WO2022183553A1 - High-gloss polyvinyl chloride resin composition, preparation method therefor and use thereof - Google Patents

High-gloss polyvinyl chloride resin composition, preparation method therefor and use thereof Download PDF

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WO2022183553A1
WO2022183553A1 PCT/CN2021/083578 CN2021083578W WO2022183553A1 WO 2022183553 A1 WO2022183553 A1 WO 2022183553A1 CN 2021083578 W CN2021083578 W CN 2021083578W WO 2022183553 A1 WO2022183553 A1 WO 2022183553A1
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polyvinyl chloride
chloride resin
resin composition
gloss
composition according
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PCT/CN2021/083578
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French (fr)
Chinese (zh)
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李支松
余华林
宋科明
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广东联塑科技实业有限公司
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Publication of WO2022183553A1 publication Critical patent/WO2022183553A1/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
    • 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 present invention relates to the technical field of modification of functional plastics, and more particularly, to a high-gloss polyvinyl chloride resin composition and a preparation method and application thereof.
  • Polyvinyl chloride is a general-purpose plastic that is made of vinyl chloride monomer (VCM) by radical polymerization. It can be used to make hard and soft products for different purposes by adding appropriate additives. PVC has unique properties such as high strength, corrosion resistance, flame retardancy, insulation, transparency, and good compatibility with a wide range of plastic additives. Therefore, it is widely used in industry, agriculture, construction, daily necessities, packaging and other fields.
  • the main products include pipe fittings, door and window profiles, plates and sheets, wire insulation, medical supplies, films, sealing strips, etc.
  • the PVC wire trough widely used in the construction field has good insulation performance, and the anti-current breakdown voltage is as high as 25KV; it has good fire resistance, is flame-retardant, and self-extinguishes immediately after leaving the fire; it will not rust like a metal wire trough, and it is resistant to acid, Alkali resistance, oil resistance and many other advantages.
  • the surface of the common polyvinyl chloride trunking basically presents a matte state, which seriously affects the appearance and product texture, and is quite different from the decoration environment; although there are different methods to improve the gloss.
  • Chinese patent (CN102875920A) discloses a kind of ABS modified PVC to improve gloss, but ABS modified PBV has poor weather resistance and cannot be used for wire grooves.
  • Chinese patent (CN405462138A) discloses a PMMA/PVC alloy material and In the preparation method, styrene-acrylonitrile resin is used as a brightening agent to improve the gloss, but the effect of the gloss is not good enough, the effect on the gloss during the demolding process is large, and the plasticizing time is too long. long, limiting its application.
  • the invention provides a high-gloss polyvinyl chloride resin composition in order to overcome the defects of poor mechanical properties caused by low gloss and uneven plasticization.
  • Another object of the present invention is to provide a preparation method of the high gloss polyvinyl chloride resin composition.
  • Another object of the present invention is to provide the application of the high gloss polyvinyl chloride resin composition.
  • a high gloss polyvinyl chloride resin composition comprising the following components calculated in parts by weight:
  • the release agent is oxidized high-density polyethylene wax.
  • acrylonitrile-styrene copolymers are used in PVC resins to improve gloss, but acrylonitrile-styrene has obvious defects, such as slow plasticization and uneven plasticization, resulting in poor mechanical properties and limiting its application.
  • oxidized high-density polyethylene wax is generally used as a lubricant, it can maintain high gloss, but the inventors found through creative work that after blending acrylonitrile-styrene copolymer and oxidized high-density polyethylene wax, it can greatly increase the gloss.
  • the plasticizing ability is greatly improved, the mechanical properties are good, and after blending, the gloss is higher than that of any one added to the PVC resin.
  • oxidized high-density polyethylene wax has strong polarity, which can promote plasticization and reduce plasticization time; on the other hand, oxidized high-density polyethylene wax has strong polarity.
  • the molecular chain of high-density polyethylene wax contains polar groups, which can be adsorbed with the metal surface of equipment or molds, forming a lubricating film isolation layer between the polyvinyl chloride melt and the metal surface, enhancing the mold release of the melt and the mold release ability. The better, the higher the gloss.
  • the melting point of the oxidized high-density polyethylene wax is 132-140°C.
  • the melting point is determined by the ASTM D3954-2015 standard.
  • the melting point of the oxidized high-density polyethylene wax is 132-140° C.
  • the blending effect with acrylonitrile-styrene is better, the plasticizing ability is improved, and the mechanical properties are further improved.
  • the acid value of the oxidized high density polyethylene wax is 16-20.
  • the oxidized high-density polyethylene wax contains polar groups on the molecular chain, and the polar groups have a greater compatibility with polyvinyl chloride.
  • the metal surface can form a strong lubricating film, so the mold release is excellent.
  • the acid value of oxidized high-density polyethylene wax is used to characterize the number of polar groups on the molecular chain. .
  • the styrene content in the acrylonitrile-styrene copolymer is 20wt% to 45wt%.
  • the average degree of polymerization of the polyvinyl chloride resin is 741-845.
  • the heat stabilizer is a thiol methyl tin heat stabilizer.
  • the impact modifier has a core-shell structure acrylate impact modifier.
  • the processing modifier is one of methyl methacrylate or butyl methacrylate copolymer.
  • the lubricant is one or more of stearic acid, monoglyceride, calcium stearate or lead stearate.
  • the present invention also provides a preparation method of the high gloss polyvinyl chloride resin composition, comprising the following steps:
  • step S2 Add the material obtained in step S1 to a conical twin-screw extruder for plasticization and molding, cooling, and cutting by length to obtain the high-gloss polyvinyl chloride resin composition.
  • the temperature of the barrel of the conical twin-screw extruder is 165-180°C, and the temperature of the molding is 165-195°C.
  • the present invention provides a high-gloss polyvinyl chloride resin composition, which is blended with acrylonitrile-styrene copolymer and oxidized high-density polyethylene wax, which can not only greatly improve gloss, good demoulding effect, but also improve The plasticization of PVC resin has good mechanical properties.
  • reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • Polyvinyl chloride resin Tianjin Dagu Chemical, DG-800T;
  • Release agent A oxidized high-density polyethylene wax Honeywell A-C 316A, melting point 140°C, acid value 16;
  • Release agent B oxidized high-density polyethylene wax BASF Luwax OA6, melting point 132°C, acid value 18;
  • Release agent C oxidized high-density polyethylene wax EUROCERAS 719, melting point 138°C, acid value 19;
  • Release agent D oxidized high-density polyethylene wax Ruile Chemical RL916A, melting point 140°C, acid value 17;
  • Release agent E ethylene bis-stearamide, melting point 143°C;
  • Release agent F paraffin, melting point 60°C;
  • Acrylonitrile-styrene copolymer A styrene content 15wt%
  • Acrylonitrile-styrene copolymer B styrene content 20wt%
  • Acrylonitrile-styrene copolymer C styrene content 30wt%
  • Acrylonitrile-styrene copolymer D styrene content 45wt%
  • Acrylonitrile-styrene copolymer E styrene content 50wt%
  • Heat stabilizer Hubei Benxing Chemical, SW-977;
  • Lubricant Zhongshan Huamingtai Chemical BS3818 calcium stearate.
  • the high gloss polyvinyl chloride resin compositions of Examples and Comparative Examples were prepared by the following method, including the following steps:
  • step S2 adding the material obtained in step S1 into the conical twin-screw extruder for plasticization and molding, cooling, and cutting by length to obtain the high-gloss polyvinyl chloride resin composition; in the step S2, the conical twin-screw
  • the temperature of the barrel of the extruder was 165 to 180°C, and the temperature of the molding was 165 to 195°C.
  • Example 1 Example 2 Example 3 Example 4 Example 5 PVC resin 90 90 90 90 90 90 90 90
  • Release agent A 0.2 — — — 0.2 Release agent B — 0.2 — — — Release agent C — — 0.2 — — Release agent D — — — 0.2 — Acrylonitrile-Styrene Copolymer C 8 8 8 — Acrylonitrile-Styrene Copolymer A — — — — 8 light calcium carbonate 15 15 15 15 15 Heat stabilizers 1 1 1 1 1 impact modifier 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 processing modifier 1 1 1 1 1 1 1 lubricant 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8
  • Example 6 Example 7 Example 8 Example 9 Example 10 PVC resin 90 90 90 80 100 Release agent A 0.2 0.2 0.2 0.1 0.3 Acrylonitrile-Styrene Copolymer C — — — 2 10 Acrylonitrile-Styrene Copolymer B 8 — — — — Acrylonitrile-Styrene Copolymer D — 8 — — — Acrylonitrile-styrene copolymer E — — 8 — — light calcium carbonate 15 15 15 30 10 Heat stabilizers 1 1 1 2 0.3 impact modifier 6 6 6 8 4 processing modifier 1 1 1 1 2 0.5 lubricant 1.8 1.8 1.8 2.5 0.3
  • Release agent A — — — 0.2 Release agent E 0.2 — — — Release agent F — 0.2 — — Acrylonitrile-Styrene Copolymer C 8 8 — light calcium carbonate 15 15 15 15 Heat stabilizers 1 1 1 1 impact modifier 6 6 6 6 processing modifier 1 1 1 1 lubricant 1.8 1.8 1.8 1.8 1.8 1.8
  • the impact properties of simply supported beams are tested according to the requirements of GB/T 1043.1-2008 "Determination of Plastic Simply Supported Beams".
  • the impact performance of the simply supported beam is better than or equal to 15kJ/m 2 .

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided are a high-gloss polyvinyl chloride resin composition, a preparation method therefor and the use thereof. The high-gloss polyvinyl chloride resin composition comprises the following components in parts by weight: 80-100 parts of a polyvinyl chloride resin, 0.1-0.3 part of a release agent, 2-20 parts of an acrylonitrile-styrene copolymer, 10-30 parts of light calcium carbonate, 0.3-2 parts of a heat stabilizer, 4-8 parts of an impact modifier, 0.5-2 parts of a processing modifier, and 0.3-2.5 parts of a lubricant, wherein the release agent is oxidized high-density polyethylene wax. The polyvinyl chloride resin composition has a relatively high glossiness and mechanical properties.

Description

一种高光泽聚氯乙烯树脂组合物及其制备方法和应用A kind of high gloss polyvinyl chloride resin composition and its preparation method and application 技术领域technical field
本发明涉及功能塑料改性技术领域，更具体地，涉及一种高光泽聚氯乙烯树脂组合物及其制备方法和应用。The present invention relates to the technical field of modification of functional plastics, and more particularly, to a high-gloss polyvinyl chloride resin composition and a preparation method and application thereof.
背景技术Background technique
聚氯乙烯(PVC)是一种是由氯乙烯单体(VCM)通过自由基聚合而成的通用塑料，可通过添加适当的助剂制得满足不同用途的硬制品和软制品。PVC具有强度高、耐腐蚀，难燃、绝缘、透明以及与范围广泛的各种塑料添加剂相容性好等独特性质。因而广泛应用于工业、农业、建筑、日用品、包装等领域，主要制品包括管材管件、门窗型材、板材和片材、电线绝缘皮、医疗用品、薄膜、密封条等。Polyvinyl chloride (PVC) is a general-purpose plastic that is made of vinyl chloride monomer (VCM) by radical polymerization. It can be used to make hard and soft products for different purposes by adding appropriate additives. PVC has unique properties such as high strength, corrosion resistance, flame retardancy, insulation, transparency, and good compatibility with a wide range of plastic additives. Therefore, it is widely used in industry, agriculture, construction, daily necessities, packaging and other fields. The main products include pipe fittings, door and window profiles, plates and sheets, wire insulation, medical supplies, films, sealing strips, etc.
建筑领域广泛使用的聚氯乙烯电线槽绝缘性能好，抗电流击穿电压高达25KV；防火性能好，具有难燃性，离火瞬间自熄；不会像金属线槽一样生锈，且耐酸、耐碱，耐油等诸多优点。目前通常的聚氯乙烯线槽由于聚氯乙烯材料本身特性制约，线槽表面基本呈现哑光状态，严重影响美观和产品质感，与装修环境存在较大差异；目前虽然有不同的方法来提高光泽度，比如中国专利(CN102875920A)公开了一种ABS改性PVC提高光泽度，但是ABS改性的PBV耐候性差，不能用于电线槽，中国专利(CN405462138A)公开了一种PMMA/PVC合金材料及其制备方法，在该方案中采用了苯乙烯-丙烯腈树脂作为光亮剂提高光泽度，但是，其光泽度的效果不够更好，脱模过程中对光泽度的影响较大、塑化时间过长，限制了其应用。The PVC wire trough widely used in the construction field has good insulation performance, and the anti-current breakdown voltage is as high as 25KV; it has good fire resistance, is flame-retardant, and self-extinguishes immediately after leaving the fire; it will not rust like a metal wire trough, and it is resistant to acid, Alkali resistance, oil resistance and many other advantages. At present, due to the limitation of the characteristics of the PVC material itself, the surface of the common polyvinyl chloride trunking basically presents a matte state, which seriously affects the appearance and product texture, and is quite different from the decoration environment; although there are different methods to improve the gloss. For example, Chinese patent (CN102875920A) discloses a kind of ABS modified PVC to improve gloss, but ABS modified PBV has poor weather resistance and cannot be used for wire grooves. Chinese patent (CN405462138A) discloses a PMMA/PVC alloy material and In the preparation method, styrene-acrylonitrile resin is used as a brightening agent to improve the gloss, but the effect of the gloss is not good enough, the effect on the gloss during the demolding process is large, and the plasticizing time is too long. long, limiting its application.
发明内容SUMMARY OF THE INVENTION
本发明为克服光泽度低、塑化不均匀导致的力学性能差的缺陷，提供一种高光泽聚氯乙烯树脂组合物。The invention provides a high-gloss polyvinyl chloride resin composition in order to overcome the defects of poor mechanical properties caused by low gloss and uneven plasticization.
本发明的另一目的在于提供所述高光泽聚氯乙烯树脂组合物的制备方法。Another object of the present invention is to provide a preparation method of the high gloss polyvinyl chloride resin composition.
本发明的另一目的在于提供所述高光泽聚氯乙烯树脂组合物的应用。Another object of the present invention is to provide the application of the high gloss polyvinyl chloride resin composition.
为实现上述目的，本发明采用的技术方案是：For achieving the above object, the technical scheme adopted in the present invention is:
一种高光泽聚氯乙烯树脂组合物，包括如下按重量份计算的组分：A high gloss polyvinyl chloride resin composition, comprising the following components calculated in parts by weight:
Figure PCTCN2021083578-appb-000001
Figure PCTCN2021083578-appb-000001
所述脱模剂为氧化高密度聚乙烯蜡。The release agent is oxidized high-density polyethylene wax.
一般地，丙烯腈-苯乙烯共聚物在PVC树脂中用来提高光泽度，但是丙烯腈-苯乙烯的缺陷也比较明显，塑化慢，塑化不均匀，导致力学性能差，限制了其应用；而氧化高密度聚乙烯蜡一般用作润滑剂，能够保持高光泽，但是本发明人通过创造性的劳动发现，将丙烯腈-苯乙烯共聚物和氧化高密度聚乙烯蜡共混后，能够大幅度提高塑化能力，力学性能好，且共混后，光泽度相对于任意一种加入到PVC树脂中的光泽度更高。这是因为丙烯腈-苯乙烯共聚物和氧化高密度聚乙烯蜡协同作用提高了光泽度，氧化高密度聚乙烯蜡极性强，能够促进塑化作用，降低塑化时间；另一方面，氧化高密度聚乙烯蜡分子链上含有极性基团，可与设备或模具的金属表面吸附，在聚氯乙烯熔体与金属表面形成润滑薄膜隔离层，增强熔体的脱模性，脱模能力越好，光泽度越高。Generally, acrylonitrile-styrene copolymers are used in PVC resins to improve gloss, but acrylonitrile-styrene has obvious defects, such as slow plasticization and uneven plasticization, resulting in poor mechanical properties and limiting its application. While oxidized high-density polyethylene wax is generally used as a lubricant, it can maintain high gloss, but the inventors found through creative work that after blending acrylonitrile-styrene copolymer and oxidized high-density polyethylene wax, it can greatly increase the gloss. The plasticizing ability is greatly improved, the mechanical properties are good, and after blending, the gloss is higher than that of any one added to the PVC resin. This is because the synergistic effect of acrylonitrile-styrene copolymer and oxidized high-density polyethylene wax improves gloss, and oxidized high-density polyethylene wax has strong polarity, which can promote plasticization and reduce plasticization time; on the other hand, oxidized high-density polyethylene wax has strong polarity. The molecular chain of high-density polyethylene wax contains polar groups, which can be adsorbed with the metal surface of equipment or molds, forming a lubricating film isolation layer between the polyvinyl chloride melt and the metal surface, enhancing the mold release of the melt and the mold release ability. The better, the higher the gloss.
优选地，所述氧化高密度聚乙烯蜡的熔滴点为132～140℃。Preferably, the melting point of the oxidized high-density polyethylene wax is 132-140°C.
所述熔滴点通过ASTM D3954-2015标准测定。The melting point is determined by the ASTM D3954-2015 standard.
所述氧化高密度聚乙烯蜡的熔滴点在132～140℃时，与丙烯腈-苯乙烯共混效果更好，提高塑化能力，力学性能进一步提高。When the melting point of the oxidized high-density polyethylene wax is 132-140° C., the blending effect with acrylonitrile-styrene is better, the plasticizing ability is improved, and the mechanical properties are further improved.
优选地，所述氧化高密度聚乙烯蜡的的酸值为16～20。Preferably, the acid value of the oxidized high density polyethylene wax is 16-20.
氧化高密度聚乙烯蜡分子链上含有极性基团，极性基团与聚氯乙烯相容度较大，由于氧化高密度聚乙烯蜡分子量较大，极性又较强，与加工设备的金属表面能形成坚固的润滑薄膜，因而脱模性优良。氧化高密度聚乙烯蜡的酸值用于表征分子链上极性基团的多少，酸值越高，氧化高密度聚乙烯蜡与聚氯乙烯相容性越好，制品脱模性就越好。The oxidized high-density polyethylene wax contains polar groups on the molecular chain, and the polar groups have a greater compatibility with polyvinyl chloride. The metal surface can form a strong lubricating film, so the mold release is excellent. The acid value of oxidized high-density polyethylene wax is used to characterize the number of polar groups on the molecular chain. .
优选地，所述丙烯腈-苯乙烯共聚物中苯乙烯含量为20wt％～45wt％。Preferably, the styrene content in the acrylonitrile-styrene copolymer is 20wt% to 45wt%.
所述丙烯腈-苯乙烯共聚物中苯乙烯含量越低，光泽度越低，塑化快，苯乙烯含量高，光泽度高，塑化慢，因此，当苯乙烯含量在20wt％～45wt％之间具有较好的光泽度和力学性能。The lower the styrene content in the acrylonitrile-styrene copolymer, the lower the gloss, the faster the plasticization, the higher the styrene content, the higher the gloss, and the slower the plasticization. Therefore, when the styrene content is between 20wt% and 45wt% It has good gloss and mechanical properties.
优选地，所述聚氯乙烯树脂的平均聚合度为741～845。Preferably, the average degree of polymerization of the polyvinyl chloride resin is 741-845.
优选地，所述热稳定剂为硫醇甲基锡热稳定剂。Preferably, the heat stabilizer is a thiol methyl tin heat stabilizer.
优选地，所述抗冲击改性剂具有核-壳结构的丙烯酸酯类抗冲击改性剂。Preferably, the impact modifier has a core-shell structure acrylate impact modifier.
优选地，所述加工改性剂为甲基丙烯酸甲酯或甲基丙烯酸丁酯共聚物中的一种。Preferably, the processing modifier is one of methyl methacrylate or butyl methacrylate copolymer.
所述润滑剂为硬脂酸、单甘酯、硬脂酸钙或硬脂酸铅中的一种或几种。The lubricant is one or more of stearic acid, monoglyceride, calcium stearate or lead stearate.
本发明还提供所述高光泽聚氯乙烯树脂组合物的制备方法，包括如下步骤：The present invention also provides a preparation method of the high gloss polyvinyl chloride resin composition, comprising the following steps:
S1.按比例称取聚氯乙烯树脂、丙烯腈-苯乙烯共聚物、脱模剂、轻质碳酸钙、热稳定剂、抗冲击改性剂、加工改性剂、润滑剂投入高速混料机组的热混缸，高速搅拌后待热混缸的温度达到115～120℃时排入冷混缸中搅拌冷却；S1. Weigh the polyvinyl chloride resin, acrylonitrile-styrene copolymer, mold release agent, light calcium carbonate, heat stabilizer, impact modifier, processing modifier, lubricant in proportion to the high-speed mixing unit After high-speed stirring, when the temperature of the hot mixing tank reaches 115-120 °C, it is discharged into the cold mixing tank for stirring and cooling;
S2.将步骤S1得到的物料加入锥形双螺杆挤出机塑化模塑成型，冷却、计长切割即得所述高光泽聚氯乙烯树脂组合物。S2. Add the material obtained in step S1 to a conical twin-screw extruder for plasticization and molding, cooling, and cutting by length to obtain the high-gloss polyvinyl chloride resin composition.
优选的，所述步骤S2中，锥形双螺杆挤出机的机筒的温度为165～180℃，模塑成型的温度为165～195℃。Preferably, in the step S2, the temperature of the barrel of the conical twin-screw extruder is 165-180°C, and the temperature of the molding is 165-195°C.
所述高光泽聚氯乙烯树脂组合物在制备电线槽中的应用。The application of the high-gloss polyvinyl chloride resin composition in the preparation of wire troughs.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
本发明提供了一种高光泽聚氯乙烯树脂组合物，采用丙烯腈-苯乙烯共聚物和氧化高密度聚乙烯蜡共混，不仅能够大幅度提高光泽度，脱模效果好，而且还能提高PVC树脂的塑化，力学性能好。The present invention provides a high-gloss polyvinyl chloride resin composition, which is blended with acrylonitrile-styrene copolymer and oxidized high-density polyethylene wax, which can not only greatly improve gloss, good demoulding effect, but also improve The plasticization of PVC resin has good mechanical properties.
具体实施方式Detailed ways
下面将对本发明实施例中的技术方案进行清楚、完整地描述，但本发明的实施方式不限于此。The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
本发明所采用的试剂、方法和设备，如无特殊说明，均为本技术领域常规试剂、方法和设备。The reagents, methods and equipment used in the present invention, unless otherwise specified, are conventional reagents, methods and equipment in the technical field.
以下实施例及对比例中采用的原料如下：The raw materials used in the following examples and comparative examples are as follows:
聚氯乙烯树脂：天津大沽化工，DG-800T；Polyvinyl chloride resin: Tianjin Dagu Chemical, DG-800T;
脱模剂A：氧化高密度聚乙烯蜡Honeywell A-C 316A，熔滴点140℃，酸值 16；Release agent A: oxidized high-density polyethylene wax Honeywell A-C 316A, melting point 140℃, acid value 16;
脱模剂B：氧化高密度聚乙烯蜡BASF Luwax OA6，熔滴点132℃，酸值18；Release agent B: oxidized high-density polyethylene wax BASF Luwax OA6, melting point 132℃, acid value 18;
脱模剂C：氧化高密度聚乙烯蜡EUROCERAS 719，熔滴点138℃，酸值19；Release agent C: oxidized high-density polyethylene wax EUROCERAS 719, melting point 138℃, acid value 19;
脱模剂D：氧化高密度聚乙烯蜡瑞勒化工RL916A，熔滴点140℃，酸值17；Release agent D: oxidized high-density polyethylene wax Ruile Chemical RL916A, melting point 140℃, acid value 17;
脱模剂E：乙撑双硬脂酰胺，熔点143℃；Release agent E: ethylene bis-stearamide, melting point 143°C;
脱模剂F：石蜡，熔点60℃；Release agent F: paraffin, melting point 60℃;
丙烯腈-苯乙烯共聚物A：苯乙烯含量15wt％；Acrylonitrile-styrene copolymer A: styrene content 15wt%;
丙烯腈-苯乙烯共聚物B：苯乙烯含量20wt％；Acrylonitrile-styrene copolymer B: styrene content 20wt%;
丙烯腈-苯乙烯共聚物C：苯乙烯含量30wt％；Acrylonitrile-styrene copolymer C: styrene content 30wt%;
丙烯腈-苯乙烯共聚物D：苯乙烯含量45wt％；Acrylonitrile-styrene copolymer D: styrene content 45wt%;
丙烯腈-苯乙烯共聚物E：苯乙烯含量50wt％；Acrylonitrile-styrene copolymer E: styrene content 50wt%;
丙烯腈-苯乙烯共聚物均为市售；Acrylonitrile-styrene copolymers are commercially available;
轻质碳酸钙：广西华纳新材料技有限公司，CCR-5；Light calcium carbonate: Guangxi Huana New Material Technology Co., Ltd., CCR-5;
热稳定剂：湖北犇星化工，SW-977；Heat stabilizer: Hubei Benxing Chemical, SW-977;
抗冲击改性剂：钟渊kaneaka ACE FM-40；Impact modifier: Zhongyuan kaneaka ACE FM-40;
加工改性剂：钟渊kane ACE PA-20；Processing modifier: Zhongyuan kane ACE PA-20;
润滑剂：中山华明泰化工BS3818硬脂酸钙。Lubricant: Zhongshan Huamingtai Chemical BS3818 calcium stearate.
实施例和对比例的高光泽聚氯乙烯树脂组合物通过下述方法制备，包括如下步骤：The high gloss polyvinyl chloride resin compositions of Examples and Comparative Examples were prepared by the following method, including the following steps:
S1.按比例称取聚氯乙烯树脂、丙烯腈-苯乙烯共聚物、脱模剂、轻质碳酸钙、热稳定剂、抗冲击改性剂、加工改性剂、润滑剂投入高速混料机组的热混缸，高速搅拌后待热混缸的温度达到115～120℃时排入冷混缸中搅拌冷却；S1. Weigh the polyvinyl chloride resin, acrylonitrile-styrene copolymer, mold release agent, light calcium carbonate, heat stabilizer, impact modifier, processing modifier, lubricant in proportion to the high-speed mixing unit After high-speed stirring, when the temperature of the hot mixing tank reaches 115-120 °C, it is discharged into the cold mixing tank for stirring and cooling;
S2.将步骤S1得到的物料加入锥形双螺杆挤出机塑化模塑成型，冷却、计长切割即得所述高光泽聚氯乙烯树脂组合物；所述步骤S2中，锥形双螺杆挤出机的机筒的温度为165～180℃，模塑成型的温度为165～195℃。S2. adding the material obtained in step S1 into the conical twin-screw extruder for plasticization and molding, cooling, and cutting by length to obtain the high-gloss polyvinyl chloride resin composition; in the step S2, the conical twin-screw The temperature of the barrel of the extruder was 165 to 180°C, and the temperature of the molding was 165 to 195°C.
实施例1～5Examples 1 to 5
表1实施例1～5的配方(份)Formulations (parts) of Table 1 Examples 1-5
   实施例1Example 1 实施例2Example 2 实施例3Example 3 实施例4Example 4 实施例5Example 5
聚氯乙烯树脂PVC resin 9090 9090 9090 9090 9090
脱模剂ARelease agent A 0.20.2 —— —— —— 0.20.2
脱模剂BRelease agent B —— 0.20.2 —— —— ——
脱模剂CRelease agent C —— —— 0.20.2 —— ——
脱模剂DRelease agent D —— —— —— 0.20.2 ——
丙烯腈-苯乙烯共聚物CAcrylonitrile-Styrene Copolymer C 88 88 88 88 ——
丙烯腈-苯乙烯共聚物AAcrylonitrile-Styrene Copolymer A —— —— —— —— 88
轻质碳酸钙light calcium carbonate 1515 1515 1515 1515 1515
热稳定剂Heat stabilizers 11 11 11 11 11
抗冲击改性剂impact modifier 66 66 66 66 66
加工改性剂processing modifier 11 11 11 11 11
润滑剂lubricant 1.81.8 1.81.8 1.81.8 1.81.8 1.81.8
实施例6～10Examples 6 to 10
表2实施例6～10的配方(份)The formula (part) of table 2 embodiment 6～10
   实施例6Example 6 实施例7Example 7 实施例8Example 8 实施例9Example 9 实施例10Example 10
聚氯乙烯树脂PVC resin 9090 9090 9090 8080 100100
脱模剂ARelease agent A 0.20.2 0.20.2 0.20.2 0.10.1 0.30.3
丙烯腈-苯乙烯共聚物CAcrylonitrile-Styrene Copolymer C —— —— —— 22 1010
丙烯腈-苯乙烯共聚物BAcrylonitrile-Styrene Copolymer B 88 —— —— —— ——
丙烯腈-苯乙烯共聚物DAcrylonitrile-Styrene Copolymer D —— 88 —— —— ——
丙烯腈-苯乙烯共聚物EAcrylonitrile-styrene copolymer E —— —— 88 —— ——
轻质碳酸钙light calcium carbonate 1515 1515 1515 3030 1010
热稳定剂Heat stabilizers 11 11 11 22 0.30.3
抗冲击改性剂impact modifier 66 66 66 88 44
加工改性剂processing modifier 11 11 11 22 0.50.5
润滑剂lubricant 1.81.8 1.81.8 1.81.8 2.52.5 0.30.3
对比例1～4Comparative Examples 1 to 4
表4对比例1～4的配方(份)Table 4 Formula (parts) of comparative examples 1 to 4
   对比例1Comparative Example 1 对比例2Comparative Example 2 对比例3Comparative Example 3 对比例4Comparative Example 4
聚氯乙烯树脂PVC resin 9090 9090 9090 9090
脱模剂ARelease agent A —— —— —— 0.20.2
脱模剂ERelease agent E 0.20.2 —— —— ——
脱模剂FRelease agent F —— 0.20.2 —— ——
丙烯腈-苯乙烯共聚物CAcrylonitrile-Styrene Copolymer C 88 88 88 ——
轻质碳酸钙light calcium carbonate 1515 1515 1515 1515
热稳定剂Heat stabilizers 11 11 11 11
抗冲击改性剂impact modifier 66 66 66 66
加工改性剂processing modifier 11 11 11 11
润滑剂lubricant 1.81.8 1.81.8 1.81.8 1.81.8
上述实施例和对比例均通过下述测试方法测试性能The above-mentioned embodiment and comparative example are all tested by the following test methods
光泽度按ASTM D2457-2003《塑料薄膜和固态塑料镜面光泽度的标准试验方法》要求进行检测；光泽度大于60Gu效果比较好。The gloss is tested according to the requirements of ASTM D2457-2003 "Standard Test Method for Specular Gloss of Plastic Films and Solid Plastics"; the effect of gloss greater than 60Gu is better.
简支梁冲击性能按GB/T 1043.1-2008《塑料简支梁方法的测定》要求进行检测。简支梁冲击性能大于等于15kJ/m 2效果比较好。 The impact properties of simply supported beams are tested according to the requirements of GB/T 1043.1-2008 "Determination of Plastic Simply Supported Beams". The impact performance of the simply supported beam is better than or equal to 15kJ/m 2 .
表5实施例和对比例的数据Table 5 Data of Examples and Comparative Examples
   光泽度，60度角/GuGloss, 60 degree angle/Gu 简支梁冲击性能/kJ/m 2 Charpy impact performance/kJ/m 2
实施例1Example 1 72.772.7 19.619.6
实施例2Example 2 65.365.3 17.217.2
实施例3Example 3 70.670.6 18.518.5
实施例4Example 4 73.573.5 20.120.1
实施例5Example 5 60.260.2 22.122.1
实施例6Example 6 65.165.1 20.820.8
实施例7Example 7 75.875.8 18.218.2
实施例8Example 8 74.374.3 15.015.0
实施例9Example 9 65.565.5 16.516.5
实施例10Example 10 70.570.5 18.518.5
对比例1Comparative Example 1 52.352.3 13.913.9
对比例2Comparative Example 2 51.851.8 13.413.4
对比例3Comparative Example 3 50.550.5 12.712.7
对比例4Comparative Example 4 35.535.5 17.617.6
从实施例1～4看，氧化高密度聚乙烯蜡的熔滴点和酸值分别在132～140℃，16～20时，简支梁冲击性能和光泽度较好，脱模性好。From Examples 1 to 4, when the melting point and acid value of the oxidized high-density polyethylene wax are 132-140°C and 16-20, respectively, the simply supported beam impact properties and glossiness are good, and the mold release properties are good.
从实施例5～8可以看出，苯乙烯含量越高光泽度越好，脱模性越好，简支梁冲击性能越差。It can be seen from Examples 5 to 8 that the higher the styrene content, the better the gloss, the better the release property, and the worse the impact performance of the simply supported beam.
从对比例1～4可以看出，聚合物制品不添加氧化高密度聚乙烯蜡或添加其它脱模剂时，其聚合物制品的光泽度或者简支梁冲击性能较低，不能满足要求。From Comparative Examples 1 to 4, it can be seen that when the polymer products do not add oxidized high-density polyethylene wax or other release agents, the gloss or simply supported beam impact properties of the polymer products are low, which cannot meet the requirements.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。Obviously, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the embodiments of the present invention. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. Any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims (10)

  1. 一种高光泽聚氯乙烯树脂组合物，其特征在于，包括如下按重量份计算的组分：A high gloss polyvinyl chloride resin composition is characterized in that, comprises the following components calculated by weight:
    Figure PCTCN2021083578-appb-100001
    Figure PCTCN2021083578-appb-100001
    所述脱模剂为氧化高密度聚乙烯蜡。The release agent is oxidized high-density polyethylene wax.
  2. 根据权利要求1所述高光泽聚氯乙烯树脂组合物，其特征在于，所述氧化高密度聚乙烯蜡的熔滴点为132～140℃。The high-gloss polyvinyl chloride resin composition according to claim 1, wherein the melting point of the oxidized high-density polyethylene wax is 132-140°C.
  3. 据权利要求1所述高光泽聚氯乙烯树脂组合物，其特征在于，所述氧化高密度聚乙烯蜡的酸值为16～20。The high gloss polyvinyl chloride resin composition according to claim 1, wherein the acid value of the oxidized high density polyethylene wax is 16-20.
  4. 根据权利要求1所述高光泽聚氯乙烯树脂组合物，其特征在于，所述丙烯腈-苯乙烯共聚物中苯乙烯含量为20wt％～45wt％。The high-gloss polyvinyl chloride resin composition according to claim 1, wherein the styrene content in the acrylonitrile-styrene copolymer is 20wt% to 45wt%.
  5. 根据权利要求1所述高光泽聚氯乙烯树脂组合物，其特征在于，所述聚氯乙烯树脂的平均聚合度为741～845。The high gloss polyvinyl chloride resin composition according to claim 1, wherein the average degree of polymerization of the polyvinyl chloride resin is 741-845.
  6. 根据权利要求1所述高光泽聚氯乙烯树脂组合物，其特征在于，所述热稳定剂为硫醇甲基锡热稳定剂。The high gloss polyvinyl chloride resin composition according to claim 1, wherein the heat stabilizer is a thiol methyl tin heat stabilizer.
  7. 根据权利要求1所述高光泽聚氯乙烯树脂组合物，其特征在于，所述抗冲击改性剂具有核-壳结构的丙烯酸酯类抗冲击改性剂。The high-gloss polyvinyl chloride resin composition according to claim 1, wherein the impact modifier has an acrylate-based impact modifier with a core-shell structure.
  8. 根据权利要求1所述高光泽聚氯乙烯树脂组合物，其特征在于，所述加工改性剂为甲基丙烯酸甲酯或甲基丙烯酸丁酯共聚物中的一种。The high gloss polyvinyl chloride resin composition according to claim 1, wherein the processing modifier is one of methyl methacrylate or butyl methacrylate copolymer.
  9. 根据权利要求1～8任一项所述高光泽聚氯乙烯树脂组合物的制备方法，其特征在于，包括如下步骤：The preparation method of the high-gloss polyvinyl chloride resin composition according to any one of claims 1 to 8, wherein the method comprises the following steps:
    S1.按比例称取聚氯乙烯树脂、丙烯腈-苯乙烯共聚物、脱模剂、轻质碳酸钙、热稳定剂、抗冲击改性剂、加工改性剂、润滑剂投入高速混料机组的热混缸， 高速搅拌后待热混缸的温度达到115～120℃时排入冷混缸中搅拌冷却；S1. Weigh the polyvinyl chloride resin, acrylonitrile-styrene copolymer, mold release agent, light calcium carbonate, heat stabilizer, impact modifier, processing modifier, lubricant in proportion to the high-speed mixing unit After high-speed stirring, when the temperature of the hot mixing tank reaches 115-120 °C, it is discharged into the cold mixing tank for stirring and cooling;
    S2.将步骤S1得到的物料加入锥形双螺杆挤出机塑化模塑成型，冷却、计长切割即得所述高光泽聚氯乙烯树脂组合物。S2. Add the material obtained in step S1 to a conical twin-screw extruder for plasticization and molding, cooling, and cutting by length to obtain the high-gloss polyvinyl chloride resin composition.
  10. 权利要求1～8任一项所述高光泽聚氯乙烯树脂组合物在制备电线槽中的应用。Application of the high-gloss polyvinyl chloride resin composition according to any one of claims 1 to 8 in the preparation of wire troughs.
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