WO2024032433A1 - 一种低后收缩聚丙烯材料及其制备方法 - Google Patents

一种低后收缩聚丙烯材料及其制备方法 Download PDF

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WO2024032433A1
WO2024032433A1 PCT/CN2023/110666 CN2023110666W WO2024032433A1 WO 2024032433 A1 WO2024032433 A1 WO 2024032433A1 CN 2023110666 W CN2023110666 W CN 2023110666W WO 2024032433 A1 WO2024032433 A1 WO 2024032433A1
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shrinkage
polypropylene
low
polypropylene material
post
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PCT/CN2023/110666
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English (en)
French (fr)
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王亚南
杨磊
尹朝清
张爽爽
杨泽
陆湛泉
杨霄云
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上海金发科技发展有限公司
江苏金发科技新材料有限公司
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Publication of WO2024032433A1 publication Critical patent/WO2024032433A1/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
    • 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
    • C08L23/12—Polypropene
    • 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
    • C08L23/14—Copolymers of propene
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K5/00—Casings, cabinets or drawers for electric apparatus
    • H05K5/02—Details
    • H05K5/0217—Mechanical details of casings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • the invention belongs to the field of polymer materials, and specifically relates to a low post-shrinkage polypropylene material and a preparation method thereof.
  • Polypropylene material is currently the most widely used general-purpose plastic.
  • polypropylene has obvious disadvantages in some performance aspects, such as large shrinkage and unstable dimensions.
  • fillers such as mineral powder and fiber are usually added in the industry.
  • mineral powder The addition of fiber fillers usually affects the surface properties of the product.
  • polypropylene composite materials prepared from the most commonly used talc powder generally have poor surface gloss, while polypropylene materials prepared from glass fiber composites often have serious surface floating fibers.
  • these traditional shrinkage adjustment components actually only reduce the original shrinkage of the material, but there will be a certain amount of post-shrinkage after the material size is stable. This part of the post-shrinkage is actually the slow movement and crystallization of the polymer molecular chains. As a result, if the product undergoes a heating process during use, the shrinkage will be greater.
  • CN111087689A discloses a polypropylene composite material for home appliance casings and a preparation method thereof. By adding components such as whiskers, talc powder, nucleating agents, etc., the obtained polypropylene composite has high gloss, scratch resistance, and low post-shrinkage. Characteristics, but as mentioned above, this material has a larger post-shrinkage rate after high-temperature annealing; CN111484671A discloses a low post-shrinkage polypropylene composite material for vehicles and a preparation method thereof.
  • the invention is formulated with ultra-high molecular weight Components such as polyethylene, talc, and nano-glass can achieve low post-shrinkage effects.
  • the ultra-high molecular weight polyethylene used in this product has poor processability and low surface gloss, making it unsuitable for some exterior plastic parts. product.
  • the object of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a low post-shrinkage polypropylene material.
  • the product components do not introduce the common filling shrinkage adjustment components in the prior art solutions, but Specific random polypropylene and long carbon chain polyamide are introduced into the polypropylene resin matrix.
  • Specific random polypropylene and long carbon chain polyamide are introduced into the polypropylene resin matrix.
  • the post-shrinkage effect can also maintain the surface gloss and cleanliness of the product within a good range, and has a wide range of applications.
  • a low post-shrinkage polypropylene material contains the following components by weight:
  • the low shrinkage regulator includes random copolymerized polypropylene and polyamide, and the molar ratio of methylene groups to amide groups in the molecular chain of the polyamide is 10 to 12.
  • the molar ratio of methylene and amide groups in the molecular chain of the polyamide can be directly obtained from the structural formula of the repeating unit of the polyamide;
  • the structural formula of the polyamide can be obtained by melting, dissolving, separating and purifying the polyamide in the low post-shrinkage polypropylene material, and then using infrared spectrum analysis and mass spectrometry analysis to test.
  • the components of the low post-shrinkage polypropylene material of the present invention in order not to introduce components such as mineral powder or glass fiber that may cause a decrease in the apparent performance of the product, random copolymerized polypropylene and polyamide are used. These two components It can be fully entangled with the short molecular chains in the polypropylene resin matrix. At the same time, the amide groups it contains can form a certain amount of hydrogen bonds in the polypropylene resin matrix, thereby increasing the number of molecules in the compounded mixture of each component. It is difficult to move between chains, and the two themselves can also achieve heterogeneous nucleation under the action of initiators during the product preparation process. There will be no phase separation or incompatibility problems, which effectively reduces the problem of product size stabilization. (especially after heat annealing treatment), while ensuring the surface properties of the product.
  • the inventor found that if the added amount of the low shrinkage regulator is too low, it will be difficult to achieve a good low post-shrinkage rate, but if the added amount is too high, the compatibility of the product components will be problematic. (It is difficult to avoid even if the compatibilizer is increased). Not only the post-shrinkage rate cannot achieve the optimal effect, but it may also cause problems with the surface gloss of the product.
  • the molar ratio of methylene to amide groups in the molecular chain of polyamide is a key factor in entanglement with the polypropylene resin matrix.
  • the ratio is too small, the density of the amide groups will decrease, so that the relationship between the amide groups The reduction of hydrogen bonds generated between them is not conducive to reducing post-shrinkage. If the ratio is too high and the amide group content is high, it will also cause compatibility problems.
  • the molar ratio of methylene groups to amide groups in the molecular chain of the polyamide is 10 to 11.
  • the mass ratio of random copolymerized polypropylene and polyamide in the low shrinkage regulator is (7-9): (1-2).
  • the content of polyamide or random copolymerized polypropylene in the low-shrinkage regulator cannot be too high, because the polypropylene resin matrix and polyamide in the product components are actually in a state of entanglement with each other, which can prevent the molecular chain segments from changing after heating. If there is too much random copolymerized polypropylene, it will be difficult to generate enough hydrogen bonds in the product, and then it will be more difficult to reduce the shrinkage to the ideal level. If there is too much polyamide, it will be difficult to produce enough hydrogen bonds in the product components. The dispersion in the product will be significantly reduced, and the surface gloss of the product may also be reduced. The inventor optimized the two and found that when the above ratio is used, the gloss and post-shrinkage of the product are relatively stable and can be maintained within an ideal range.
  • the random copolymerized polypropylene is a random propylene-ethylene copolymer.
  • the random copolymerized polypropylene is in accordance with GB/T 3682.1-2018 "Testing Methods for Plastic Thermoplastic Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR)" at 230°C, 2.16
  • MFR Plastic Thermoplastic Melt Mass Flow Rate
  • MVR Melt Volume Flow Rate
  • any type of random copolymerized polypropylene that can be entangled with polyamide can be used in the product components of the present invention.
  • the melt mass flow rate of random copolymerized polypropylene is 10-30g/min, the post-shrinkage rate of the product can be lower.
  • the polypropylene is at least one of block copolymerized polypropylene and homopolymerized polypropylene.
  • the polypropylene is tested in accordance with GB/T 3682.1-2018 "Testing Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastic Thermoplastics" at 230°C and 2.16kg.
  • the melt mass flow rate is 1 ⁇ 60g/10min.
  • the compatibilizer is maleic anhydride graft.
  • the maleic anhydride graft is ethylene-propylene copolymer grafted with maleic anhydride, ethylene-octene copolymer grafted with maleic anhydride, ethylene-butene copolymer grafted with maleic anhydride, polypropylene At least one of grafted maleic anhydride and polyethylene grafted maleic anhydride.
  • maleic anhydride grafts have a good effect on improving the compatibility of random copolymerization of polypropylene and polyamide (especially polyamide) in polypropylene and the compatibility between the two. It can make the two key components in the low shrinkage regulator well compatible and evenly entangled with the molecular chains of the polypropylene resin matrix.
  • the initiator is at least one of an organic peroxide initiator, an azo initiator, and a benzoyl peroxide initiator.
  • the processing aid includes at least one of an antioxidant and a lubricant.
  • the antioxidant is at least one of a hindered phenolic antioxidant and a phosphite antioxidant.
  • the lubricant is erucamide.
  • the processing aid is a mixture of hindered phenolic antioxidants, phosphite antioxidants and lubricants, and the mass ratio of the three is 1:2:2.
  • Another object of the present invention is to provide a preparation method of the low post-shrinkage polypropylene material, which includes the following steps:
  • the preparation method of the low post-shrinkage polypropylene material of the present invention has simple operation steps and can realize industrial-scale production.
  • the mixing speed is 600-1200 rpm, the time is 5-8 min, and the temperature is 40-60°C.
  • the temperature of the twin-screw extruder during extrusion is 210 to 230°C.
  • the low shrinkage regulator, compatibilizer and initiator are added in the form of masterbatch.
  • the optimal melting and crystallization temperature can be selected to achieve early crystallization heterogeneous nucleation.
  • the masterbatch is mixed with the polypropylene resin matrix, the hydrogen bond strength generated is better, which further suppresses the problem of possible phase separation. Not only can it further It can inhibit the post-shrinkage of the product and make its surface gloss comparable to that of pure polypropylene products.
  • the preparation method of the masterbatch is:
  • the mixing speed in step (1) is 600-800 rpm and the time is 3-5 min; the temperature during one-stage extrusion is 190-200°C.
  • the mixing speed in step (2) is 400 to 600 rpm, the time is 1 to 3 minutes, and the temperature during the two-stage extrusion is 200 to 220°C.
  • Another object of the present invention is to provide the application of the low post-shrinkage polypropylene material in the preparation of home appliance parts.
  • the product of the present invention not only has surface properties (glossiness, appearance) that meet the high appearance requirements of components in the field of home appliances, but can also ensure a low post-shrinkage rate after long-term use or heat treatment, and is especially suitable for preparing some Such as home appliance casings and other components that are used in changing environments but have greater requirements for dimensional stability.
  • the invention provides a low post-shrinkage polypropylene material.
  • the material introduces a specific low-shrinkage regulator into the polypropylene, and the random copolymerized polypropylene and polyamide contained in the material can form a composite molecular chain between the three parties with the polypropylene. Entanglement, thereby effectively suppressing the post-shrinkage effect after the product is dimensionally stabilized and even after heat treatment, and the dimensional stability is strong and durable; since there is no need to add fillers such as minerals or fibers to the components to maintain product dimensional stability, the appearance and performance of the product are also can be guaranteed.
  • the invention also provides a preparation method of the low post-shrinkage polypropylene material and its application in preparing home appliance parts.
  • the raw material information used in the examples and comparative examples of the present invention is as follows:
  • Polypropylene 1 Homopolypropylene, PPH-T03 product produced by Zhenhai Refining and Chemical Co., Ltd., with a melt mass flow rate of 2.0g/10min at 230°C and 2.16kg load;
  • Polypropylene 2 Block copolymer polypropylene, PP K8003 product produced by Yangzi Petrochemical, with a melt mass flow rate of 2.2g/10min at 230°C and 2.16kg load;
  • Polypropylene 3 Homopolymer polypropylene, PP M60T product produced by Zhenhai Refining and Chemical Co., Ltd., with a melt mass flow rate of 60.0g/10min at 230°C and 2.16kg load;
  • Polypropylene 4 block copolymer polypropylene, PP M60RHC product produced by Zhenhai Refining and Chemical Co., Ltd., at 230°C, The melt mass flow rate under 2.16kg load is 59.8g/10min;
  • Random copolymerized polypropylene 1 Random propylene-ethylene copolymerized polypropylene PP RP346R, a product produced by LyondellBasell Industries, with a melt mass flow rate of 24g/10min;
  • Random copolymerized polypropylene 2 Random propylene-ethylene copolymerized polypropylene PP SM198, produced by Lotte Chemical Titan (M) Sdn. Bhd., with a melt mass flow rate of 2.3g/10min;
  • Random copolymerized polypropylene 3 Random propylene-ethylene copolymerized polypropylene PP K4912, a product produced by Shanghai Secco, with a melt mass flow rate of 12g/10min;
  • Random copolymerized polypropylene 4 Random propylene-ethylene copolymerized polypropylene PP R340S, a product produced by Braskem, with a melt mass flow rate of 45g/10min;
  • Polyamide 1 Nylon 1012, the molar ratio of methylene to amide groups in the molecular chain is 11, a product produced by Shandong Dongchen Ruisen;
  • Polyamide 2 Nylon 1010, the molar ratio of methylene to amide groups in the molecular chain is 10, a product produced by Shandong Dongchen Ruisen;
  • Polyamide 3 nylon 1212, the ratio of methylene to amide groups in the molecular chain is 12, a product produced by Shandong Dongchen Ruisen;
  • Organic peroxide initiator Organic peroxide initiator Enox 101, China Qiangsheng Co., Ltd.
  • Processing aids a mixture of commercially available hindered phenolic antioxidants, commercially available phosphite antioxidants, and commercially available erucamide, the mass ratio of the three is 1:2:2;
  • Example 17 The only difference between Example 17 and Example 1 is that the preparation method of the polypropylene composite material in this example is:
  • the preparation method of the masterbatch is:
  • the low post-shrinkage polypropylene material of the present invention has good stability. After heat treatment, it still has a low post-shrinkage rate (the shrinkage rate after 6 hours is less than 1%), and it can also maintain good gloss. From the comparison between Example 1 and Example 17, it can be seen that when the low shrinkage regulator is combined with When introduced in the form of masterbatch to prepare products, the gloss retention effect is better and is closer to the original polypropylene resin matrix. From the comparison of Examples 5 to 7, it can be seen that the melt mass flow rate of the random copolymerized polypropylene in the product components has a certain impact on the performance of the product.
  • the product The performance can take into account good gloss and low post-shrinkage; from the product performance of Example 1, Example 8, Example 9, and Comparative Example 4, it can be seen that the number of methylene groups in the molecular chain of polyamide and the amide group The ratio is a key factor affecting product performance. Only when the ratio is maintained at 10 to 12 can polyamide exert its ideal effect. From the comparison of product performance in Example 1 and Examples 10 to 14, it can be seen that when the random copolymerized polypropylene and The total amount of polyamide is constant, but when the ratio changes, the gloss and post-shrinkage rate of the product will also be affected.
  • the gloss of the product can only be maintained when the ratio of the two is (7 ⁇ 9): (1 ⁇ 2) Both the degree and post-shrinkage rate can be maintained in a stable and ideal range.
  • the product of Comparative Example 1 does not introduce a low post-shrinkage regulator, and the post-shrinkage rate of the product is higher;
  • Comparative Examples 2 and 3 only introduce random copolymerized polypropylene and polyamide as conditioning components respectively, of which Comparative Example 2
  • the shrinkage rate of the product after 6 hours reached 3.2%, which is not significantly different from the product of Comparative Example 1.
  • the post-shrinkage rate of the product of Comparative Example 3 has been reduced to a certain extent, it is still difficult to achieve the ideal shrinkage effect after adjustment.

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Abstract

本发明涉及一种低后收缩聚丙烯材料及其制备方法，属于高分子材料领域。本发明所述低后收缩聚丙烯材料在聚丙烯中引入特定的低收缩调节剂，其含有的无规共聚聚丙烯和聚酰胺可以和聚丙烯发生三者间的复合分子链纠缠，从而有效抑制产品尺寸稳定后乃至加热处理后的后收缩效应，尺寸稳定持久性强；由于组分中并未需要加入诸如矿物或纤维等填料以维持产品尺寸稳定，因此产品的外观性能也能得到保障。本发明还公开了所述低后收缩聚丙烯材料的制备方法及其在制备家电零部件中的应用。

Description

一种低后收缩聚丙烯材料及其制备方法 技术领域
本发明属于高分子材料领域，具体涉及一种低后收缩聚丙烯材料及其制备方法。
背景技术
聚丙烯材料是目前应用最多、最广泛的通用塑料，近年来随着国内改性聚丙烯材料的普及率越来越高，聚丙烯材料工程化比例越来越高。但是聚丙烯在一些性能方面有明显的劣势，比如收缩率大、尺寸不稳定等，行业内为了降低聚丙烯的收缩率改善尺寸稳定性，通常会加入矿粉、纤维等填充物，但是矿粉纤维类填充物的加入通常会影响产品的表面性质，如最常用的滑石粉制备的聚丙烯复合材料一般表面光泽度较差，而玻璃纤维复合制备的聚丙材料常常出现表面浮纤严重的情况。此外，这些传统的收缩率调节组分实际上只降低了材料的原始收缩率，但是材料尺寸稳定以后还会有一定的后收缩，这部分后收缩实际上是聚合物分子链在缓慢运动结晶的结果，若产品在使用过程中需要经历加热过程，则收缩程度更大。
CN111087689A公开了一种家电外壳用聚丙烯复合材料及其制备方法，通过加入晶须、滑石粉、成核剂等组分，得到的聚丙烯复合物具有高光泽、耐刮擦、低后收缩的特点，但正如上所述，这种材料在高温退火以后的后收缩率较大；CN111484671A公开了一种低后收缩率车用聚丙烯复合材料及其制备方法，该发明通过复配超高分子量聚乙烯、滑石粉、纳米玻璃体等组分达到低后收缩的效果，但是该产品中用到的超高分子量聚乙烯加工性差，并且表面光泽度不高，并不适用于一些外观型塑料零部件产品。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种低后收缩聚丙烯材料，该产品组分中不引入现有技术方案中常见的填充类收缩率调节组分，而是在聚丙烯树脂基体中引入特定的无规聚丙烯及长碳链聚酰胺，通过这两者与聚丙烯树脂基体的复合分子链纠缠效应，进而抑制产品在尺寸稳定后因分子链缓慢运动而产生的后收缩效应，同时也能维持产品表面光泽度及洁净度在较好的范围之内，应用范围广阔。
为实现上述目的，本发明采取的技术方案为：
一种低后收缩聚丙烯材料，包含如下重量份的组分：
聚丙烯70～90份、低收缩调节剂15～25份、相容剂0.5～1.5份、引发剂0.03～0.05份、加工助剂0.2～0.6份；
所述低收缩调节剂中包括无规共聚聚丙烯和聚酰胺，所述聚酰胺的分子链中亚甲基与酰胺基的摩尔比为10～12。
所述聚酰胺上分子链的亚甲基及酰胺基的摩尔比可以通过聚酰胺的重复单元的结构分子式直接得到；
优选地，所述聚酰胺的结构分子式可通过将所述低后收缩聚丙烯材料中的聚酰胺经熔融、溶解分离提纯后，采用红外光谱分析及质谱分析测试得到。
本发明所述低后收缩聚丙烯材料的组分中，为了不引入矿物粉或者玻璃纤维等可能造成产品表观性能下降的成分，采用无规共聚聚丙烯和聚酰胺搭配，这两种组分可充分与聚丙烯树脂基体中的分子短链相互纠缠在一起，同时其含有的酰胺基团在聚丙烯树脂基体内可形成一定量的氢键，从而增加了各组分复合后的混合物中分子链间相互运动的难度，而这两者本身在产品制备过程中也能在引发剂的作用下实现异相成核，不会出现相分离或不相容的问题，有效降低了产品尺寸稳定后(尤其是经过加热退火处理后)的后收缩率，同时可保障产品的表面性能。
此外，经过发明人组分探讨后发现，所述低收缩调节剂的添加量过低则难以实现良好的低后收缩率，但如果添加量过高，产品组分的相容性将出现问题 (即使相容剂增多也难以避免)，不仅后收缩率无法达到最优效果，可能还会造成产品表面光泽度问题。另一方面，聚酰胺中分子链中的亚甲基与酰胺基的摩尔比是与聚丙烯树脂基体发生纠缠的关键因素，如果比值过小，会造成酰胺基团密度降低，这样酰胺基团之间产生的氢键减少，不利于降低后收缩，而如果比值过高，酰胺基含量较高，同样会造成相容性问题。
优选地，所述聚酰胺的分子链中亚甲基与酰胺基的摩尔比为10～11。
优选地，所述低收缩调节剂中无规共聚聚丙烯和聚酰胺的质量比为(7～9)：(1～2)。
低收缩调节剂中聚酰胺或无规共聚聚丙烯的含量不能过高，因为产品组分中聚丙烯树脂基体、聚酰胺两者实际处于一种相互纠缠的状态才可以阻碍分子链段在加热后的排列重组，如果无规共聚聚丙烯过多，则难以在产品中生成足够的氢键，其后收缩率降低至理想程度的难度加大，而如果聚酰胺过多，则其在产品组分中的分散性将显著降低，产品表面光泽度也可能会有所降低。经发明人对两者进行优选，以上述配比搭配时产品的光泽度和后收缩率均较为稳定，可维持在一个理想的范围。
优选地，所述无规共聚聚丙烯为无规丙烯-乙烯共聚物。
更优选地，所述无规共聚聚丙烯的按照GB/T 3682.1-2018《塑料热塑性塑料熔体质量流动速率(MFR)和熔体体积流动速率(MVR)的测试方法》，在230℃，2.16kg条件下的熔体质量流动速率为10～30g/10min。
经发明人实验筛选，发现只要可与聚酰胺实现纠缠结合的无规共聚聚丙烯种类均可在本发明所述产品组分中使用。而在此基础上，若无规共聚聚丙烯的熔体质量流动速率在10～30g/min，可以使产品的后收缩率更低。
优选地，所述聚丙烯为嵌段共聚聚丙烯、均聚聚丙烯中的至少一种。
优选地，所述聚丙烯根据按照GB/T 3682.1-2018《塑料热塑性塑料熔体质量流动速率(MFR)和熔体体积流动速率(MVR)的测试方法》，在230℃，2.16kg条件下的熔体质量流动速率为1～60g/10min。
优选地，所述相容剂为马来酸酐接枝物。
更优选地，所述马来酸酐接枝物为乙烯-丙烯共聚物接枝马来酸酐、乙烯-辛烯共聚物接枝马来酸酐、乙烯-丁烯共聚物接枝马来酸酐、聚丙烯接枝马来酸酐、聚乙烯接枝马来酸酐中的至少一种。
经发明实验，马来酸酐接枝物对于无规共聚聚丙烯和聚酰胺(尤其是聚酰胺)在聚丙烯中各自的相容性以及两者之间的相容性提升均有较好效果，可使得低收缩调节剂中的两种关键组分很好地相容并与聚丙烯树脂基体分子链实现均匀地纠缠。
优选地，所述引发剂为有机过氧化物类引发剂、偶氮类引发剂、过氧化苯甲酰类引发剂中的至少一种。
优选地，所述加工助剂包括抗氧剂、润滑剂中的至少一种。
更优选地，所述抗氧剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂中的至少一种。
更优选地，所述润滑剂为芥酸酰胺。
更优选地，所述加工助剂为受阻酚类抗氧剂、亚磷酸酯类抗氧剂和润滑剂的混合物，三者的质量比为1:2:2。
本发明的另一目的在于提供所述低后收缩聚丙烯材料的制备方法，包括以下步骤：
将各组分混合均匀，随后置入双螺杆挤出机中挤出，经冷却、切粒后，即得所述低后收缩聚丙烯材料。
本发明所述低后收缩聚丙烯材料的制备方法操作步骤简单，可实现工业化规模生产。
优选地，所述混合时的速率为600～1200rpm，时间为5～8min，温度为40～60℃。
优选地，所述双螺杆挤出机在挤出时的温度为210～230℃。
优选地，所述各组分混合时，低收缩调节剂、相容剂和引发剂以母粒形式加入。
发明人发现，当低收缩调节剂中的无规共聚聚丙烯和聚酰胺预先混合，并在相容剂和引发剂的作用下制备成母粒引入制备最终产品，无规共聚聚丙烯和聚酰胺可以选择最佳的熔融结晶温度实现提前结晶异相成核，此时母粒与聚丙烯树脂基体混合时，其产生的氢键作用强度更好，进一步抑制了相性可能分离的问题，不仅可进一步抑制产品的后收缩，还能使其表面光泽度与纯聚丙烯产品相当。
更优选地，所述母粒的制备方法为：
(1)将无规共聚聚丙烯、相容剂和引发剂混合均匀，随后置入双螺杆挤出机中进行一段挤出，得第一产物；
(2)将第一产物和聚酰胺混合均匀，随后置入双螺杆挤出机中进行二段挤出，切粒，即得所述母粒。
更优选地，所述步骤(1)中混合时的速率为600～800rpm，时间为3～5min；一段挤出时的温度为190～200℃。
更优选地，所述步骤(2)中混合时的速率为400～600rpm，时间为1～3min，二段挤出时的温度为200～220℃。
本发明的另一目的在于提供所述低后收缩聚丙烯材料在家电零部件制备中的应用。
本发明所述产品不仅表面性能(光泽度、表观度)符合家电领域零部件的外观高要求，同时在经过长时间使用或者热处理后依然可保障较低的后收缩率，尤其适用于制备一些如家电外壳等使用环境多变，但对尺寸稳定性又有较大要求的零部件。
与现有技术相比，本发明的有益效果为：
本发明提供了一种低后收缩聚丙烯材料，该材料在聚丙烯中引入特定的低收缩调节剂，其含有的无规共聚聚丙烯和聚酰胺可以和聚丙烯发生三者间的复合分子链纠缠，从而有效抑制产品尺寸稳定后乃至加热处理后的后收缩效应，尺寸稳定持久性强；由于组分中并未需要加入诸如矿物或纤维等填料以维持产品尺寸稳定，因此产品的外观性能也能得到保障。本发明还提供了所述低后收缩聚丙烯材料的制备方法及其在制备家电零部件中的应用。
具体实施方式
为更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。其目的在于详细地理解本发明的内容，而不是对本发明的限制。本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。本发明实施所涉及的实验试剂及仪器，除非特别说明，均为常用的普通试剂及仪器。
本发明实施例(除实施例17)及对比例中聚丙烯复合材料的制备方法为：
将各组分在高混机中以800rpm速率、50℃下混合5～8min至均匀，随后置入双螺杆挤出机中控制温度为190～220℃挤出，经冷却、切粒后，即得所述低后收缩聚丙烯材料。
本发明实施例及对比例中使用的原料信息如下：
聚丙烯1：均聚聚丙烯，镇海炼化生产PPH-T03产品，在230℃、2.16kg负荷下的熔体质量流动速率为2.0g/10min；
聚丙烯2：嵌段共聚聚丙烯，扬子石化生产PP K8003产品，在230℃、2.16kg负荷下的熔体质量流动速率为2.2g/10min；
聚丙烯3：均聚聚丙烯，镇海炼化生产PP M60T产品，在230℃、2.16kg负荷下的熔体质量流动速率为60.0g/10min；
聚丙烯4：嵌段共聚聚丙烯，镇海炼化生产PP M60RHC产品，在230℃、 2.16kg负荷下的熔体质量流动速率为59.8g/10min；
无规共聚聚丙烯1：无规丙烯-乙烯共聚聚丙烯PP RP346R，LyondellBasell Industries生产产品，熔体质量流动速率为24g/10min；
无规共聚聚丙烯2：无规丙烯-乙烯共聚聚丙烯PP SM198，Lotte Chemical Titan(M)Sdn.Bhd.生产产品，熔体质量流动速率为2.3g/10min；
无规共聚聚丙烯3：无规丙烯-乙烯共聚聚丙烯PP K4912，上海赛科生产产品，熔体质量流动速率为12g/10min；
无规共聚聚丙烯4：无规丙烯-乙烯共聚聚丙烯PP R340S，Braskem生产产品，熔体质量流动速率为45g/10min；
聚酰胺1：尼龙1012，分子链亚甲基与酰胺基摩尔比值为11，山东东辰瑞森生产产品；
聚酰胺2：尼龙1010，分子链亚甲基与酰胺基摩尔比值为10，山东东辰瑞森生产产品；
聚酰胺3：尼龙1212，分子链亚甲基与酰胺基比值为12，山东东辰瑞森生产产品；
聚酰胺4；PA66EPR24，分子链亚甲基与酰胺基比值为6，平顶山神马生产产品；
相容剂；聚丙烯接枝马来酸酐，佛山南海柏晨AD-105；
有机过氧化物类引发剂：机过氧化物类引发剂Enox 101，中国强盛股份有限公司。
加工助剂：市售受阻酚类抗氧剂、市售亚磷酸酯类抗氧剂、市售芥酸酰胺的混合物，三者的质量之比为1:2:2；
各实施例和对比例所用原料除非上述特殊说明，否则在进行平行实验时用的均为同种。
实施例1～16
各实施例所述低后收缩聚丙烯材料的各组分及用量如表1所示。
实施例17
实施例17与实施例1的差别仅在于，本实施例中聚丙烯复合材料的制备方法为：
将各组分在高混机中以800rpm速率、50℃下混合5～8min至均匀，随后置入双螺杆挤出机中控制温度为190～220℃挤出，经冷却、切粒后，即得所述低后收缩聚丙烯材料；其中，低收缩调节剂、相容剂和引发剂以母粒形式加入；
所述母粒的制备方法为：
(1)将无规共聚聚丙烯、相容剂和引发剂以700rpm速率混合4min至均匀，随后置入双螺杆挤出机中控制190～200℃进行一段挤出，得第一产物；
(2)将第一产物和聚酰胺以500rpm速率混合2min至均匀，随后置入双螺杆挤出机中控制200～220℃进行二段挤出，切粒，即得所述母粒。
对比例1～6
各对比例所述聚丙烯复合材料的各组分及用量如表2所示。
表1


表2
效果例1
为了考察本发明所述低后收缩聚丙烯材料的性能，对各实施例和对比例所得产品进行如下测试：
(1)收缩率测试：根据GB/T 15585-1995标准方法，将各实施例和对比例产品注塑成型后，置于21～25℃、相对湿度45～55％的环境下静置24h，测定各产品的注塑成型收缩率L1；
(2)后收缩率测试：根据步骤(1)方法进行测试并得到结果收缩率L1，随后将各样品放入80℃烘箱中分别放置2h、4h和6h，随后取出样品并在置于21～25℃、相对湿度45～55％的环境下静置24h后进行收缩率测试，得到结果收 缩率L2，则后收缩率L0＝L2-L1(最终统计后收缩率)；
(3)光泽度测试：将各样品裁切成100*100*2mm的方板，21～25℃、相对湿度45～55％的环境下静置24h后，采用光泽度仪根据GB/T 8807-1988标准方法进行光泽度测试(角度为60°)；
各产品测试结果如表3和表4所示。
表3
表4
从表1可以看出，本发明所述低后收缩聚丙烯材料具有良好的稳定性，在 加热处理后依然具有较低的后收缩率(6h后收缩率均不足1％)，同时也能维持良好的光泽度，而从实施例1和实施例17比较可知，当低收缩调节剂等组分以母粒形式引入制备产品时，光泽度的保持效果更佳，更接近原始聚丙烯树脂基体。从实施例5～7对比可知，产品组分中无规共聚聚丙烯的熔体质量流动速率对产品的性能有一定影响，当其熔体质量流动速率维持在10～30g/10min范围内时产品性能可兼顾良好的光泽度和较低的后收缩率；从实施例1、实施例8、实施例9、对比例4产品性能可以看出，聚酰胺的分子链中亚甲基数与酰胺基比值是是产品性能的关键影响因素，只有比值维持在10～12时聚酰胺才能发挥理想功效；从实施例1、实施例10～14产品性能对比可知，当组分中无规共聚聚丙烯与聚酰胺的总量一定，但配比变化时，产品的光泽度和后收缩率也会有所影响，只有维持在两者配比为(7～9)：(1～2)时产品的光泽度和后收缩率均可维持在一个稳定且理想的范围。相比之下，对比例1产品不引入低后收缩调节剂，产品后收缩率较高；对比例2和3分别只引入了无规共聚聚丙烯和聚酰胺作为调节组分，其中对比例2产品6h后收缩率达到了3.2％，与对比例1产品无明显差距，而对比例3产品虽然后收缩率有一定降低，但仍同样难以实现理想的调节后收缩率效果，同时产品对比例3产品的光泽度还出现了显著下降的情况；对比例5和6中虽然均引入了两者低收缩调节组分，但总量添加过多或过少，同样达不到兼顾表面性能光泽度和长效尺寸稳定性的效果。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种低后收缩聚丙烯材料，其特征在于，包含如下重量份的组分：
    聚丙烯70～90份、低收缩调节剂15～25份、相容剂0.5～1.5份、引发剂0.03～0.05份、加工助剂0.2～0.6份；
    所述低收缩调节剂中包括无规共聚聚丙烯和聚酰胺，所述聚酰胺的分子链中亚甲基与酰胺基的摩尔比为10～12。
  2. 如权利要求1所述的低后收缩聚丙烯材料，其特征在于，所述低收缩调节剂中无规共聚聚丙烯和聚酰胺的质量比为(7～9)：(1～2)。
  3. 如权利要求1所述的低后收缩聚丙烯材料，其特征在于，所述无规共聚聚丙烯为无规丙烯-乙烯共聚物。
  4. 如权利要求1所述的低后收缩聚丙烯材料，其特征在于，所述无规共聚聚丙烯在230℃、2.16kg负荷下的熔体质量流动速率为10～30g/10min。
  5. 如权利要求1所述的低后收缩聚丙烯材料，其特征在于，所述聚丙烯为嵌段共聚聚丙烯、均聚聚丙烯中的至少一种；所述聚丙烯在230℃、2.16kg负荷下的熔体质量流动速率为1～60g/10min。
  6. 如权利要求1所述的低后收缩聚丙烯材料，其特征在于，所述相容剂为马来酸酐接枝物；所述引发剂为有机过氧化物类引发剂、偶氮类引发剂、过氧化苯甲酰类引发剂中的至少一种。
  7. 如权利要求1所述的低后收缩聚丙烯材料，其特征在于，所述加工助剂包括抗氧剂、润滑剂中的至少一种。
  8. 如权利要求1～7任一项所述低后收缩聚丙烯材料的制备方法，其特征在于，包括以下步骤：
    将各组分混合均匀，随后置入双螺杆挤出机中挤出，经冷却、切粒后，即得所述低后收缩聚丙烯材料。
  9. 如权利要求8所述低后收缩聚丙烯材料的制备方法，其特征在于，所述各组分混合时，低收缩调节剂、相容剂和引发剂以母粒形式加入；
    优选地，所述母粒的制备方法为：
    (1)将无规共聚聚丙烯、相容剂和引发剂混合均匀，随后置入双螺杆挤出机中进行一段挤出，得第一产物；
    (2)将第一产物和聚酰胺混合均匀，随后置入双螺杆挤出机中进行二段挤出，切粒，即得所述母粒。
  10. 如权利要求1～7任一项所述低后收缩聚丙烯材料在家电零部件制备中的应用。
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