WO2023001312A1 - 一种热塑性聚烯烃材料及其制备方法和应用 - Google Patents

一种热塑性聚烯烃材料及其制备方法和应用 Download PDF

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Publication number
WO2023001312A1
WO2023001312A1 PCT/CN2022/107860 CN2022107860W WO2023001312A1 WO 2023001312 A1 WO2023001312 A1 WO 2023001312A1 CN 2022107860 W CN2022107860 W CN 2022107860W WO 2023001312 A1 WO2023001312 A1 WO 2023001312A1
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Prior art keywords
hand mold
thermoplastic polyolefin
polyolefin material
parts
glass fiber
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PCT/CN2022/107860
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English (en)
French (fr)
Inventor
简思强
杨友强
丁超
陈平绪
程文建
许齐勇
李振华
魏金刚
余小鸽
戴剑
夏超
张龙飞
杨方强
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金发科技股份有限公司
广东金发科技有限公司
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Publication of WO2023001312A1 publication Critical patent/WO2023001312A1/zh

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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
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to the technical field of polymer materials, and more specifically, to a thermoplastic polyolefin material and its preparation method and application.
  • the hand mold is a hand mold used to produce plastic gloves by dipping method.
  • the production process of rubber gloves using liquid latex as raw material is: the ceramic hand mold is dipped with plastic liquid material, dried and demoulded.
  • the hand molds used in production should be acid-resistant, alkali-resistant, chemical-resistant, and have a certain thermal shock resistance.
  • Existing hand mold bodies are generally made of ceramics. Ceramic hand molds are easy to make and have good surface hydrophilicity, but they are heavy in proportion (high production energy consumption), fragile and not durable (the service life is generally less than one year), and cannot Recycling (poor environmental protection).
  • Polypropylene has become one of the most widely used general-purpose plastics because of its excellent comprehensive properties, good cost performance, light specific gravity, excellent acid and alkali resistance, and wide processing and molding conditions. Polypropylene is a typical hydrophobic material, and its water contact angle is greater than 90°.
  • Chinese patent CN103756236A discloses a thermoplastic elastomer composition made of polypropylene as a matrix, which can be used to prepare hand molds.
  • Chinese patent CN107053564A discloses a plastic hand mold. The manufacturing method of mold is to utilize fluoroplastics to prepare hand molds to improve the wear resistance and acid resistance of plastic hand molds, but the heat resistance of these plastic hand molds is not good.
  • the technical problem to be solved by the present invention is to overcome the defects and deficiencies of the poor heat resistance of existing plastic hand molds, and provide a thermoplastic polyolefin material with good heat resistance, which can be used to prepare plastic hand molds and obtain Heat-resistant plastic hand mold, excellent solvent resistance, good wettability and high yield.
  • Another object of the present invention is to provide a method for preparing thermoplastic polyolefin materials.
  • Another object of the present invention is to provide an application of thermoplastic polyolefin material.
  • thermoplastic polyolefin material comprising the following components calculated in parts by weight:
  • the flat glass fiber has a thickness of 2-5 ⁇ m, a flatness ratio of 2:1-6:1, and a retained length of 0.1-0.5 mm;
  • the hydrophilic modifier is a polymer containing carboxyl groups, hydroxyl groups, ester bonds, and amide groups with a weight average molecular weight of 50,000 to 200,000, and/or a C5 ⁇ C50 alkyl oligomer.
  • the present invention uses cycloolefin copolymer as the matrix, which has good heat resistance, and adds flat glass fiber and hydrophilic modifier in a certain proportion, wherein the flat glass fiber can effectively improve the heat resistance, deformation and surface properties of the material, When the amount of flat glass fiber added is too small, the heat resistance and rigidity of the material are correspondingly poor; The additive can form a synergistic effect with the flat glass fiber to improve the hydrophilic wetting effect on the surface of the material. When the amount of the hydrophilic modifier is too small, the hydrophilic effect on the surface will be correspondingly poor; The performance is not significantly improved, but the processability and mechanical properties of the material will deteriorate.
  • the invention obtains a thermoplastic polyolefin material with excellent heat resistance through the adjustment of the components and their dosage, and also has better wettability and higher yield rate.
  • Hydrophilic modifier 5-15 parts Hydrophilic modifier 5-15 parts.
  • the cyclic olefin copolymer is a copolymer of bicycloheptene (norbornene) as the main functional monomer.
  • the flat glass fiber has a thickness of 3-4 ⁇ m, a flatness ratio of 3:1-5:1, and a retained length of 0.1-0.3 mm.
  • the original length of the flat glass fibers is 3-5mm.
  • the flat glass fibers with an original length of 3-5 mm are fed into the screw position of the extruder to obtain flat glass fibers with a retained length of 0.1-0.5 mm.
  • the cycloolefin copolymer is a cycloolefin homopolymer obtained by polymerization of bicycloheptene under the action of a metallocene catalyst and/or a copolymer of bicycloheptene and ethylene under the action of a metallocene catalyst Cycloolefin copolymers.
  • the hydrophilic modifier is polyetheramide, PA6, ethylene-acrylic acid copolymer, polyether polyol, polyethylene glycol octyl phenyl ether, hydroxyl-terminated stearamide, pentaerythritol stearate, One or several kinds of erucamide.
  • one or more of graft compatibilizer, antioxidant and lubricant are also included.
  • it also includes 1-5 parts by weight of compatibilizer, 0.1-0.5 parts of antioxidant and 0.1-0.5 parts of lubricant.
  • the graft compatibilizer is a graft polymer of a polar monomer and polypropylene.
  • the polar monomer in the present invention includes but not limited to one or more of maleic anhydride, acrylic acid and acrylate derivatives.
  • the antioxidants in the present invention include but not limited to one or more of hindered amines, hindered phenols or phosphites, calixarenes and thioesters.
  • the lubricant in the present invention includes but not limited to one or more of amides, metal soaps and low molecular weight esters.
  • thermoplastic polyolefin material protected by the present invention comprises the following steps:
  • thermoplastic polyolefin material After weighing each component in proportion, mix each component uniformly, then melt extrude at 180-250°C, granulate, and dry to obtain a thermoplastic polyolefin material.
  • the present invention protects the application of the above-mentioned thermoplastic polyolefin material in the preparation of plastic hand molds.
  • a plastic hand mold is made of the above-mentioned thermoplastic polyolefin material.
  • the preparation method of the above-mentioned plastic hand mold protected by the present invention comprises the following steps:
  • thermoplastic polyolefin material is dried at 80-120°C for 2-6 hours, then blow-molded at 180-250°C into the hand mold body and the hand mold support block, and then the hand mold body and the hand mold support block are welded by friction Or glued together to get a complete plastic hand mold product.
  • the present invention adopts cycloolefin copolymer with good heat resistance as the matrix, adds flat glass fiber and hydrophilic modifier, and improves the heat resistance and rigidity of the material through the adjustment of the components and their dosage.
  • the hydrophilic modifier and the flat glass fiber form a synergistic effect, which can improve the hydrophilic wetting effect on the surface of the material, and the prepared thermoplastic polyolefin material can be further prepared into a plastic hand mold, and the obtained plastic hand mold has excellent durability.
  • Thermal properties, light specific gravity, high surface hydrophilicity, good wettability, can evenly soak nitrile latex or latex, the thickness of the produced gloves is uniform, excellent performance, high yield, in addition, plastic gloves
  • the adhesion and easy-cleaning performance of the mold to the glove are significantly better than ceramic hand molds, which reduces the difficulty of demoulding, reduces the washing process of hand molds, and improves production efficiency; the material can also be reused, which significantly improves the environmental protection of hand molds sexuality, which greatly reduces the cost of using hand molds; the weight of plastic hand molds is significantly lower than that of ordinary ceramic hand molds, which can significantly reduce the energy consumption of glove production lines.
  • the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
  • Cycloolefin copolymer Cycloolefin copolymer obtained by copolymerization of bicycloheptene and ethylene under the action of metallocene catalyst, 5013LS, German TOPAS company.
  • Polypropylene resin N-Z30S, China Petrochemical Corporation.
  • Flat glass fiber A the thickness is 3 ⁇ m, the flatness ratio is 4:1, and the original length is 3-5 mm, China Jushi Co., Ltd.
  • Flat glass fiber B the thickness is 3 ⁇ m, the flatness ratio is 5:1, and the original length is 3-5 mm, China Jushi Co., Ltd.
  • Flat glass fiber C the thickness is 5 ⁇ m, the flat ratio is 2:1, and the original length is 3-5 mm, China Jushi Co., Ltd.
  • Flat glass fiber D the thickness is 2 ⁇ m, the flatness ratio is 6:1, and the original length is 3-5 mm, China Jushi Co., Ltd.
  • Flat glass fiber E the thickness is 4 ⁇ m, the flat ratio is 3:1, and the original length is 3-5 mm, China Jushi Co., Ltd.
  • Flat glass fiber F the thickness is 6 ⁇ m, the flatness ratio is 2:1, and the original length is 3-5 mm, China Jushi Co., Ltd.
  • Flat glass fiber G thickness 1.5 ⁇ m, flatness ratio 7:1, original length 3-5mm, China Jushi Co., Ltd.
  • Round glass fiber ECS10-03-508A, fiber diameter 10 ⁇ m, original length 3-5mm, China Jushi Co., Ltd.
  • Hydrophilic modifier A polyetheramide, weight average molecular weight 100,000, MH2030, Arkema, France.
  • Hydrophilic modifier B ethylene-acrylic acid copolymer, weight average molecular weight 100,000, PRIMACO 3460, Dow Chemical.
  • Hydrophilic modifier C hydroxyl-terminated stearylamide, weight average molecular weight 2000, Kingfa Technology.
  • Hydrophilic modifier D erucamide, with a weight average molecular weight of 1000, produced by Croda Hepp Chemicals.
  • Hydrophilic modifier E pentaerythritol stearate, weight-average molecular weight 5000, German Cogning.
  • Hydrophilic modifier F polyethylene glycol octylphenyl ether, weight average molecular weight 20000, Dow Chemical.
  • Graft compatibilizer maleic anhydride grafted polypropylene, CA 100, Arkema, France.
  • Antioxidant Antioxidant Thanox 1010+Thanox 168, Tianjin Lianlong New Material Co., Ltd.
  • Lubricant EBS, Zhongshan Huamingtai Chemical Co., Ltd.
  • thermoplastic polyolefin materials prepared in each example and comparative example include components calculated in parts by weight as shown in Tables 1 to 3 below.
  • thermoplastic polyolefin material comprises the steps:
  • thermoplastic polyolefin material After weighing each component in proportion, mix each component uniformly, then melt extrude at 180-200°C, granulate, and dry to obtain a thermoplastic polyolefin material.
  • thermoplastic polyolefin material that above-mentioned embodiment and comparative example are made is used for preparing plastic hand mold, comprises the steps:
  • thermoplastic polyolefin material place the thermoplastic polyolefin material at 80-120°C and dry it for 2-6 hours, then inject the hand mold body and the hand mold support block through the injection molding machine at 180-220°C; finally, pass the hand mold body and the hand mold support block through Join by friction welding or gluing to get a complete plastic hand mold product.
  • Hydrophilicity of the composite material According to the ISO 8296:2006-9 standard method, the dyne index is used to characterize the hydrophilicity of the material. The higher the dyne index, the better the hydrophilicity.
  • Solvent resistance of the hand mold Soak the hand mold in 5wt% nitric acid solution for one week, then soak it in 5wt% sodium hydroxide solution for one week, take it out and observe, the hand mold cannot be embrittled after being soaked in acid and alkali , pits, surface roughness, etc., if satisfied, record as "PASS".
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Example 8
  • Example 9 HDT 140 136 138 134 132 137 132 136 134 heat resistance PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS Hydrophilic 43 41 41 39 41 47 40 41 41 Yield/% 99.5 99 99.2 98 99 99.6 97 99.5 98
  • Example 10 Example 11
  • Example 12 Example 13
  • Example 14 Example 15
  • Example 16 Example 17
  • Example 18 Example 19 HDT 139 134 138 136 128 134 135 135 133 136 heat resistance PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS Hydrophilic 40 42 44 46 42 42 43 39.5 40 42 Yield/% 97 98 99.5 99.6 98 98.2 99.5 97 97.8 99.3
  • the plastic hand mold prepared by the present invention has the characteristics of light specific gravity, excellent heat resistance and solvent resistance, and the surface of the material is excellent in hydrophilicity and good in wettability.
  • the appearance and performance of the prepared glove are excellent, and the finished product rate reaches more than 97 percent stably.
  • Comparative Example 1 polypropylene resin was used instead of cycloolefin polymer. Since the polarity of polypropylene itself is too low, the hydrophilic effect is relatively poor, and HDT is also relatively low, resulting in a low yield. The thickness, aspect ratio, and retention length of the flat glass fibers used in Comparative Examples 2 and 3 are too high or too low, which will also affect the hydrophilicity, HDT and yield of the hand mold. Comparative Example 4 uses ordinary round glass fiber, and the hydrophilicity, HDT and yield of the hand mold are also significantly lower than flat glass fiber. The addition of hydrophilic modifier must be within a certain level to ensure better hydrophilic performance and yield.
  • Comparative Examples 5 to 8 too little or too much hydrophilic modifier is added, corresponding to the hydrophilicity of the hand mold. Both performance and yield are significantly lower.
  • polyethylene glycol octyl phenyl ether with too large molecular weight was used, and its heat resistance and migration to the surface of the material were poor, so the hydrophilicity, HDT and yield were also low.
  • No hydrophilic modifier was added in comparative example 10, comparative example 11 was pure cycloolefin polymer, and comparative example 12 adopted polypropylene resin instead of cycloolefin polymer, and did not contain hydrophilic modifier. These comparative examples made The hydrophilicity and yield of hand molds are poor.

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Abstract

本发明公开了一种热塑性聚烯烃材料及其制备方法和应用，采用环烯烃类共聚物作为基体，添加了扁平玻璃纤维和亲水改性剂，提高了材料的耐热性和刚性，亲水改性剂与扁平玻璃纤维形成协效作用，可以提高材料表面的亲水润湿效果，可以进一步制备塑料手模，所获得的塑料手模具有优异的耐热性能，比重轻，高表面亲水性能，具有较好的润湿性，可以均匀的浸湿丁腈胶乳或乳胶，所生产的手套厚薄均匀，性能优异，成品率较高，另外，塑料手模对手套的粘附性和易清洗性能都明显优于陶瓷手模，材料可以重复利用，显著提升了手模的环保性，大幅降低了手模的使用成本；塑料手模的重量显著低于普通陶瓷手模，可显著降低手套生产线的能耗。

Description

一种热塑性聚烯烃材料及其制备方法和应用 技术领域
本发明涉及高分子材料技术领域，更具体地，涉及一种热塑性聚烯烃材料及其制备方法和应用。
背景技术
手模是用于浸渍法生产塑胶手套的手形模具。采用液态胶乳为原料的橡胶手套的生产过程是：通过陶瓷手模沾挂塑胶液料，经烘干、脱模而制成。生产中使用的手模应该耐酸、耐碱、耐化学腐蚀，并具有一定的耐热震性。现有的手模本体一般是陶瓷制成，陶瓷手模制作方便、表面亲水性好，但是比重大(生产能耗高)、易碎且不耐用(使用周期一般低于1年)、无法回收利用(环保性差)。
聚丙烯因其优异的综合性能和良好的性价比、比重轻、耐酸碱性能优异、较宽的加工成型条件成为应用最为广泛的通用塑料之一。聚丙烯是典型的疏水性材料，水接触角大于90°，中国专利CN103756236A公开了利用聚丙烯为基体制得热塑性弹性体组合物，可以用于制备手模，中国专利CN107053564A公开了一种塑料手模的制作方法，利用氟塑料制备手模，提升塑料手模的耐磨性和耐酸性，但是这些塑料手模的耐热性能不好。
发明内容
本发明要解决的技术问题是克服现有塑料手模的耐热性能不好的缺陷和不足，提供一种热塑性聚烯烃材料，具有较好的耐热性能，可以用于制备塑料手模，获得耐热塑料手模，耐溶剂性优异，还具有较好的润湿性和较高的成品率。
本发明的又一目的是提供一种热塑性聚烯烃材料的制备方法。
本发明的另一目的是提供一种热塑性聚烯烃材料的应用。
本发明上述目的通过以下技术方案实现：
一种热塑性聚烯烃材料，包括如下按照重量份计算的组分：
环烯烃类共聚物                                60～90份；
扁平玻璃纤维                                  10～30份；
亲水改性剂                                    1～20份；
所述扁平玻璃纤维的厚度为2～5μm，扁平比为2：1～6：1，保留长度为0.1～0.5mm；
所述亲水改性剂为重均分子量50000～200000的含羧基、羟基、酯键、酰胺基聚合物和/或重均分子量500～10000的含羧基、羟基、酯键、酰胺基的C5～C50烷基寡聚物。
本发明利用环烯烃类共聚物作为基体，耐热性能较好，添加了一定配比的扁平玻璃纤维和亲水改性剂，其中扁平玻璃纤维可有效提升材料的耐热、变形和表面性能，扁平玻璃纤维添加量太少时，材料的耐热性和刚性相应差些；添加量过高时，刚性和耐热性提升不大，反而材料的外观和表面性能会下降；另外，亲水改性剂可与扁平玻璃纤维形成协效作用，提高材料表面的亲水润湿效果，当亲水改性剂添加量太少时，表面的亲水效果会相应差些；添加量过高时，亲水性能无显著提升，反而材料的加工性能和力学性能会恶化，本发明通过组分及其用量的调整获得具有优异的耐热性能的热塑性聚烯烃材料，还具有较好的润湿性和较高的成品率。
优选地，包括如下按照重量份计算的组分：
环烯烃类共聚物                             70～85份；
扁平玻璃纤维                               15～25份；
亲水改性剂                                 5～15份。
优选地，所述环烯烃类共聚物为双环庚烯(降冰片烯)作为主要功能单体的共聚物。
优选地，所述扁平玻璃纤维的厚度为3～4μm，扁平比为3：1～5：1，保留长度为0.1～0.3mm。
优选地，所述扁平玻璃纤维的原始长度为3～5mm。
优选地，所述原始长度为3～5mm的扁平玻璃纤维通过调节喂入挤出机螺杆的位置，得到保留长度为0.1～0.5mm的扁平玻璃纤维。
更优选地，所述环烯烃类共聚物为双环庚烯在金属茂催化剂作用下发生聚合得到的环烯烃类均聚物和/或双环庚烯和乙烯在金属茂催化剂作用下发生共聚合得到的环烯烃类共聚物。
优选地，所述亲水改性剂为聚醚酰胺、PA6、乙烯-丙烯酸共聚物、聚醚多元醇、聚乙二醇辛基苯基醚、端羟基硬酯酰胺、季戊四醇硬脂酸酯、芥酸酰胺中的一种或几种。
优选地，还包括接枝相容剂、抗氧剂、润滑剂中的一种或几种。
优选地，还包括按照重量份计算的相容剂1～5份、抗氧剂0.1～0.5份、润滑剂0.1～0.5份。
优选地，所述接枝相容剂为极性单体与聚丙烯的接枝聚合物。
本发明所述极性单体包括但不限于马来酸酐、丙烯酸和丙烯酸酯类衍生物中的一种或几种。
本发明所述抗氧剂包括但不限于受阻胺类、受阻酚类或亚磷酸酯类、杯芳烃类和硫代酯中的一种或几种。
本发明所述润滑剂包括但不限于酰胺类、金属皂类和低分子酯类中的一种或几种。
本发明保护上述热塑性聚烯烃材料的制备方法，包括如下步骤：
按比例称量各组分后，将各组分经过混合均匀，然后在180～250℃下熔融挤出、造粒，干燥后即得热塑性聚烯烃材料。
本发明保护上述热塑性聚烯烃材料在制备塑料手模中的应用。
一种塑料手模，由上述热塑性聚烯烃材料制得。
本发明保护上述塑料手模的制备方法，包括如下步骤：
首先将热塑性聚烯烃材料置于80～120℃烘干2～6h后，在180～250℃下吹塑成手模本体和手模支撑块，随后将手模本体和手模支撑块通过摩擦焊接或胶粘的形式连接起来，得到完整的塑料手模产品。
与现有技术相比，本发明的有益效果是：
本发明采用耐热性较好的环烯烃类共聚物作为基体，添加了扁平玻璃纤维和亲水改性剂，通过组分及其用量的调整，提高了材料的耐热性和刚性，另外，亲水改性剂与扁平玻璃纤维形成协效作用，可以提高材料表面的亲水润湿效果，所制得的热塑性聚烯烃材料可以进一步制备塑料手模，所获得的塑料手模具有优异的耐热性能，比重轻，高表面亲水性能，具有较好的润湿性，可以均匀的浸湿丁腈胶乳或乳胶，所生产的手套厚薄均匀，性能优异，成品率较高，另外，塑料手模对手套的粘附性和易清洗性能都明显优于陶瓷手模，降低了脱模难度，减少了手模洗涤程序，提升了生产效率；材料还可以重复利用，显著提升了手模的环保性，大幅降低了手模的使用成本；塑料手模的重量显著低于普通陶瓷手模，可显著降低手套生产线的能耗。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。
各实施例和对比例使用的原料：
环烯烃类共聚物：双环庚烯和乙烯在金属茂催化剂作用下发生共聚合得到的环烯烃类共聚物，5013LS，德国TOPAS公司。
聚丙烯树脂：N-Z30S，中国石油化工集团公司。
扁平玻璃纤维A：厚度为3μm，扁平比为4：1，原始长度3～5mm，中国巨石股份有限公司。
扁平玻璃纤维B：厚度为3μm，扁平比为5：1，原始长度3～5mm，中国巨石股份有限公司。
扁平玻璃纤维C：厚度为5μm，扁平比为2：1，原始长度3～5mm，中国巨石股份有限公司。
扁平玻璃纤维D：厚度为2μm，扁平比为6：1，原始长度3～5mm，中国巨石股份有限公司。
扁平玻璃纤维E：厚度为4μm，扁平比为3：1，原始长度3～5mm，中国巨石股份有限公司。
扁平玻璃纤维F：厚度为6μm，扁平比为2：1，原始长度3～5mm，中国巨石股份有限公司。
扁平玻璃纤维G：厚度为1.5μm，扁平比为7：1，原始长度3～5mm，中国巨石股份有限公司
圆形玻璃纤维：ECS10-03-508A，纤维直径10μm，原始长度3～5mm，中国巨石股份有限公司。
亲水改性剂A：聚醚酰胺，重均分子量100000，MH2030，法国阿科玛。
亲水改性剂B：乙烯-丙烯酸共聚物，重均分子量100000，PRIMACO 3460，陶氏化学。
亲水改性剂C：端羟基硬酯酰胺，重均分子量2000，金发科技。
亲水改性剂D：芥酸酰胺，重均分子量1000，禾大西普化学。
亲水改性剂E：季戊四醇硬脂酸酯，重均分子量5000，德国科宁。
亲水改性剂F：聚乙二醇辛基苯基醚，重均分子量20000，陶氏化学。
接枝相容剂：马来酸酐接枝聚丙烯，CA 100，法国阿科玛。
抗氧剂：抗氧剂Thanox 1010+Thanox 168，天津利安隆新材料股份有限公司。
润滑剂：EBS，中山华明泰化工股份有限公司。
实施例1～19和对比例1～12
各实施例和对比例制得的热塑性聚烯烃材料，包括如下表1～表3所示按照重量份计算的组分。
表1各实施例的组分及其重量份
Figure PCTCN2022107860-appb-000001
Figure PCTCN2022107860-appb-000002
Figure PCTCN2022107860-appb-000003
表2各对比例的组分及其重量份
Figure PCTCN2022107860-appb-000004
Figure PCTCN2022107860-appb-000005
上述热塑性聚烯烃材料的制备方法，包括如下步骤：
按比例称量各组分后，将各组分经过混合均匀，然后在180～200℃下熔融挤出、造粒，干燥后即得热塑性聚烯烃材料。
应用
进一步将上述实施例和对比例制得的热塑性聚烯烃材料用于制备塑料手模，包括如下步骤：
首先将热塑性聚烯烃材料置于80～120℃烘干2～6h后，通过注塑机在180～220℃下分别注塑出手模本体和手模支撑块；最后将手模本体和手模支撑块通过摩擦焊接或胶粘的形式连接起来，得到完整的塑料手模产品。
性能测试
1、测试方法
上述实施例和对比例的复合材料，或者由上述复合材料制成的手模均通过下述性能测试方法进行测试：
(1)复合材料的亲水性：按照ISO 8296：2006-9标准方法，采用达因指数表征材料亲水性，达因指数越高，亲水性越好。
(2)复合材料的耐热性能：按照ISO 75-2:2003标准B方法，测试材料的热变形温度(HDT)，HDT越高，材料耐热性能越好。
(3)手模成品率：采用挂水法测试，统计30000个手套的挂水测试漏液的比率。
(4)手模耐热性：将手模置于120℃烘箱中烘烤8h，评估手模的变形或软化情况，手模经烘烤后不能出现明显变形或软化现象，则记录为“PASS”。
(5)手模耐溶剂性：将手模先置于5wt％硝酸溶液中浸泡一周后再置于5wt％氢氧化钠溶液中浸泡一周，取出观察，手模经酸碱浸泡后不能出现脆化、凹坑、表 面粗糙等现象，若满足则记录为“PASS”。
2、测试结果
表4各实施例和对比例制得的塑料手模的测试结果
  实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 实施例7 实施例8 实施例9
HDT 140 136 138 134 132 137 132 136 134
耐热性 PASS PASS PASS PASS PASS PASS PASS PASS PASS
耐溶剂性 PASS PASS PASS PASS PASS PASS PASS PASS PASS
亲水性 43 41 41 39 41 47 40 41 41
成品率/％ 99.5 99 99.2 98 99 99.6 97 99.5 98
  实施例10 实施例11 实施例12 实施例13 实施例14 实施例15 实施例16 实施例17 实施例18 实施例19
HDT 139 134 138 136 128 134 135 135 133 136
耐热性 PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS
耐溶剂性 PASS PASS PASS PASS PASS PASS PASS PASS PASS PASS
亲水性 40 42 44 46 42 42 43 39.5 40 42
成品率/％ 97 98 99.5 99.6 98 98.2 99.5 97 97.8 99.3
Figure PCTCN2022107860-appb-000006
从上述表4的实施例测试数据可以看出，本发明制得的塑料手模，具有比重轻、耐热性和耐溶剂性优异的特点，材料的表面亲水性优异，润湿性好，制备的手套的外观和性能优良，成品率稳定达到97％以上。
对比例1采用聚丙烯树脂代替环烯烃聚合物，由于聚丙烯本身的极性太低，因此亲水性效果也相对较差，同时HDT也相对更低，导致成品率较低。对比例 2、3使用的扁平玻璃纤维的厚度、扁平比、保留长度太高或太低，同样会影响手模的亲水性、HDT和成品率。对比例4使用普通圆形玻璃纤维，手模的亲水性、HDT和成品率明显也低于扁平玻璃纤维。亲水改性剂的添加必须在一定水平内才能保证较好的亲水性能和成品率，对比例5～8中，添加的亲水改性剂太少或太多，对应手模的亲水性和成品率都明显更低。对比例9使用了分子量过大的聚乙二醇辛基苯基醚，其耐热性能和迁移至材料表面的效果较差，因此亲水性、HDT和成品率也较低。对比例10中未添加亲水改性剂，对比例11为单纯的环烯烃聚合物，对比例12采用聚丙烯树脂代替环烯烃聚合物，且不含有亲水改性剂，这些对比例制得的手模的亲水性和成品率都较差。
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。

Claims (10)

  1. 一种热塑性聚烯烃材料，其特征在于，包括如下按照重量份计算的组分：
    环烯烃类共聚物                                 60～90份；
    扁平玻璃纤维                                   10～30份；
    亲水改性剂                                     1～20份；
    所述扁平玻璃纤维的厚度为2～5μm，扁平比为2：1～6：1，保留长度为0.1～0.5mm；
    所述亲水改性剂为重均分子量50000～200000的含羧基、羟基、酯键、酰胺基聚合物和/或重均分子量500～10000的含羧基、羟基、酯键、酰胺基的C5～C50烷基寡聚物。
  2. 根据权利要求1所述热塑性聚烯烃材料，其特征在于，包括如下按照重量份计算的组分：
    环烯烃类共聚物                              70～85份；
    扁平玻璃纤维                                15～25份；
    亲水改性剂                                  5～15份。
  3. 根据权利要求1所述热塑性聚烯烃材料，其特征在于，所述环烯烃类共聚物为双环庚烯作为主要功能单体的共聚物。
  4. 根据权利要求1所述热塑性聚烯烃材料，其特征在于，所述扁平玻璃纤维的厚度为3～4μm，扁平比为3：1～5：1，保留长度为0.1～0.3mm。
  5. 根据权利要求1所述热塑性聚烯烃材料，其特征在于，所述亲水改性剂为聚醚酰胺、PA6、乙烯-丙烯酸共聚物、聚醚多元醇、聚乙二醇辛基苯基醚、端羟基硬酯酰胺、季戊四醇硬脂酸酯、芥酸酰胺中的一种或几种。
  6. 根据权利要求1所述热塑性聚烯烃材料，其特征在于，还包括接枝相容剂、抗氧剂、润滑剂中的一种或几种。
  7. 权利要求1～6任一项所述热塑性聚烯烃材料的制备方法，其特征在于，包括如下步骤：
    按比例称量各组分后，将各组分经过混合均匀，然后在180～250℃下熔融挤出、造粒，干燥后即得热塑性聚烯烃材料。
  8. 权利要求1～6任一项所述热塑性聚烯烃材料在制备塑料手模中的应用。
  9. 一种塑料手模，其特征在于，由权利要求1～6任一项所述热塑性聚烯烃 材料制得。
  10. 权利要求9所述塑料手模的制备方法，其特征在于，包括如下步骤：
    首先将热塑性聚烯烃材料置于80～120℃烘干2～6h后，在180～250℃下吹塑成手模本体和手模支撑块，随后将手模本体和手模支撑块通过摩擦焊接或胶粘的形式连接起来，得到完整的塑料手模产品。
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