WO2021212820A1 - 一种增强聚丙烯材料及其制备方法 - Google Patents

一种增强聚丙烯材料及其制备方法 Download PDF

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WO2021212820A1
WO2021212820A1 PCT/CN2020/130134 CN2020130134W WO2021212820A1 WO 2021212820 A1 WO2021212820 A1 WO 2021212820A1 CN 2020130134 W CN2020130134 W CN 2020130134W WO 2021212820 A1 WO2021212820 A1 WO 2021212820A1
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Prior art keywords
reinforced
polypropylene material
component
fiber
reinforced polypropylene
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English (en)
French (fr)
Inventor
陆湛泉
黄险波
叶南飚
程书文
关安南
刘乐文
杨霄云
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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Priority to PL20932283.3T priority Critical patent/PL4119613T3/pl
Priority to ES20932283T priority patent/ES3003814T3/es
Priority to US17/916,800 priority patent/US12428528B2/en
Priority to EP20932283.3A priority patent/EP4119613B1/en
Publication of WO2021212820A1 publication Critical patent/WO2021212820A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/009—Additives being defined by their hardness
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

  • the invention relates to the technical field of engineering plastics, in particular to a reinforced polypropylene material and a preparation method thereof.
  • Polypropylene material is currently the most used polymer material. It has excellent processing properties and mechanical properties. It is widely used in daily life and industrial production, such as agricultural films, wires and cables, communications, housing construction, and aviation manufacturing. Wait.
  • Conventional reinforced polypropylene materials usually use glass fiber as a reinforcing medium, and use the high strength and high rigidity of glass fiber to improve product strength and heat resistance.
  • conventional glass fiber reinforced polypropylene materials have the disadvantages of poor light aging and thermal aging resistance, and poor low-temperature toughness, and cannot be used for a long time in harsh environments.
  • the inventor of the present invention was surprised to find after a large number of experiments that the selection of the reinforced polypropylene material formula to adjust the length and content distribution of the reinforced fiber greatly maintains the retained length of the reinforced fiber in the reinforced polypropylene material, and combines a specific content of low-hardness toner , And supplemented by a specific content of compatibilizer, without adding tougheners and conventional weathering additives, the low temperature toughness and long weather resistance of the reinforced polypropylene material obtained are significantly improved, which can meet the long-term use of the material Require.
  • the purpose of the present invention is to provide a reinforced polypropylene material with significantly improved low temperature toughness and long weather resistance.
  • Another object of the present invention is to provide a method for preparing the above reinforced polypropylene material.
  • a reinforced polypropylene material in parts by weight, includes the following components:
  • the reinforcing fiber includes component I, component II and component III:
  • Component I It is composed of reinforcing fibers with a length of 0.1mm-0.6mm, which account for 35%-50% of the number of reinforcing fibers;
  • Component II It is composed of reinforcing fibers with a length of 0.7mm-1.3mm, and its percentage of the number of reinforcing fibers is 35%-45%;
  • Component III It is composed of reinforcing fibers with a length of 1.4mm-2.0mm, which account for 5%-20% of the number of reinforcing fibers.
  • the effect of reinforcing fiber reinforcement is related to the dispersion state, uniformity of distribution, orientation and interface state of the reinforcing fiber in the matrix resin.
  • the longer the retained length of the glass fiber the higher the mechanical properties and heat resistance.
  • the rigidity and heat resistance of the material will be greatly reduced; when the length of the reinforcing fiber is too long, the plastic particles are too long, which affects the feeding during processing.
  • the component I in the reinforcing fiber accounts for 38%-45% of the number of reinforcing fibers.
  • the component II in the reinforcing fiber accounts for 37%-42% of the number of reinforcing fibers.
  • the component III in the reinforcing fiber accounts for 8%-15% of the number of reinforcing fibers.
  • the reinforcing fiber is selected from one or more of glass fiber, quartz fiber, and basalt fiber; the diameter of the reinforcing fiber is 5-20 microns.
  • the low-hardness toner has a Mohs hardness of ⁇ 6; preferably, the Mohs hardness is 0.1-4.
  • the low-hardness toner is selected from one or more of zinc white, zinc sulfide, barium white, antimony white, lithopone, lead white, calcium carbonate, talc, kaolin, barium sulfate, and titanium dioxide.
  • the polypropylene resin is selected from one or more of homopolypropylene PP-H, block copolymer polypropylene PP-B, and random copolymer polypropylene PP-R.
  • the present invention also provides a method for preparing the above-mentioned reinforced polypropylene material, which includes the following steps:
  • the position of the side feeding system of the twin-screw extruder can be adjusted, and the reinforcing fiber can enter the screw in the first to tenth zones, and then be added after the extruder die, and then directly combined with the polypropylene melt.
  • the temperature of the first to second zone of the twin-screw extruder is 120°C-160°C
  • the temperature of the third to fifth zone is 180°C-300°C
  • the temperature of the fifth to ten zone is 180°C-300°C
  • the screw speed is 300rpm-600rpm.
  • the present invention has the following beneficial effects:
  • the present invention chooses to adjust the length and content distribution of the reinforcing fiber in the reinforced polypropylene material formula, which greatly maintains the retained length of the reinforcing fiber in the reinforced polypropylene material, and combines a specific content of low-hardness toner, supplemented by a specific content of phase Compatibility, without the addition of toughening agents and conventional weathering additives, the low temperature toughness and long weather resistance of the obtained reinforced polypropylene material are significantly improved, thereby being able to meet the long-term use requirements of the material.
  • the test method of the length and distribution of the reinforcing fiber the notched impact strength spline after injection is first used to separate the reinforcing fiber from the matrix by a high-temperature burning scheme, and then the automatic imaging analysis technology is used to measure the length of the reinforcing fiber.
  • the number of tests is Around 2000.
  • Low temperature resistance toughness measure the notched impact strength at room temperature and the notched impact strength at -40°C at the same time; test standard: ISO 180/1A;
  • Polypropylene resin used in the present invention is a polypropylene resin used in the present invention.
  • Polypropylene resin block copolymer polypropylene PP-B: PP SP179, Lanzhou Petrochemical;
  • Maleic anhydride grafted polypropylene PP-g-MAH Manufacturer Polyram; Model: 1001CN;
  • Glass fiber 10 microns in diameter, ER4305PM-2400, boulder glass fiber;
  • Quartz fiber 5 microns in diameter, quartz fiber non-twisted yarn SJ114, Henan Shenjiu Tianhang New Material Co., Ltd.;
  • Basalt fiber 15 microns in diameter, basalt fiber untwisted yarn, Zhejiang Shijin Basalt Fiber Co., Ltd.;
  • the low-hardness toner used in the present invention is the low-hardness toner used in the present invention.
  • Zinc white Mohs hardness of 3.0, Cangzhou Jiewei Zinc Industry Co., Ltd.;
  • Toughening agent POE DF610, Singapore Mitsui Chemicals Co., Ltd.;
  • Weathering additives UV-531, Hubei Meifeng Trading Co., Ltd.
  • the position of the side feeding system of the extruder can be adjusted, and the reinforcing fiber can enter the extruder screw in the first to tenth zones, and then add it after the extruder die, and then directly combine with the polypropylene melt.
  • the temperature of the first to second zone of the extruder is 120°C-160°C
  • the temperature of the third to fifth zone is 180°C-300°C
  • the temperature of the fifth to ten zone is 180°C-300°C
  • the screw speed is 300rpm-600rpm.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开了一种增强聚丙烯材料，按重量份计，包括： a、10-90份的聚丙烯树脂； b、0.5-25份的相容剂； c、5-60份增强纤维； d、0.1-20份的低硬度色粉；所述增强纤维包括组分I、组分II和组分Ⅲ：组分I：由长度为0.1-0.6mm的增强纤维组成，其占增强纤维的根数百分比为35-50％；组分II：由长度为0.7-1.3mm的增强纤维组成，其占增强纤维的根数百分比为35-45％；组分Ⅲ：由长度为1.4-2.0mm的增强纤维组成，其占增强纤维的根数百分比为5-20％。本发明选用在增强聚丙烯材料配方中调节增强纤维的长度及含量分布，极大地在增强聚丙烯材料中保持增强纤维保留长度，并结合特定含量的低硬度色粉，并辅以特定含量的相容剂，得到的增强聚丙烯材料的低温韧性和长耐候性能得到明显改善。

Description

一种增强聚丙烯材料及其制备方法 技术领域
本发明涉及工程塑料技术领域，特别涉及一种增强聚丙烯材料及其制备方法。
背景技术
聚丙烯材料是目前用量最大的高分子材料，具有优异的加工性能和力学性能等优点，被广泛应用于日常生活和工业生产领域，如：农用薄膜、电线电缆、通讯、房屋建筑和航空制造业等。
常规的增强聚丙烯材料通常使用玻璃纤维作为增强介质，利用玻璃纤维的高强度高刚性提高产品强度和耐热。但是常规的玻璃纤维增强聚丙烯材料具有耐光老化和热老化性能差，低温韧性不好等缺陷，无法在环境较恶劣的场合长期使用。
本发明人经过大量实验惊讶地发现，选用在增强聚丙烯材料配方中调节增强纤维的长度及含量分布，极大地在增强聚丙烯材料中保持增强纤维保留长度，并结合特定含量的低硬度色粉，并辅以特定含量的相容剂，在不添加增韧剂和常规耐候助剂的情况下，得到的增强聚丙烯材料的低温韧性和长耐候性能得到明显改善，从而能够满足材料的长期使用要求。
发明内容
为了克服现有技术的缺点与不足，本发明的目的在于提供一种低温韧性和长耐候性能得到明显改善的增强聚丙烯材料。
本发明的另一目的是提供上述增强聚丙烯材料的制备方法。
本发明是通过以下技术方案实现的：
一种增强聚丙烯材料，按重量份计，包括以下组成：
a、10份-90份的聚丙烯树脂；
b、0.5份-25份的相容剂；
c、5份-60份增强纤维；
d、0.1份-20份的低硬度色粉；
所述增强纤维包括组分I、组分II和组分III：
组分I：由长度为0.1mm-0.6mm的增强纤维组成，其占增强纤维的根数百分比为35％-50％；
组分II：由长度为0.7mm-1.3mm的增强纤维组成，其占增强纤维的根数百分比为35％-45％；
组分Ⅲ：由长度为1.4mm-2.0mm的增强纤维组成，其占增强纤维的根数百分比为5％-20％。
增强纤维增强作用的效果，与增强纤维在基体树脂中分散状态、分布均匀性、取向以及 与基体树脂的界面状态有关，一般地玻纤保留长度越长，力学性能和耐热性能就越高。当增强纤维的长度过短，玻纤的保留长度过短，材料的刚性，耐热都会大打折扣；当增强纤维的长度过长，塑料粒子太长，影响加工过程中投料。
其中，所述增强纤维中组分I占增强纤维的根数百分比为38％-45％。
其中，所述增强纤维中组分II占增强纤维的根数百分比为37％-42％。
其中，所述增强纤维中组分Ⅲ占增强纤维的根数百分比为8％-15％。
其中，所述增强纤维选自玻璃纤维、石英纤维、玄武岩纤维中的一种或一种以上；所述增强纤维的直径为5-20微米。
其中，所述低硬度色粉的莫氏硬度＜6；优选为莫氏硬度为0.1-4。
其中，所述低硬度色粉选自锌白、硫化锌、钡白、锑白、锌钡白、铅白、碳酸钙、滑石粉、高岭土、硫酸钡、二氧化钛中的一种或一种以上。
其中，所述聚丙烯树脂选自均聚聚丙烯PP-H、嵌段共聚聚丙烯PP-B、无规共聚聚丙烯PP-R中的一种或一种以上。
其中，所述相容剂为极性单体与聚丙烯的接枝聚合物，其中极性单体选自马来酸酐、丙烯酸和丙烯酸酯类衍生物中的一种或几种的混合物。
本发明还提供上述增强聚丙烯材料的制备方法，包括如下步骤：
按照配方含量称量各组分，并将除增强纤维外的各组分混合均匀，随后将混合物加入双螺杆挤出机的主喂料系统；同时将增强纤维加入双螺杆挤出机的侧喂料系统，然后通过双螺杆挤出机熔融共混、挤出造粒制备得到增强聚丙烯材料。
其中双螺杆挤出机侧喂系统可以调节位置，增强纤维可以在第一至第十区进入螺杆，以及在挤出机模头后再加入，然后和聚丙烯熔体直接结合。
其中双螺杆挤出机一至二区温度为120℃-160℃，三至五区温度为180℃-300℃，五至十区温度为180℃-300℃，螺杆转速为300rpm-600rpm。
本发明与现有技术相比，具有如下有益效果：
本发明选用在增强聚丙烯材料配方中调节增强纤维的长度及含量分布，极大地在增强聚丙烯材料中保持增强纤维保留长度，并结合特定含量的低硬度色粉，并辅以特定含量的相容剂，在不添加增韧剂和常规耐候助剂的情况下，得到的增强聚丙烯材料的低温韧性和长耐候性能得到明显改善，从而能够满足材料的长期使用要求。
具体实施方式
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但 本发明的实施方式并不受下述实施例的限制。
各性能的测试标准或方法：
增强纤维的长度以及分布的测试方法：注塑后的缺口冲击强度样条首先采用高温灼烧的方案将增强纤维在基体中分离出，再使用自动成像分析技术对增强纤维长度进行测量，测试数目在2000根左右。
耐低温韧性：同时测量常温缺口冲击强度和-40℃缺口冲击强度；测试标准：ISO 180/1A；
长耐候性能：ISO 4892-2氙灯老化100h后测量色差。
本发明中使用的聚丙烯树脂：
聚丙烯树脂：嵌段共聚聚丙烯PP-B：PP SP179，兰州石化；
本发明中使用的相容剂：
马来酸酐接枝聚丙烯PP-g-MAH：厂家Polyram；型号：1001CN；
本发明中使用的增强纤维：
玻璃纤维：直径为10微米，ER4305PM-2400，巨石玻纤；
石英纤维：直径为5微米，石英纤维无捻纱SJ114，河南神玖天航新材料股份有限公司；
玄武岩纤维：直径为15微米，玄武岩纤维无捻纱，浙江石金玄武岩纤维有限公司；
本发明中使用的低硬度色粉：
锌白，莫氏硬度为3.0，沧州杰威锌业有限公司；
锑白，莫氏硬度为3.5，常德辰州锑品有限公司；
二氧化钛-1，莫氏硬度为5.0，BX-200，河北廊坊奇彩钛白粉制造有限公司；
二氧化钛-2，莫氏硬度为7.5，RX-237，河北廊坊奇彩钛白粉制造有限公司；
增韧剂：POE DF610，新加坡三井化学有限公司；
耐候助剂：UV-531，湖北美峰贸易有限公司。
实施例1-8及对比例1-6：增强聚丙烯材料的制备
按照配方含量称量各组分，并将除增强纤维外的各组分混合均匀，随后将混合物加入双螺杆挤出机的主喂料系统；同时将增强纤维加入双螺杆挤出机的侧喂料系统，然后通过双螺杆挤出机熔融共混、挤出造粒制备得到增强聚丙烯材料。
其中挤出机侧喂系统可以调节位置，增强纤维可以在第一至第十区进入挤出机螺杆，以及在挤出机模头后再加入，然后和聚丙烯熔体直接结合。
其中挤出机一至二区温度为120℃-160℃，三至五区温度为180℃-300℃，五至十区温度为180℃-300℃，螺杆转速为300rpm-600rpm。
表1各实施例与对比例中各组分的具体配比(重量份)及各性能测试结果
Figure PCTCN2020130134-appb-000001
续表1
Figure PCTCN2020130134-appb-000002

Claims (12)

  1. 一种增强聚丙烯材料，其特征在于，按重量份计，包括以下组成：
    a、10份-90份的聚丙烯树脂；
    b、0.5份-25份的相容剂；
    c、5份-60份增强纤维；
    d、0.1份-20份的低硬度色粉；
    所述增强纤维包括组分I、组分II和组分III：
    组分I：由长度为0.1mm-0.6mm的增强纤维组成，其占增强纤维的根数百分比为35％-50％；
    组分II：由长度为0.7mm-1.3mm的增强纤维组成，其占增强纤维的根数百分比为35％-45％；
    组分Ⅲ：由长度为1.4mm-2.0mm的增强纤维组成，其占增强纤维的根数百分比为5％-20％。
  2. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述增强纤维中组分I占增强纤维的根数百分比为38％-45％。
  3. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述增强纤维中组分II占增强纤维的根数百分比为37％-42％。
  4. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述增强纤维中组分Ⅲ占增强纤维的根数百分比为8％-15％。
  5. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述增强纤维选自玻璃纤维、石英纤维，玄武岩纤维中的一种或一种以上；所述增强纤维的直径为5-20微米。
  6. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述低硬度色粉的莫氏硬度＜6；优选为莫氏硬度为0.1-4。
  7. 根据权利要求1或3所述的增强聚丙烯材料，其特征在于，所述低硬度色粉选自锌白、硫化锌、钡白、锑白、锌钡白、铅白、碳酸钙、滑石粉、高岭土、硫酸钡、二氧化钛中的一种或一种以上。
  8. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述聚丙烯树脂选自均聚聚丙烯PP-H、嵌段共聚聚丙烯PP-B、无规共聚聚丙烯PP-R中的一种或一种以上。
  9. 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述相容剂为极性单体与聚丙烯的接枝聚合物，其中极性单体选自马来酸酐、丙烯酸和丙烯酸酯类衍生物中的一种或几种的混合物。
  10. 一种包含权利要求1-9任一项所述的增强聚丙烯材料的制备方法，其特征在于，包括如下步骤：
    按照配方含量称量各组分，并将除增强纤维外的各组分混合均匀，随后将混合物加入双螺杆 挤出机的主喂料系统；同时将增强纤维加入双螺杆挤出机的侧喂料系统，然后通过双螺杆挤出机熔融共混、挤出造粒制备得到增强聚丙烯材料。
  11. 根据权利要求10所述的增强聚丙烯材料的制备方法，其特征在于，所述双螺杆挤出机的侧喂料系统可以调节位置，增强纤维可以在第一至第十区进入螺杆，以及在挤出机模头后再加入，然后和聚丙烯熔体直接结合。
  12. 根据权利要求10或11所述的增强聚丙烯材料的制备方法，其特征在于，所述双螺杆挤出机一至二区温度为120℃-160℃，三至五区温度为180℃-300℃，五至十区温度为180℃-300℃，螺杆转速为300rpm-600rpm。
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