴리에틸렌(LDEP)과 고밀도 폴리에틸렌(HDPE)으로 구별된다. Polyethylene is a chain-like high molecular compound produced by polymerization of ethylene, and is classified into low density polyethylene (LDEP) and high density polyethylene (HDPE) according to density.
고밀도 폴리에틸렌은 일반적으로 지글러-나타 촉매를 사용하여 대략 70 ℃ 및 10 atm 내외에서 에틸렌을 중합시켜 제조할 수 있다. High density polyethylene can generally be prepared by polymerizing ethylene at about 70 ° C. and around 10 atm using a Ziegler-Natta catalyst.
고밀도 폴리에틸렌은 연화점, 굳기, 강도 및 전기절연성이 뛰어나, 각종 용기, 포장용 필름, 섬유, 파이프, 패킹, 절연재료 등에 사용된다. High density polyethylene has excellent softening point, firmness, strength and electrical insulation, and is used in various containers, packaging films, fibers, pipes, packings, insulating materials and the like.
염소화 폴리에틸렌(chlorinated polyethylene)은 폴리에틸렌을 클로린(chlorine)으로 처리하여 염소화한 것이다.Chlorinated polyethylene is chlorinated polyethylene treated with chlorine.
염소화 폴리에틸렌은 일반적으로 폴리에틸렌을 현탁액 상태에서 클로린과 반응시켜 제조하거나, 폴리에틸렌을 HCl 수용액에서 클로린과 반응시켜 제조할 수 있다. Chlorinated polyethylene is generally prepared by reacting polyethylene with chlorine in suspension, or by reacting polyethylene with chlorine in aqueous HCl.
염소화 폴리에틸렌은 내화학성, 내후성, 난연성, 가공성 및 충격강도 보강효과 등이 우수하여 PVC 파이프 및 윈도우 프로파일(Window Profile)의 충격보강제 등으로 많이 사용된다.Chlorinated polyethylene is widely used as an impact modifier for PVC pipes and window profiles because of its excellent chemical resistance, weather resistance, flame retardancy, processability and impact strength reinforcement.
본 기재는 염소화(chlorination) 시 폴리에틸렌 내의 염소 분포 균일성이 우수해지는 폴리에틸렌을 제공하는 것을 목적으로 한다. The present invention aims to provide a polyethylene which is excellent in uniformity of chlorine distribution in polyethylene upon chlorination.
또한, 본 기재는 PVC와의 상용성 및 충격보강 성능이 뛰어나고 가소화 시간(Fusion Time)을 크게 단축시키는 염소화 폴리에틸렌을 제공하는 것을 목적으로 한다. It is also an object of the present invention to provide a chlorinated polyethylene having excellent compatibility with PVC and impact reinforcing performance and greatly shortening the plasticization time.
또한, 본 기재는 충격강도 및 가공성이 뛰어난 PVC 조성물을 제공하는 것을 목적으로 한다.In addition, the present invention aims to provide a PVC composition excellent in impact strength and workability.
본 기재의 상기 목적 및 기타 목적들은 하기 설명된 본 기재에 의하여 모두 달성될 수 있다.The above and other objects of the present disclosure can be achieved by the present disclosure described below.
상기의 목적을 달성하기 위하여, 본 기재는 평균입도가 30 내지 170 ㎛, 또는 30 내지 150 ㎛이고, 용융지수(5.0㎏)가 0.001 내지 20, 또는 0.01 내지 100이며, 중량평균분자량이 10,000 내지 1,000,000 g/mol이고, 분자량분포도(MWD)가 20 이하, 또는 3 내지 20이며, 용융온도가 125 내지 140 ℃이고, 밀도가 0.94 g/㎤ 이상으로, 염소화 폴리에틸렌의 제조에 사용되는 것을 특징으로 하는 폴리에틸렌을 제공한다.In order to achieve the above object, the present substrate has an average particle size of 30 to 170 ㎛, or 30 to 150 ㎛, melt index (5.0 kg) is 0.001 to 20, or 0.01 to 100, the weight average molecular weight 10,000 to 1,000,000 polyethylene having a molecular weight distribution (MWD) of 20 or less, or 3 to 20, a melting temperature of 125 to 140 ° C., a density of 0.94 g / cm 3 or more, and used for the production of chlorinated polyethylene To provide.
또한, 본 기재는 평균입도가 50 내지 150 ㎛, 또는 50 내지 130 ㎛이고, 용융지수(5.0㎏)가 0.001 내지 5, 또는 0.1 내지 10이며, 중량평균분자량이 50,000 내지 300,000 g/mol이고, 분자량분포도(MWD)가 3.5 내지 15, 또는 10 이하이며, 용융온도가 125 내지 140 ℃이고, 밀도가 0.94 g/㎤ 이상으로, 염소화 폴리에틸렌의 제조에 사용되는 것을 특징으로 하는 폴리에틸렌을 제공한다.In addition, the present substrate has an average particle size of 50 to 150 μm, or 50 to 130 μm, a melt index (5.0 kg) of 0.001 to 5, or 0.1 to 10, a weight average molecular weight of 50,000 to 300,000 g / mol, and a molecular weight Provided is a polyethylene having a distribution degree (MWD) of 3.5 to 15, or 10 or less, a melting temperature of 125 to 140 ° C., and a density of 0.94 g / cm 3 or more, used for producing chlorinated polyethylene.
또한, 본 기재는 상기 폴리에틸렌으로부터 제조되는 염소화 폴리에틸렌을 제공한다. The present disclosure also provides chlorinated polyethylene made from the polyethylene.
또한 본 기재는 상기 염소화 폴리에틸렌 및 염화비닐 중합체(PVC)를 포함하여 이루어진 PVC 조성물을 제공한다.The present disclosure also provides a PVC composition comprising the chlorinated polyethylene and vinyl chloride polymer (PVC).
상기에서 살펴본 바와 같이, 본 기재에 따르면 염소화(chlorination) 시 폴리에틸렌 내의 염소 분포 균일성이 우수해지는 저입도 폴리에틸렌; PVC와의 상용성 및 충격보강 성능이 뛰어나고 가소화 시간(Fusion Time)을 크게 단축시키는 염소화 폴리에틸렌; 및 충격강도, 가공성 및 생산성이 뛰어난 PVC 조성물을 제공하는 효과가 있다. As described above, according to the present disclosure, a low particle size polyethylene having excellent uniformity of chlorine distribution in polyethylene during chlorination; Chlorinated polyethylene having excellent compatibility with PVC and impact reinforcing performance and greatly shortening the Fusion Time; And it is effective to provide a PVC composition excellent in impact strength, processability and productivity.
이하, 본 기재의 폴리에틸렌, 이의 염소화 폴리에틸렌 및 이를 포함하는 PVC 조성물에 대하여 상세하게 설명한다. Hereinafter, the polyethylene of the present disclosure, chlorinated polyethylene thereof, and a PVC composition including the same will be described in detail.
본 기재의 폴리에틸렌은 평균입도가 30 내지 150 ㎛이고, 용융지수(5.0㎏)가 0.01 내지 100이며, 중량평균분자량이 10,000 내지 1,000,000 g/mol이고, 분자량분포도(MWD)가 3 내지 20이며, 용융온도가 125 내지 140 ℃이고, 밀도가 0.94 g/㎤ 이상으로, 염소화 폴리에틸렌의 제조에 사용되는 것을 특징으로 한다.The polyethylene of the present disclosure has an average particle size of 30 to 150 μm, a melt index (5.0 kg) of 0.01 to 100, a weight average molecular weight of 10,000 to 1,000,000 g / mol, a molecular weight distribution (MWD) of 3 to 20, and melting The temperature is 125 to 140 ° C. and the density is 0.94 g / cm 3 or more, and is used for the production of chlorinated polyethylene.
본 기재의 폴리에틸렌은 일례로 150 ㎛ 이하의 저입도 폴리에틸렌의 함량이 20 내지 100 중량%, 50 내지 90 중량%, 혹은 60 내지 90 중량%이고, 이 범위 내에서 염소화 시 폴리에틸렌 내의 염소 분포 균일성이 우수해지고, PVC에 충격보강제로 적용 시 충격보강 성능, 가소화 속도 및 생산성이 크게 향상되는 효과가 있다.The polyethylene of the present disclosure has, for example, 20 to 100% by weight, 50 to 90% by weight, or 60 to 90% by weight of low particle size polyethylene having a particle size of 150 μm or less. It is excellent, and when applied as an impact modifier in PVC, the impact reinforcing performance, plasticization rate and productivity is greatly improved.
본 기재의 폴리에틸렌은 평균입도가 또 다른 예로 50 내지 150 ㎛, 70 내지 150 ㎛, 90 내지 130 ㎛, 혹은 50 내지 130 ㎛이고, 이 범위 내에서 염소화 시 폴리에틸렌 내의 염소 분포 균일성이 우수해지고, PVC에 충격보강제로 적용 시 충격보강 성능, 가소화 속도 및 생산성이 크게 향상되는 효과가 있다.As another example, the polyethylene of the present disclosure has an average particle size of 50 to 150 μm, 70 to 150 μm, 90 to 130 μm, or 50 to 130 μm, and has excellent chlorine distribution uniformity in polyethylene when chlorinated within this range, When applied as an impact modifier, the impact reinforcement performance, plasticization speed and productivity are greatly improved.
본 기재의 폴리에틸렌은 용융지수(5.0㎏)가 또 다른 예로 0.1 내지 10, 0.1 내지 3.0, 혹은 0.1 내지 2.0이고, 이 범위 내에서 충격보강 효과가 우수하다.As another example, the polyethylene of the present disclosure has a melt index (5.0 kg) of 0.1 to 10, 0.1 to 3.0, or 0.1 to 2.0, and has excellent impact reinforcing effect within this range.
본 기재의 폴리에틸렌은 중량평균분자량이 또 다른 예로 50,000 내지 300,000 g/mol, 100,000 내지 250,000 g/mol, 혹은 150,000 내지 250,000 g/mol이다.The polyethylene of the present disclosure has a weight average molecular weight of another example of 50,000 to 300,000 g / mol, 100,000 to 250,000 g / mol, or 150,000 to 250,000 g / mol.
본 기재의 폴리에틸렌은 분자량분포도(MWD)가 또 다른 예로 3.5 내지 15, 혹은 4 내지 10이고, 이 범위 내에서 PVC에 충격보강제로 적용 시 가소화 속도 및 생산성이 크게 향상되는 효과가 있다.As another example, the polyethylene of the present disclosure has a molecular weight distribution (MWD) of 3.5 to 15, or 4 to 10, and has an effect of greatly improving plasticization rate and productivity when applied as an impact modifier to PVC within this range.
본 기재의 폴리에틸렌은 용융온도가 또 다른 예로 130 내지 140 ℃, 혹은 130 내지 136 ℃이다.As another example, the polyethylene of the present disclosure has a melting temperature of 130 to 140 ° C, or 130 to 136 ° C.
본 기재의 폴리에틸렌은 밀도가 또 다른 예로 0.94 내지 0.960 g/㎤이다. The polyethylene of the present disclosure has a density of 0.94 to 0.960 g / cm 3 as another example.
본 기재의 폴리에틸렌은 일례로 공단량체가 포함되지 않은 공단량체 프리 폴리에틸렌일 수 있다.The polyethylene of the present disclosure may be, for example, a comonomer free polyethylene that does not contain a comonomer.
상기 염소화 폴리에틸렌의 제조는 일례로 수상법 또는 산상법에 의한 것일 수 있고, 이 경우 CPE 염화 시간, 및 중화, 수세 등 후처리 시간이 크게 단축되는 효과가 있다.The chlorinated polyethylene may be produced by, for example, an aqueous phase method or an acid phase method. In this case, the CPE chloride time and the post-treatment time such as neutralization and water washing are greatly shortened.
본 기재의 폴리에틸렌은 일례로 연속 교반형 반응기(CSTR)에서 에틸렌 단량체를 분자량 조절제 하에서 촉매와 반응시켜 제조할 수 있다.The polyethylene of the present disclosure may be prepared, for example, by reacting an ethylene monomer with a catalyst under a molecular weight modifier in a continuous stirred reactor (CSTR).
상기 분자량 조절제는 일례로 수소일 수 있다.The molecular weight modifier may be hydrogen, for example.
상기 촉매는 일례로 지글러-나타 촉매, 혹은 용매에 희석된 지글러-나타 촉매일 수 있다.The catalyst may be, for example, a Ziegler-Natta catalyst or a Ziegler-Natta catalyst diluted in a solvent.
상기 지글러-나타 촉매는 일례로 평균입도가 3 내지 10 ㎛, 혹은 5 내지 8 ㎛이고, 이 범위 내에서 저입도 및 일정한 분자량분포도(MWD)의 폴리에틸렌을 효과적으로 얻을 수 있다.For example, the Ziegler-Natta catalyst has an average particle size of 3 to 10 μm, or 5 to 8 μm, and can effectively obtain polyethylene having a low particle size and a constant molecular weight distribution (MWD) within this range.
본 기재의 염소화 폴리에틸렌은 본 기재의 폴리에틸렌으로부터 제조됨을 특징으로 한다.The chlorinated polyethylene of the present disclosure is characterized in that it is made from the polyethylene of the present disclosure.
상기 염소화는 일례로 수상법 또는 산상법에 의하여 실시될 수 있고, 이 경우 염소화 폴리에틸렌 내의 염소 분포가 균일하여 제조되는 CPE의 유연성(elastic)을 향상시키는 효과가 있다.The chlorination may be carried out by an aqueous phase method or an acid phase method, for example, in this case, there is an effect of improving the elasticity (elastic) of the CPE produced by uniform chlorine distribution in the chlorinated polyethylene.
상기 수상법은 일례로 물(water)과 함께 유화제 및 분산제를 사용하여 염소화시키는 방법이고, 상기 산상법은 일례로 염산(HCl) 수용액 등과 같은 산 수용액을 유화제 및 분산제를 사용하여 염소화시키는 방법이다.The aqueous phase method is, for example, a method of chlorination using an emulsifier and a dispersant together with water, and the acidic method is, for example, a method of chlorination of an acid aqueous solution such as an aqueous hydrochloric acid (HCl) solution using an emulsifier and a dispersant.
상기 염소화 폴리에틸렌은 일례로 염소 함량이 20 내지 45 중량%, 31 내지 40 중량%, 혹은 33 내지 38 중량%일 수 있다.The chlorinated polyethylene may for example have a chlorine content of 20 to 45% by weight, 31 to 40% by weight, or 33 to 38% by weight.
상기 염소화 폴리에틸렌은 일례로 랜덤 염소화 폴리에틸렌일 수 있다.The chlorinated polyethylene may be, for example, random chlorinated polyethylene.
상기 염소화 폴리에틸렌은 일례로 체적저항이 1013 내지 1017 Ω㎝, 1014 내지 1017 Ω㎝, 또는 1015 내지 1016 Ω㎝이고, 이 범위 내에서 전선 용도로 사용될 때 절연 효과가 우수하다.The chlorinated polyethylene, for example, has a volume resistance of 10 13 to 10 17 Ωcm, 10 14 to 10 17 Ωcm, or 10 15 to 10 16 Ωcm, and is excellent in insulation effect when used for electric wires within this range.
상기 염소화 폴리에틸렌은 일례로 열안정성이 160 내지 180 ℃, 또는 170 내지 175 ℃이고, 이 범위 내에서 가교 반응에 사용될 때 분해가 잘 되지 않는 효과가 있다The chlorinated polyethylene, for example, has a thermal stability of 160 to 180 ℃, or 170 to 175 ℃, when used in the cross-linking reaction within this range there is an effect that the decomposition is not good.
상기 염소화 폴리에틸렌은 일례로 MDR 가교토크가 1.0 내지 3.0 Nm, 또는 1.5 내지 2.5 Nm이고, 이 범위 내에서 가교밀도 및 인장강도가 우수한 효과가 있다For example, the chlorinated polyethylene has an MDR crosslinking torque of 1.0 to 3.0 Nm, or 1.5 to 2.5 Nm, and has excellent crosslinking density and tensile strength within this range.
본 기재의 염소화 폴리에틸렌은 일례로 폴리에틸렌을 물, 유화제 및 분산제에 의해 분산시킨 후, 촉매와 클로린(chlorine)을 투입하여 반응시키는 것에 의해 제조할 수 있다.The chlorinated polyethylene of the present disclosure can be produced by, for example, dispersing polyethylene with water, an emulsifier and a dispersant, and then reacting with a catalyst and chlorine.
상기 유화제는 일례로 폴리이써(polyether) 혹은 폴리알킬렌 옥사이드(polyalkylene oxide)이다.The emulsifier is for example polyether or polyalkylene oxide.
상기 분산제는 일례로 중합체 염 혹은 유기산 중합체 염이다.The dispersant is for example a polymer salt or an organic acid polymer salt.
상기 유기산은 일례로 메타크릴산, 아크릴산 등일 수 있다.The organic acid may be, for example, methacrylic acid, acrylic acid, or the like.
상기 촉매는 일례로 염소화 촉매이고, 또 다른 예로 과산화물, 혹은 유기 과산화물이다.The catalyst is, for example, a chlorination catalyst, and in another example, a peroxide or an organic peroxide.
상기 클로린은 일례로 단독 또는 비활성 가스와 혼합하여 사용할 수 있다.The chlorine may be used alone or in combination with an inert gas, for example.
상기 최종 염소화 반응온도는 일례로 60 내지 150 ℃, 70 내지 145 ℃, 90 내지 140 ℃, 혹은 130 내지 137 ℃이다.The final chlorination reaction temperature is for example 60 to 150 ℃, 70 to 145 ℃, 90 to 140 ℃, or 130 to 137 ℃.
상기 염소화 반응시간은 일례로 10 분 내지 10 시간, 1 내지 6 시간, 혹은 2 내지 4 시간이다.The chlorination reaction time is, for example, 10 minutes to 10 hours, 1 to 6 hours, or 2 to 4 hours.
본 기재의 염소화 폴리에틸렌은 또 다른 일례로 폴리에틸렌 100 중량부, 유화제 0.01 내지 1.0 중량부 혹은 0.05 내지 0.5 중량부 및 분산제 0.1 내지 10 중량부 혹은 0.5 내지 5.0 중량부를 물에 분산시킨 후, 촉매 0.01 내지 1.0 중량부 혹은 0.05 내지 0.5 중량부와 클로린 80 내지 200 중량부 혹은 100 내지 150 중량부를 투입하여 반응시키는 것에 의해 제조할 수 있다.As another example, the chlorinated polyethylene of the present disclosure may be dispersed in water by 100 parts by weight of polyethylene, 0.01 to 1.0 parts by weight or 0.05 to 0.5 parts by weight of an emulsifier, and 0.1 to 10 parts by weight or 0.5 to 5.0 parts by weight of a dispersant, and then 0.01 to 1.0 catalyst. It can manufacture by making it react by adding a weight part or 0.05-0.5 weight part and 80-200 weight part or 100-150 weight part of chlorine.
상기 반응 또는 염소화 공정으로 제조된 염소화 폴리에틸렌은 일례로 중화공정(neutralization), 세정공정(washing) 및 건조공정(drying)을 더 거쳐 분말상의 염소화 폴리에틸렌으로 수득할 수 있다.The chlorinated polyethylene prepared by the above reaction or chlorination process may be obtained as a powdered chlorinated polyethylene through further neutralization, washing and drying.
상기 중화공정은 일례로 염소화 공정을 거친 반응물을 염기 용액으로 70 내지 90 ℃ 혹은 75 내지 80 ℃에서 4 내지 8 시간 동안 중화하는 공정일 수 있다.The neutralization process may be, for example, a process of neutralizing a reactant that has undergone a chlorination process with a base solution at 70 to 90 ° C. or 75 to 80 ° C. for 4 to 8 hours.
본 기재의 PVC 조성물은 본 기재의 염소화 폴리에틸렌 및 염화비닐 중합체(PVC)를 포함하여 이루어진 것을 특징으로 한다.The PVC composition of the present disclosure is characterized by comprising the chlorinated polyethylene and vinyl chloride polymer (PVC) of the present disclosure.
상기 PVC 조성물은 일례로 본 기재의 염소화 폴리에틸렌 1 내지 40 중량% 및 염화비닐 중합체(PVC) 60 내지 99 중량%를 포함하여 이루어질 수 있다.The PVC composition may include, for example, 1 to 40% by weight of chlorinated polyethylene and 60 to 99% by weight of vinyl chloride polymer (PVC).
상기 염소화 폴리에틸렌은 일례로 1 내지 15 중량%, 혹은 5 내지 10 중량%일 수 있다.The chlorinated polyethylene may be, for example, 1 to 15% by weight, or 5 to 10% by weight.
상기 염화비닐 중합체(PVC)는 일례로 85 내지 99 중량%, 혹은 90 내지 95 중량%일 수 있다.The vinyl chloride polymer (PVC) may be, for example, 85 to 99% by weight, or 90 to 95% by weight.
또 다른 일례로, 본 기재의 PVC 조성물은 본 기재의 염소화 폴리에틸렌 1 내지 20 중량%, 염화비닐 중합체(PVC) 70 내지 90 중량%, TiO2 1 내지 10 중량%, CaCO3 1 내지 10 중량% 및 복합 스테아레이트(Ca, Zn-stearate) 1 내지 10 중량%를 포함하여 이루어질 수 있다.In another example, the PVC composition of the present disclosure may comprise 1 to 20% by weight of chlorinated polyethylene, 70 to 90% by weight of vinyl chloride polymer (PVC), 1 to 10% by weight of TiO 2, 1 to 10% by weight of CaCO 3 , and It may comprise 1 to 10% by weight of composite stearate (Ca, Zn-stearate).
상기 PVC 조성물은 일례로 가소화 시간이 170 초 이하, 150 초 이하, 또는 150 내지 100 초이고, Izod 충격강도는 100 ㎏·㎝/㎝ 이상, 125 ㎏·㎝/㎝ 이상, 또는 125 내지 145 ㎏·㎝/㎝일 수 있고, 이 범위 내에서 물성 밸런스 및 생산성이 우수한 효과가 있다.The PVC composition has, for example, a plasticization time of 170 seconds or less, 150 seconds or less, or 150 to 100 seconds, and an Izod impact strength of 100 kg · cm / cm or more, 125 kg · cm / cm or more, or 125 to 145 kg. * Cm / cm, there is an effect excellent in the physical properties balance and productivity within this range.
이하, 본 기재의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 기재를 예시하는 것일 뿐 본 기재의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are provided to help the understanding of the present disclosure, but the following examples are merely exemplified by the present disclosure, and it is obvious to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present disclosure. It is natural that such variations and modifications fall within the scope of the appended claims.
[실시예]EXAMPLE
실시예 1Example 1
<고밀도 폴리에틸렌><High density polyethylene>
평균입도 5.5 ㎛의 지글러-나타 촉매로 제조된 고밀도 폴리에틸렌(CE6040X, LG화학 제조)을 사용하였다. 이 고밀도 폴리에틸렌은 분말형태이고, 평균밀도, MI, MWD, 용융온도 및 밀도 등은 하기 표 1에 기재하였다.High-density polyethylene (CE6040X, manufactured by LG Chemical) manufactured with a Ziegler-Natta catalyst having an average particle size of 5.5 μm was used. This high density polyethylene is in powder form, and the average density, MI, MWD, melting temperature and density are shown in Table 1 below.
<염소화 폴리에틸렌의 제조>Production of Chlorinated Polyethylene
반응기에 물 5,000 L와 상기 고밀도 폴리에틸렌 550 kg을 투입한 다음, 분산제로 소듐 폴리메타크릴레이트(sodium polymethacrylate), 유화제로 옥시프로필렌 및 옥시에틸렌 코폴리이써(oxypropylene and oxyethylene copolyether), 촉매로 벤조일 퍼옥사이드(benzoyl peroxide)를 넣고, 최종온도 132 ℃로, 3 시간 동안 기체상의 클로린을 주입하여 염소화하였다. 5,000 L of water and 550 kg of the dense polyethylene were charged into the reactor, followed by sodium polymethacrylate as a dispersant, oxypropylene and oxyethylene copolyether as an emulsifier, and benzoyl peroxide as a catalyst. (benzoyl peroxide) was added and chlorinated by injecting gaseous chlorine for 3 hours at a final temperature of 132 ° C.
상기 염소화된 반응물을 NaOH 또는 Na2CO3을 투입하여 4 시간 동안 중화하고, 이를 다시 흐르는 물에 의해 4 시간 동안 세정한 다음, 마지막으로 120 ℃에서 건조하여 분말형태의 염소화 폴리에틸렌을 제조하였다.The chlorinated reactant was neutralized with NaOH or Na 2 CO 3 for 4 hours, washed again with running water for 4 hours, and finally dried at 120 ° C. to prepare chlorinated polyethylene in powder form.
<PVC 조성물의 제조><Production of PVC Composition>
상기 염소화 폴리에틸렌 6.5 중량%, 염화비닐 중합체(PVC) 81.6 중량%, TiO2 3.2 중량%, CaCO3 4.1 중량% 및 복합 스테아레이트(Ca, Zn) 4.5 중량%를 배합한 다음 가공하여 PVC 조성물 시편을 제조하였다.6.5% by weight of the chlorinated polyethylene, 81.6% by weight of vinyl chloride polymer (PVC), 3.2% by weight of TiO 2 , 4.1% by weight of CaCO 3 and 4.5% by weight of composite stearate (Ca, Zn) and then processed to prepare a PVC composition specimen Prepared.
실시예 2Example 2
상기 실시예 1에서 고밀도 폴리에틸렌으로 평균입도 3.5 ㎛의 지글러-나타 촉매를 사용하여 제조된 HDPE를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 염소화 폴리에틸렌 및 PVC 조성물 시편을 제조하였다.A chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that HDPE prepared using a Ziegler-Natta catalyst having an average particle size of 3.5 μm was used as the high density polyethylene in Example 1.
실시예 3Example 3
상기 실시예 1에서 고밀도 폴리에틸렌으로 평균입도 8.5 ㎛의 지글러-나타 촉매를 사용하여 제조된 LG화학 CE6040K를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 염소화 폴리에틸렌 및 PVC 조성물 시편을 제조하였다.A chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chemical CE6040K prepared using Ziegler-Natta catalyst having an average particle size of 8.5 μm as a high density polyethylene was used in Example 1.
비교예 1Comparative Example 1
상기 실시예 1에서 고밀도 폴리에틸렌으로 평균입도 12 ㎛의 지글러-나타 촉매를 사용하여 제조된 LG화학 CE6040을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 염소화 폴리에틸렌 및 PVC 조성물 시편을 제조하였다. 비교예 1 내지 6에서 사용된 고밀도 폴리에틸렌은 분말형태이고, 평균밀도, MI, MWD, 용융온도 및 밀도 등은 하기 표 2에 기재하였다.A chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chemical CE6040 prepared using Ziegler-Natta catalyst having an average particle size of 12 μm as the high density polyethylene was used in Example 1. The high density polyethylene used in Comparative Examples 1 to 6 is in the form of a powder, and the average density, MI, MWD, melting temperature and density are shown in Table 2 below.
비교예 2Comparative Example 2
상기 실시예 1에서 고밀도 폴리에틸렌으로 시중에 판매되는 평균입도 220 ㎛의 HDPE를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 염소화 폴리에틸렌 및 PVC 조성물 시편을 제조하였다.A chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that HDPE having an average particle size of 220 μm was commercially available as high density polyethylene in Example 1.
비교예 3Comparative Example 3
상기 실시예 1에서 고밀도 폴리에틸렌으로 평균입도 12 ㎛의 지글러-나타 촉매를 사용하여 제조된 LG화학 CE2080을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 염소화 폴리에틸렌 및 PVC 조성물 시편을 제조하였다.A chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chem CE2080, which was prepared using Ziegler-Natta catalyst having an average particle size of 12 μm as the high density polyethylene, was used in Example 1.
비교예 4Comparative Example 4
상기 실시예 1에서 고밀도 폴리에틸렌으로 평균입도 10 ㎛의 메탈로센 촉매를 사용하여 제조된 LG화학 CE2080M을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 염소화 폴리에틸렌 및 PVC 조성물 시편을 제조하였다.A chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chem CE2080M prepared using a metallocene catalyst having an average particle size of 10 μm as a high density polyethylene was used in Example 1.
비교예 5Comparative Example 5
상기 실시예 1에서 고밀도 폴리에틸렌으로 평균입도 12 ㎛의 지글러-나타 촉매를 사용하여 제조된 LG화학 CE2080T1을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 염소화 폴리에틸렌 및 PVC 조성물 시편을 제조하였다.A chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chemical CE2080T1 prepared using a Ziegler-Natta catalyst having an average particle size of 12 μm was used as the high density polyethylene in Example 1.
비교예 6Comparative Example 6
상기 실시예 1에서 고밀도 폴리에틸렌으로 평균입도 8.5 ㎛의 지글러-나타 촉매를 사용하여 제조된 LG화학 CE2030K를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 염소화 폴리에틸렌 및 PVC 조성물 시편을 제조하였다.A chlorinated polyethylene and PVC composition specimens were prepared in the same manner as in Example 1, except that LG Chem CE2030K prepared using Ziegler-Natta catalyst having an average particle size of 8.5 μm as a high density polyethylene was used in Example 1.
[시험예][Test Example]
상기 실시예 1 내지 4 및 비교예 1 내지 6에서 제조된 염소화 폴리에틸렌(CPE) 및 PVC 조성물 시편의 특성을 하기의 방법으로 측정하였고, 그 결과를 하기 표 1, 2에 나타내었다.The properties of the chlorinated polyethylene (CPE) and PVC composition specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were measured by the following method, and the results are shown in Tables 1 and 2 below.
* 용융지수(dg/min): ASTM D-1238에 의거하여 190 ℃, 5 ㎏의 조건으로 측정하였다.* Melt index (dg / min): measured at 190 ° C. and 5 kg in accordance with ASTM D-1238.
* 중량평균분자량(g/mol): 겔 투과 크로마토그래피로 측정하였다. 사용한 측정기기는 Agilent(Polymer Laboratories)의 PL-GPC 220이다. 시료는 TCB(Trichlorobenzene)에 0.2 중량%의 HDPE와 125 ppm의 BHT를 첨가한 뒤 165 ℃에서 2 시간 동안 녹인 후, 이 시료를 Agilent(Polymer Laboratories) 사에서 제조된 Mixed-B Column 3 개와 Mixed-B Guard Column 1 개에 통과시켜 분석하였다.Weight average molecular weight (g / mol): Measured by gel permeation chromatography. The measuring instrument used was PL-GPC 220 from Agilent (Polymer Laboratories). The sample was dissolved in TCB (Trichlorobenzene) by adding 0.2% by weight of HDPE and 125 ppm of BHT and then dissolved at 165 ° C. for 2 hours.The samples were then mixed with three Mixed-B Columns manufactured by Agilent (Polymer Laboratories). Analyzed by passing through one B Guard Column.
* 분자량분포도: 겔 투과 크로마토그래피에 의해 측정된 수평균분자량(Mn)과 중량평균분자량(Mw)의 비(Mw/Mn)로 측정하였다.* Molecular weight distribution: Measured by the ratio (Mw / Mn) of the number average molecular weight (Mn) and the weight average molecular weight (Mw) measured by gel permeation chromatography.
* 용융온도: DSC를 이용하여 10 ℃/min의 승온 속도로 측정하였다.Melting temperature: measured at a rate of temperature increase of 10 ° C./min using DSC.
* 저입도 함량(150 ㎛ 이하): 150 ㎛ 메쉬의 체를 이용하여 중량%로 계산하였다.Low particle size content (150 μm or less): Calculated in weight percent using a sieve of 150 μm mesh.
* 평균입도: 입도분석기 Taylor 방식의 Auto shaker에 총 9개의 Sieve를 장착(63~850 ㎛)하여 시료의 총 중량의 50 %에 해당하는 입도의 값을 계산하였다.* Average particle size: A particle size analyzer corresponding to 50% of the total weight of the sample was calculated by mounting a total of nine Sieves (63 ~ 850 ㎛) in Taylor type auto shaker.
* 밀도: ASTM D-792에 의거하여 측정하였다.Density: measured according to ASTM D-792.
* 클로린 함량: Automatic Quick Furnace을 이용하여 시료를 1000 ℃에서 태워 가스를 H2O에 포집하고 IC(Ion Chromatograph) 기기로 Cl 함량분석을 하였다.* Chlorine content: The sample was burned at 1000 ℃ using Automatic Quick Furnace to collect the gas in H 2 O and Cl content analysis by IC (Ion Chromatograph) device.
* 가소화 시간: PVC와 염소화 폴리에틸렌이 배합될 때 PVC가 용융되어, 가소화가 안정화되는 시간으로 측정하였다. Thermo Haake를 사용하여 온도 170 ℃, Screw speed 60 rpm, 수지 충진량(PVC 조성물) 63 g 조건으로 측정하였다. 상기 PVC 조성물은 PVC 100 중량부, 염소화 폴리에틸렌 8 중량부, TiO2 4 중량부, CaCO3 5.5 중량부 및 복합 스테아레이트(Ca, Zn) 5.5 중량부로 이루어졌다.* Plasticization time: Measured by the time when the PVC is melted and the plasticization is stabilized when the PVC and the chlorinated polyethylene are combined. Thermo Haake was used under conditions of temperature 170 ° C., Screw speed 60 rpm, and resin filling amount (PVC composition) 63 g. The PVC composition was composed of 100 parts by weight of PVC, 8 parts by weight of chlorinated polyethylene, 4 parts by weight of TiO 2 , 5.5 parts by weight of CaCO 3 and 5.5 parts by weight of composite stearate (Ca, Zn).
* Izod 충격강도(1/4" notched at 0 ℃, ㎏·㎝/㎝): ASTM D256에 의거하여 측정하였다.Izod impact strength (1/4 "notched at 0 ° C., kg · cm / cm): measured in accordance with ASTM D256.
* 체적저항: ASTM D257 방법에 의거하여 측정면적 19.625 cm3 및 시편두께 0.2 cm를 가진 CPE 시트의 체적저항을 측정하여다.* Volume resistivity: Measure the volume resistivity of CPE sheet with measuring area 19.625 cm 3 and specimen thickness 0.2 cm according to ASTM D257 method.
* 열안정성: 시험관에 염소화 폴리에틸렌 원료를 넣고 오일 bath의 온도를 분당 10 ℃로 상승시킬 때 HCl에 분해되는 시점을 측정하였다.* Thermal Stability: When the chlorinated polyethylene raw material was added to the test tube and the temperature of the oil bath was raised to 10 ° C. per minute, the point of decomposition of HCl was measured.
* 가교밀도: 염소화 폴리에틸렌에 탈크 및 탄산칼슘과 함께 가교제, 가교 보조제, 활제 및 가교제를 130 ℃에서 2분 동안 Roll-mill 혼합하여 150 ℃에서 2분 동안 프레스 성형하여 시트를 제조하였고, ASTM D-2080에 의거하여 165 ℃에서 Scorch Time 및 경화 속도 등을 측정하였다.* Cross-link density: The cross-linking agent, cross-linking aid, lubricant and cross-linking agent together with talc and calcium carbonate in chlorinated polyethylene were roll-milled at 130 ° C. for 2 minutes and press-molded at 150 ° C. for 2 minutes to prepare a sheet. ASTM D- Based on 2080, the Scorch Time and the curing rate were measured at 165 ° C.
표 1
구분 실시예 1 실시예 2 실시예 3
PE 저입도 함량 75 85 53
평균입도 120 95 145
MI(5kg) 0.9 0.8 0.45
Mw 175,000 185,000 200,000
MWD 5.5 5.5 5
용융온도 133 133 133
밀도 0.952 0.953 0.952
CPE 클로린 함량 36 36 36
체적저항(*1014) 170 240 130
열안정성 172 174 175
가교토크 2.0 2.1 2.3
PVC 가소화 시간 140 130 150
Izod 충격강도 125 130 145
Table 1
division Example 1 Example 2 Example 3
PE Low particle content 75 85 53
Average particle size 120 95 145
MI (5 kg) 0.9 0.8 0.45
Mw 175,000 185,000 200,000
MWD 5.5 5.5 5
Melting temperature 133 133 133
density 0.952 0.953 0.952
CPE Chlorine Content 36 36 36
Volume resistivity (* 10 14 ) 170 240 130
Thermal stability 172 174 175
Bridging torque 2.0 2.1 2.3
PVC Plasticization time 140 130 150
Izod impact strength 125 130 145
표 2
구분 비교예1 비교예2 비교예3 비교예4 비교예5 비교예6
PE 저입도 함량 30 20 23 25 25 53
평균입도 180 220 200 200 200 145
MI(5kg) 0.45 0.5 1.3 3 0.35 1.7
Mw 200,000 205,000 180,000 140,000 270,000 160,000
MWD 5 5 12 2.8 13.5 24
용융온도 133 133 132 132 133 131
밀도 0.952 0.952 0.957 0.954 0.956 0.957
CPE 클로린 함량 36 36 36 36 36 36
체적저항(*1014) 83 62 5.2 90 13 1.2
열안정성 171 170 164 173 166 158
가교토크 1.8 1.7 1.4 1.6 1.7 1.2
PVC 가소화 시간 180 190 90 180 150 70
Izod충격강도 145 140 86 130 95 73
TABLE 2
division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6
PE Low particle content 30 20 23 25 25 53
Average particle size 180 220 200 200 200 145
MI (5 kg) 0.45 0.5 1.3 3 0.35 1.7
Mw 200,000 205,000 180,000 140,000 270,000 160,000
MWD 5 5 12 2.8 13.5 24
Melting temperature 133 133 132 132 133 131
density 0.952 0.952 0.957 0.954 0.956 0.957
CPE Chlorine Content 36 36 36 36 36 36
Volume resistivity (* 10 14 ) 83 62 5.2 90 13 1.2
Thermal stability 171 170 164 173 166 158
Bridging torque 1.8 1.7 1.4 1.6 1.7 1.2
PVC Plasticization time 180 190 90 180 150 70
Izod impact strength 145 140 86 130 95 73
상기 표 1, 2에 나타낸 바와 같이, 본 기재에 따른 염소화 폴리에틸렌을 포함하는 PVC 조성물(실시예 1 내지 3)은, 평균입도가 180 또는 220 ㎛인 폴리에틸렌으로부터 제조된 염소화 폴리에틸렌을 포함하는 PVC 조성물(비교예 1 내지 5)와 비교하여, 가소화 시간이 크게 단축되고(생산성 향상), 동시에 Izod 충격강도도 우수함을 확인할 수 있었다.As shown in Tables 1 and 2, the PVC composition comprising chlorinated polyethylene according to the present invention (Examples 1 to 3) is a PVC composition comprising chlorinated polyethylene prepared from polyethylene having an average particle size of 180 or 220 µm ( Compared with Comparative Examples 1 to 5), it was confirmed that the plasticization time was greatly shortened (productivity improved) and the Izod impact strength was also excellent.
상기 비교예 6의 경우 사용된 폴리에틸렌의 평균입도는 145 ㎛이나 MWD가 24로 본 기재에 따른 폴리에틸렌의 MWD의 범위와 크게 상이하여, Izod 충격강도가 크게 열악함을 확인할 수 있었다.In Comparative Example 6, the average particle size of polyethylene used was 145 μm but MWD was 24, which is significantly different from the range of MWD of polyethylene according to the present disclosure, and it was confirmed that Izod impact strength was significantly poor.

Claims (18)

  1. 평균입도가 30 내지 150 ㎛이고, 용융지수(5.0㎏)가 0.01 내지 100이며, 중량평균분자량이 10,000 내지 1,000,000이고, 분자량분포도(MWD)가 3 내지 20이며, 용융온도가 125 내지 140 ℃이고, 밀도가 0.94 g/㎤ 이상으로, 염소화 폴리에틸렌의 제조에 사용되는 것을 특징으로 하는The average particle size is 30 to 150 ㎛, the melt index (5.0 kg) is 0.01 to 100, the weight average molecular weight is 10,000 to 1,000,000, the molecular weight distribution (MWD) is 3 to 20, the melting temperature is 125 to 140 ℃, Characterized by being used for the production of chlorinated polyethylene with a density of at least 0.94 g / cm 3
    폴리에틸렌.Polyethylene.
  2. 제 1항에 있어서,The method of claim 1,
    상기 폴리에틸렌은, 150 ㎛ 이하의 저입도 함량이 20 내지 100 중량%인 것을 특징으로 하는The polyethylene has a low particle size content of less than 150 ㎛ 20 to 100% by weight, characterized in that
    폴리에틸렌.Polyethylene.
  3. 제 1항에 있어서,The method of claim 1,
    상기 평균입도는, 50 내지 130 ㎛인 것을 특징으로 하는The average particle size is characterized in that 50 to 130 ㎛
    폴리에틸렌.Polyethylene.
  4. 제 1항에 있어서, The method of claim 1,
    상기 용융지수(5.0㎏)는, 0.1 내지 10인 것을 특징으로 하는The melt index (5.0 kg), characterized in that 0.1 to 10
    폴리에틸렌.Polyethylene.
  5. 제 1항에 있어서,The method of claim 1,
    상기 중량평균분자량은, 50,000 내지 300,000 g/mol인 것을 특징으로 하는The weight average molecular weight is 50,000 to 300,000 g / mol, characterized in that
    폴리에틸렌.Polyethylene.
  6. 제 1항에 있어서,The method of claim 1,
    상기 분자량분포도(MWD)는, 3.5 내지 15인 것을 특징으로 하는The molecular weight distribution (MWD) is characterized in that 3.5 to 15
    폴리에틸렌.Polyethylene.
  7. 제 1항에 있어서,The method of claim 1,
    상기 용융온도는, 130 내지 140 ℃인 것을 특징으로 하는The melting temperature is characterized in that 130 to 140 ℃
    폴리에틸렌.Polyethylene.
  8. 제 1항에 있어서,The method of claim 1,
    상기 밀도는, 0.94 내지 0.96 g/㎤인 것을 특징으로 하는The density is characterized in that from 0.94 to 0.96 g / cm 3
    폴리에틸렌.Polyethylene.
  9. 제 1항에 있어서,The method of claim 1,
    상기 염소화 폴리에틸렌의 제조는, 수상법 또는 산상법에 의하는 것을 특징으로 하는Production of the chlorinated polyethylene is characterized by the aqueous phase method or the acid phase method
    폴리에틸렌.Polyethylene.
  10. 제 1항에 있어서,The method of claim 1,
    상기 폴리에틸렌은, 지글러-나타 촉매로 제조됨을 특징으로 하는The polyethylene is characterized by being made of a Ziegler-Natta catalyst
    폴리에틸렌.Polyethylene.
  11. 제 1항 내지 제 10항 중 어느 한 항의 폴리에틸렌으로부터 제조됨을 특징으로 하는It is made from the polyethylene of any one of claims 1 to 10
    염소화 폴리에틸렌.Chlorinated polyethylene.
  12. 제 11항에 있어서,The method of claim 11,
    상기 염소화 폴리에틸렌은, 랜덤 염소화 폴리에틸렌인 것을 특징으로 하는The chlorinated polyethylene is random chlorinated polyethylene, characterized in that
    염소화 폴리에틸렌.Chlorinated polyethylene.
  13. 제 11항에 있어서,The method of claim 11,
    상기 염소화 폴리에틸렌은, 염소 함량이 20 내지 45 중량%인 것을 특징으로 하는The chlorinated polyethylene, characterized in that the chlorine content of 20 to 45% by weight
    염소화 폴리에틸렌.Chlorinated polyethylene.
  14. 제 11항에 있어서,The method of claim 11,
    상기 염소화 폴리에틸렌은, 체적저항이 1013 내지 1017 Ω㎝이고, 열안정성이 160 내지 180 ℃이며, 가교토크가 1.0 내지 3.0 Nm인 것을 특징으로 하는The chlorinated polyethylene has a volume resistance of 10 13 to 10 17 Ωcm, thermal stability of 160 to 180 ° C, and crosslinking torque of 1.0 to 3.0 Nm.
    염소화 폴리에틸렌.Chlorinated polyethylene.
  15. 제 11항의 염소화 폴리에틸렌 및 염화비닐 중합체(PVC)를 포함하여 이루어진 것을 특징으로 하는It comprises a chlorinated polyethylene and vinyl chloride polymer (PVC) of claim 11
    PVC 조성물.PVC composition.
  16. 제 15항에 있어서,The method of claim 15,
    상기 PVC 조성물은, 가소화 시간이 170 초 이하인 것을 특징으로 하는The PVC composition is characterized in that the plasticization time is 170 seconds or less.
    염소화 폴리에틸렌.Chlorinated polyethylene.
  17. 제 1항 내지 제 9항 중 어느 한 항의 폴리에틸렌 100 중량부, 유화제 0.01 내지 1.0 중량부, 및 분산제 0.1 내지 10 중량부를 물에 분산시킨 후, 촉매 0.01 내지 1.0 중량부와 클로린 80 내지 200 중량부를 투입하여 반응시키는 것을 특징으로 하는10 to 100 parts by weight of polyethylene according to any one of claims 1 to 9, 0.01 to 1.0 parts by weight of an emulsifier, and 0.1 to 10 parts by weight of a dispersant are dispersed in water, and then 0.01 to 1.0 parts by weight of a catalyst and 80 to 200 parts by weight of chlorine. To react by
    염소화 폴리에틸렌의 제조방법.Method for producing chlorinated polyethylene.
  18. 제 17항에 있어서,The method of claim 17,
    상기 반응은, 최종온도가 60 내지 150 ℃인 것을 특징으로 하는The reaction is characterized in that the final temperature is 60 to 150 ℃
    염소화 폴리에틸렌의 제조방법.Method for producing chlorinated polyethylene.
PCT/KR2014/003375 2013-04-19 2014-04-17 Low-particle-size polyethylene, chlorinated polyethylene thereof, and pvc composition containing same WO2014171772A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108047358A (en) * 2017-12-07 2018-05-18 青海盐湖工业股份有限公司 A kind of polyvinyl chloride Joint Production system and its interlocking control method
US11613639B2 (en) * 2017-10-13 2023-03-28 Shin-Etsu Chemical Co., Ltd. Polyvinyl chloride-based resin molded product and method for manufacturing the same

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Publication number Priority date Publication date Assignee Title
JPS6031503A (en) * 1983-07-28 1985-02-18 Osaka Soda Co Ltd Production of chlorinated polyethylene rubber of good moldability
JPH06248015A (en) * 1993-02-24 1994-09-06 Showa Denko Kk Production of chlorinated polyethylene
JP2757210B2 (en) * 1989-07-17 1998-05-25 東ソー株式会社 Chlorinated polyethylene and method for producing the same
KR100929114B1 (en) * 2008-02-15 2009-11-30 삼성토탈 주식회사 Chlorinated Polyethylene Resin
KR20120073947A (en) * 2010-12-27 2012-07-05 호남석유화학 주식회사 Chlorinated polyethylene resin and molded article manufactured using composition having the resin

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JPS6031503A (en) * 1983-07-28 1985-02-18 Osaka Soda Co Ltd Production of chlorinated polyethylene rubber of good moldability
JP2757210B2 (en) * 1989-07-17 1998-05-25 東ソー株式会社 Chlorinated polyethylene and method for producing the same
JPH06248015A (en) * 1993-02-24 1994-09-06 Showa Denko Kk Production of chlorinated polyethylene
KR100929114B1 (en) * 2008-02-15 2009-11-30 삼성토탈 주식회사 Chlorinated Polyethylene Resin
KR20120073947A (en) * 2010-12-27 2012-07-05 호남석유화학 주식회사 Chlorinated polyethylene resin and molded article manufactured using composition having the resin

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11613639B2 (en) * 2017-10-13 2023-03-28 Shin-Etsu Chemical Co., Ltd. Polyvinyl chloride-based resin molded product and method for manufacturing the same
CN108047358A (en) * 2017-12-07 2018-05-18 青海盐湖工业股份有限公司 A kind of polyvinyl chloride Joint Production system and its interlocking control method
CN108047358B (en) * 2017-12-07 2020-09-15 青海盐湖工业股份有限公司 Polyvinyl chloride joint production system and interlocking control method thereof

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