WO2022105149A1 - Matériau de polyoléfine cyclique renforcé ayant une transparence élevée et une faible perte diélectrique, et son procédé de préparation - Google Patents

Matériau de polyoléfine cyclique renforcé ayant une transparence élevée et une faible perte diélectrique, et son procédé de préparation Download PDF

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Publication number
WO2022105149A1
WO2022105149A1 PCT/CN2021/092787 CN2021092787W WO2022105149A1 WO 2022105149 A1 WO2022105149 A1 WO 2022105149A1 CN 2021092787 W CN2021092787 W CN 2021092787W WO 2022105149 A1 WO2022105149 A1 WO 2022105149A1
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WO
WIPO (PCT)
Prior art keywords
styrene
cyclic polyolefin
toughened
dielectric loss
butadiene
Prior art date
Application number
PCT/CN2021/092787
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English (en)
Chinese (zh)
Inventor
赵汪洋
黄险波
叶南飚
杨霄云
王林
陆湛泉
姜向新
尹朝清
Original Assignee
金发科技股份有限公司
成都金发科技新材料有限公司
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Publication date
Application filed by 金发科技股份有限公司, 成都金发科技新材料有限公司 filed Critical 金发科技股份有限公司
Publication of WO2022105149A1 publication Critical patent/WO2022105149A1/fr

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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
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the field of polymer material modification, in particular to a toughened cyclic polyolefin material with high transparency and low dielectric loss and a preparation method thereof.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a toughened cyclic polyolefin material with high transparency and low dielectric loss.
  • the technical solution adopted in the present invention is: a high-transparency and low-dielectric loss toughened cyclic polyolefin material, comprising the following components by weight: 70-85 parts of COC resin, 10-20 parts of elastomer and 5-10 parts of a compatibilizer; the elastomer is a styrene-butadiene-styrene block copolymer (SBS elastomer), a styrene-ethylene-butadiene-styrene block copolymer ( SEBS elastomer) at least one.
  • SBS elastomer styrene-butadiene-styrene block copolymer
  • SEBS elastomer styrene-ethylene-butadiene-styrene block copolymer
  • the material involved in the invention mainly improves the impact strength on the basis of ensuring the low dielectric loss performance and high transparency of the cyclic polyolefin material.
  • the impact strength of the material is improved on the one hand, and the low dielectric constant, dielectric loss and high transparency of the cyclic polyolefin are maintained on the other hand.
  • the compatibility between the two is not good.
  • the present invention adopts a compatibilizer, which effectively improves the light transmittance and impact toughness of the material.
  • the mass percentage of PS is 28%-33%, and the styrene-ethylene-butadiene-styrene
  • the weight average molecular weight of the block copolymer is 50,000 to 80,000.
  • the styrene-butadiene-styrene block copolymer has a linear structure; in the styrene-butadiene-styrene block copolymer, when the mass percentage of PS is 10% -15%, the weight average molecular weight of the styrene-butadiene-styrene block copolymer is 70,000 to 80,000; when the styrene-butadiene-styrene block copolymer, when PS When the mass percentage of the styrene-butadiene-styrene block copolymer is 28%-33%, the molecular weight of the styrene-butadiene-styrene block copolymer is 110,000-120,000.
  • the light transmittance of the COC resin is greater than 90%; the light transmittance test standard is GB/T 2410-2008; the COC resin is an injection molding grade COC material; the COC resin is 260°C, 2.16Kg The melt flow rate under the condition is greater than 15g/10min.
  • the compatibilizer is at least one of maleic anhydride grafted polyethylene (PE-g-MAH) and maleic anhydride grafted cyclic polyolefin copolymer (COC-g-MAH); the In the compatibilizer, the graft ratio of maleic anhydride is 1% to 2%.
  • PE-g-MAH maleic anhydride grafted polyethylene
  • COC-g-MAH maleic anhydride grafted cyclic polyolefin copolymer
  • the high transparency and low dielectric loss toughened cyclic polyolefin material further comprises the following components by weight: 0.1-0.3 part of antioxidant and 0.1-0.2 part of lubricant.
  • the antioxidant is a hindered amine antioxidant
  • the lubricant is ethylene bis-stearic acid amide.
  • the present invention also provides the preparation method of the high-transparency low-dielectric loss toughened cyclic polyolefin material.
  • the method is as follows: mixing the components, adding them to the main feeding system of the extruder, and passing the extruder through the extruder. Mixing, extruding and granulating to obtain the high-transparency and low-dielectric-loss toughened cyclic polyolefin material.
  • the present invention also discloses the application of the high transparent and low dielectric loss toughened cyclic polyolefin material in the fields of communication, radar, aerospace, smart wear, imaging and global positioning.
  • the present invention is a thermoplastic resin, which can be processed by common injection molding process, with convenient molding and high production efficiency.
  • COC resin 1# the light transmittance of the COC resin is greater than 90%; the COC resin is an injection molding grade COC material; the melt flow rate of the COC resin at 260°C and 2.16Kg is greater than 15g/10min (manufacturer : Mitsui Chemicals APEL6015);
  • SBS Elastomer 1# The mass percentage of PS is 10%-15%, and the weight average molecular weight is 70,000-80,000 (Baling Petrochemical YH-796);
  • SBS Elastomer 2# The mass percentage of PS is 28%-33%, and the weight average molecular weight is 110,000-120,000; (Baling Petrochemical YH-791);
  • SBS Elastomer 3# The mass percentage of PS is 35%-40%, and the weight-average molecular weight is 140,000-150,000 (Baling Petrochemical YH-792);
  • SEBS Elastomer 1# The mass percentage of PS is 28-33%, and the weight average molecular weight is 50,000-80,000; (Kraton G1652);
  • SEBS Elastomer 2# The mass percentage of PS is 35-40%, and the weight average molecular weight is 90,000-100,000; (Kraton G1654);
  • POE elastomer Dow Chemical, POE ENGAGE 7467, the melt flow rate is about 2g/10min at 190°C, 2.16Kg;
  • COC-g-MAH maleic anhydride grafting rate of 1%; Kingfa Technology Co., Ltd.;
  • PE-g-MAH maleic anhydride grafting rate 1%; Coace W1H;
  • PP-g-MAH maleic anhydride grafting rate of 1%, Nanhai Baichen PC-1;
  • Antioxidants RIANOX 1010 and RIANOX 168;
  • Lubricant EBS lubricant, Guangzhou Jinyang Chemical B50;
  • Light transmittance refer to GB/T 2410-2008
  • the preparation method of the toughened cyclic polyolefin material with high transparency and low dielectric loss is as follows:
  • twin-screw extruder one to two
  • the temperature of zone is 200°C ⁇ 220°C
  • the temperature of zone three to five is 220°C ⁇ 240°C
  • the temperature of zone five to ten is 240°C ⁇ 260°C
  • the screw speed is 300rpm ⁇ 600rpm.
  • the application sets Examples 1 to 12 and Comparative Examples 1 to 3.
  • the content and performance data of each component in Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1; the content of each component in Examples 6 to 12, The performance data are shown in Table 2.
  • Comparing Examples 1 to 5 with Comparative Example 2 it can be seen that under the same other conditions, the elastomer in Comparative Example 2 is not styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene
  • the block copolymer of diene-styrene has lower light transmittance and notched impact strength than Examples 1-5, and higher dielectric loss than Examples 1-5.
  • Example 4 Comparing Example 4 with Example 5, it can be seen that the SEBS elastomer in Example 4 has a mass percentage content of PS of 33% and a weight-average molecular weight of 50,000 to 80,000; the SEBS elastomer in Example 5 is not in the above-mentioned range.
  • the transmittance and notched impact strength in Example 5 were lower than those in Example 4, and the dielectric loss was higher than that in Example 4.
  • Example 12 Comparing Examples 10, 11 and 12, it can be seen that the compatibilizer in Example 12 is not PE-g-MAH or COC-g-MAH, and the transmittance and notched impact strength of Example 12 are lower than those of Examples 10 ⁇ 11. The dielectric loss is higher than that of Examples 10-11.
  • Comparing Example 1 with Comparative Example 3 it can be seen that the content of elastomer in Comparative Example 3 is not within the scope of the present application, its transmittance is significantly lower than that of Example 1, and the dielectric loss is significantly higher than that of Example 1.

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

Abstract

Est divulgué un matériau de polyoléfine cyclique renforcé ayant une transparence élevée et une faible perte diélectrique, comprenant les composants suivants en parties en poids : 70 à 85 parties d'une résine COC, 10 à 20 parties d'un élastomère et 5 à 10 parties d'un agent de compatibilité, l'élastomère étant au moins l'un d'un copolymère séquencé de styrène-butadiène-styrène et d'un copolymère séquencé de styrène-éthylène-butadiène-styrène. Le matériau de polyoléfine cyclique a une propriété d'impact élevée et une propriété d'impact marquée de > 13 KJ/m2, pouvant satisfaire aux exigences d'impact de base et aux exigences de transmission de lumière des industries de communication, de l'électronique et des appareils ménagers. Est également divulgué un procédé de préparation du matériau de polyoléfine cyclique.
PCT/CN2021/092787 2020-11-23 2021-05-10 Matériau de polyoléfine cyclique renforcé ayant une transparence élevée et une faible perte diélectrique, et son procédé de préparation WO2022105149A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011325146.5A CN112457617B (zh) 2020-11-23 2020-11-23 一种高透明低介电损耗增韧环状聚烯烃材料及其制备方法
CN202011325146.5 2020-11-23

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WO2022105149A1 true WO2022105149A1 (fr) 2022-05-27

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Cited By (1)

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CN115746488A (zh) * 2022-11-28 2023-03-07 金发科技股份有限公司 一种聚烯烃组合物及其制备方法和应用

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* Cited by examiner, † Cited by third party
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CN112457617B (zh) * 2020-11-23 2022-09-13 金发科技股份有限公司 一种高透明低介电损耗增韧环状聚烯烃材料及其制备方法
CN113956596B (zh) * 2021-10-18 2022-10-25 金旸（厦门）新材料科技有限公司 一种低介电高韧性cop/ldpe合金材料及其制备方法

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JPH1095881A (ja) * 1996-09-26 1998-04-14 Mitsui Petrochem Ind Ltd ノルボルネン系樹脂組成物およびその用途
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CN112457617A (zh) * 2020-11-23 2021-03-09 金发科技股份有限公司 一种高透明低介电损耗增韧环状聚烯烃材料及其制备方法

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EP3662016A1 (fr) * 2017-08-03 2020-06-10 PolyOne Corporation Composés polymères coc translucides pour impression 3d
CN108912578B (zh) * 2018-06-13 2021-02-02 金发科技股份有限公司 一种改性环状聚烯烃材料及其应用

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CN1134958A (zh) * 1995-02-07 1996-11-06 三井石油化学工业株式会社 环烯烃树脂组合物
JPH1095881A (ja) * 1996-09-26 1998-04-14 Mitsui Petrochem Ind Ltd ノルボルネン系樹脂組成物およびその用途
US6331591B1 (en) * 1997-07-02 2001-12-18 Kaneka Corporation Cycloolefin copolymer resin composition and process for preparing the same
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CN112457617A (zh) * 2020-11-23 2021-03-09 金发科技股份有限公司 一种高透明低介电损耗增韧环状聚烯烃材料及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115746488A (zh) * 2022-11-28 2023-03-07 金发科技股份有限公司 一种聚烯烃组合物及其制备方法和应用
CN115746488B (zh) * 2022-11-28 2023-11-21 金发科技股份有限公司 一种聚烯烃组合物及其制备方法和应用

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