WO2022135249A1 - 一种晶须纤维改性的acs/pbat合金及其制备方法和应用 - Google Patents

一种晶须纤维改性的acs/pbat合金及其制备方法和应用 Download PDF

Info

Publication number
WO2022135249A1
WO2022135249A1 PCT/CN2021/138632 CN2021138632W WO2022135249A1 WO 2022135249 A1 WO2022135249 A1 WO 2022135249A1 CN 2021138632 W CN2021138632 W CN 2021138632W WO 2022135249 A1 WO2022135249 A1 WO 2022135249A1
Authority
WO
WIPO (PCT)
Prior art keywords
acs
pbat
whisker
parts
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2021/138632
Other languages
English (en)
French (fr)
Inventor
林士文
黄险波
叶南飚
郭少华
官焕祥
李玉虎
何超雄
付锦锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kingfa Science and Technology Co Ltd
Original Assignee
Kingfa Science and Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kingfa Science and Technology Co Ltd filed Critical Kingfa Science and Technology Co Ltd
Publication of WO2022135249A1 publication Critical patent/WO2022135249A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • 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
    • C08L2205/24—Crystallisation aids

Definitions

  • the invention relates to the technical field of engineering plastics, and more particularly, to a whisker fiber-modified ACS/PBAT alloy and a preparation method and application thereof.
  • Polybutylene adipate terephthalate is a copolymer of butylene adipate and butylene terephthalate, which has both the properties of PBA and PBT.
  • PBAT contains flexible aliphatic chains and rigid aromatic chains and thus has high toughness and high temperature resistance.
  • ACS resin is a chlorinated polyethylene rubber toughened acrylonitrile-styrene copolymer. Because chlorinated polyethylene rubber does not contain double bond structure, the double bond content in ACS resin is very small, so it has good weather resistance. By compounding ACS resin and PBAT resin, the weather resistance of PBAT can be effectively improved.
  • PBAT resin is a crystalline material with a large shrinkage rate, while ACS resin is an amorphous material, and the shrinkage rates of ACS and PBAT are very different.
  • the shrinkage rate of the compounded ACS/PBAT alloy system is not only affected by the respective shrinkage rates of ACS resin and PBAT resin, but also closely related to the compatibility and crystallinity of the two resin matrices. For occasions that are very sensitive to size, such as the front frame and rear shell of TVs, the material needs to have a low shrinkage rate to achieve common mode in the injection molding process, reduce the cost of re-opening the mold, and improve the industrial application value. Therefore, improving the shrinkage rate of ACS/PBAT alloy has important application value without affecting its properties.
  • Chinese patent CN108659476A discloses a low shrinkage 3D printing material, including PBAT resin, inorganic whisker material, inorganic minerals, starch, plasticizer and other components, through which the shrinkage of the 3D printing material is reduced by the inorganic whisker material and inorganic minerals Rate.
  • the low shrinkage 3D printing material is a PBAT resin matrix, not an ACS/PBAT system. It is impossible to predict whether the shrinkage rate of the ACS/PBAT system can still maintain a low level.
  • the present invention provides an ACS/PBAT alloy in order to overcome the above-mentioned defects in the prior art.
  • the ACS/PBAT alloy is modified with whisker fibers and has an extremely low shrinkage rate.
  • Another object of the present invention is to provide a method for preparing the above-mentioned ACS/PBAT alloy.
  • Another object of the present invention is to provide the application of the above-mentioned ACS/PBAT alloy.
  • the technical scheme adopted in the present invention is:
  • a whisker fiber-modified ACS/PBAT alloy comprising the following components by weight:
  • the whisker fibers are one or more of calcium sulfate whiskers, magnesium sulfate whiskers or calcium carbonate whiskers.
  • Whisker fibers are micro- and nano-scale short fibers grown from high-purity single crystals. Their mechanical strength is equal to the strength generated by the force between adjacent atoms. The highly oriented structure of whisker fibers makes them have high strength, high modulus and high strength. Elongation.
  • the inventor's research found that introducing the calcium sulfate whiskers, magnesium sulfate whiskers or calcium carbonate whiskers of the present application into the ACS/PBAT alloy system, on the one hand, makes the whisker fibers distribute in the resin matrix along the flow direction, and on the other hand. , Calcium sulfate whiskers, magnesium sulfate whiskers and calcium carbonate whiskers have excellent thermal stability.
  • ACS/PBAT and alloys have extremely low shrinkage and high flexural modulus without losing their high weather resistance and toughness.
  • the ACS/PBAT alloy includes the following components in parts by weight: 60-80 parts by weight of ACS resin, 10-20 parts by weight of PBAT resin, 20-30 parts by weight of whisker fibers, and 3-30 parts by weight of compatibilizer. 8 parts, 0.1-1 part of nucleating agent.
  • the whisker fibers are a mixture of calcium sulfate whiskers and calcium carbonate whiskers.
  • the inventors have found that when the whisker fibers are a mixture of calcium sulfate whiskers and calcium carbonate whiskers, the ACS/PBAT alloy has a lower shrinkage rate and a higher flexural modulus.
  • the weight ratio of the calcium sulfate whiskers to the calcium carbonate whiskers is (1-9):3.
  • the diameter of the whisker fiber is less than or equal to 3 ⁇ m, and the length is 30-70 ⁇ m.
  • the diameter of the whisker fibers is relatively low, which can effectively avoid the influence of the addition of whisker fibers on the toughness of the ACS/PBAT alloy.
  • the length of whisker fibers is longer, and correspondingly, the aspect ratio is larger, which is beneficial to reduce the shrinkage rate of ACS/PBAT alloy and improve the flexural modulus.
  • the intrinsic viscosity of the PBAT resin is 2.0 ⁇ 2.8 dl/g.
  • the intrinsic viscosity of the ACS resin is 3.0 ⁇ 3.8 dl/g.
  • the intrinsic viscosity of PBAT resin and ACS resin is tested according to the standard method of GB/T1632-2008.
  • the nucleating agent is a commonly used nucleating agent in plastics.
  • the nucleating agent is preferably nano-montmorillonite and/or nano-talc.
  • the compatibilizer is preferably styrene-acrylonitrile-glycidyl methacrylate, styrene-acrylonitrile-maleic anhydride copolymer, ethylene-acrylate-glycidyl ester copolymer, ethylene-glycidyl One or more of ethylene-n-butyl acrylate-glycidyl ester copolymer.
  • the ACS/PBAT alloy further includes 0-4 parts by weight of other additives.
  • the other auxiliary agents include 0-2 parts by weight of antioxidants and 0-2 parts by weight of lubricants.
  • the antioxidant is preferably one or more of hindered phenolic antioxidants or phosphite antioxidants.
  • the antioxidants are antioxidants 1010 and 168.
  • the lubricant is one of vinyl bis-stearamide, polysiloxane, calcium stearate, magnesium stearate, zinc stearate, PE wax, PP wax or ethylene bis-stearamide species or several.
  • the present invention also protects the preparation method of the above-mentioned whisker fiber-modified ACS/PBAT alloy, comprising the following steps:
  • the whisker fiber-modified ACS/PBAT alloy is obtained by mixing, melting, extrusion and granulation.
  • the extruder is a twin-screw extruder
  • the temperature of the first to second zones of the twin-screw extruder is 120 ⁇ 190°C
  • the temperature of the third to fifth zone is 200 ⁇ 30°C
  • the temperature of the fifth to tenth zone is 200 ⁇ 190°C 230°C
  • the screw speed is 350 ⁇ 450rpm.
  • the invention also protects the application of the above-mentioned whisker fiber-modified ACS/PBAT alloy in the preparation of large-size TV sets and display casings.
  • the invention develops a whisker fiber-modified ACS/PBAT alloy.
  • the ACS/PBAT alloy can make the ACS/PBAT alloy without losing its high weather resistance and toughness.
  • has extremely low shrinkage rate and high flexural modulus which helps to make the alloy and injection mold realize common mode, reduce the cost of reopening the mold, and improve the industrial application value.
  • the raw materials in the embodiment and the comparative example can be obtained through commercially available, and the details are as follows:
  • the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
  • the temperature of the first to second zones of the twin-screw extruder is 120 to 190°C
  • the temperature of the third to fifth zones is 200 to 30°C
  • the temperature of the fifth to tenth zones is 200 to 230°C
  • the screw speed is 350 to 450rpm.
  • the temperature of the first to second zones of the twin-screw extruder is 120 to 190°C
  • the temperature of the third to fifth zones is 200 to 30°C
  • the temperature of the fifth to tenth zones is 200 to 230°C
  • the screw speed is 350 to 450rpm.
  • Flexural modulus tested according to ISO 178-2010 standard, the bending rate is 2mm/min;
  • Notched impact strength Tested in accordance with ISO 180-2001, the notch type is Type A, and the unit is kJ/m 2 .
  • Shrinkage rate According to the GB/T 17037.4-2003 standard, it is tested with a secondary instrument at room temperature.
  • Notched impact strength tested according to GB/T 1843-2008 standard method.
  • the flexural modulus of the ACS/PBAT alloy prepared by each embodiment of the present invention is all ⁇ 1800MPa, the shrinkage rate is all less than or equal to 0.7%, and the notched impact strength is all greater than or equal to 14kJ/m 2 .
  • the mixture of calcium sulfate whisker and calcium carbonate whisker can be ACS/PBAT alloys offer higher flexural modulus and notched impact strength, as well as lower shrinkage. More preferably, the mass ratio of calcium sulfate whiskers to calcium carbonate whiskers is (1-9):3.
  • Example 1 From Example 1, Examples 12-13, and Examples 14-15, it can be seen that the content of PBAT resin increases, which improves the toughness of ACS/PBAT alloy on the one hand, but also affects the shrinkage of ACS/PBAT alloy on the other hand.
  • the increase of whisker fiber content increases the flexural modulus and shrinkage rate of ACS/PBAT alloy on the one hand, and also makes the material toughness worse on the other hand.
  • the ACS resin is 60-80 parts by weight
  • the PBAT resin is 10-20 parts by weight
  • the whisker fiber is 20-30 parts by weight.
  • Comparative Example 1 the content of PBAT resin was too large, which made the shrinkage rate of the ACS/PBAT alloy too large, and the flexural modulus was only 1300 MPa; in Comparative Example 2, the whisker fibers were replaced by nano-calcium carbonate with a non-whisker morphology, which was obtained.
  • the ACS/PBAT alloy has a high shrinkage rate and a low flexural modulus, which cannot meet the actual needs; in Comparative Example 3, the whisker fibers are replaced by potassium titanate whiskers. Although the ACS/PBAT alloy has a good shrinkage rate, the toughness becomes poor.
  • the notched impact strength is only 7kJ/m 2 ; in Comparative Examples 4 to 5, the whisker fibers in the technical solution of the present invention are not added or the content is too high, so that ACS with good toughness, flexural modulus and low shrinkage cannot be obtained. /PBAT alloy.
  • Comparative Example 6 using ACS resin with whisker fibers, compatibilizers and nucleating agents, without PBAT resin, the material has low shrinkage but poor toughness; in Comparative Example 7, using PBAT resin with whisker fibers, compatible with It does not contain ACS resin, and the material shrinkage rate is extremely high, reaching 0.94%, which is difficult to apply to industrial large-scale production to achieve common mode.

Landscapes

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

Abstract

本发明公开了一种晶须纤维改性的ACS/PBAT合金及其制备方法和应用。所述晶须纤维改性的ACS/PBAT合金，包括如下重量份的组分：ACS树脂40～80份，PBAT树脂10～30份，相容剂3～8份，成核剂0.1～1份，晶须纤维10～30份；所述晶须纤维为硫酸钙晶须、硫酸镁晶须或碳酸钙晶须中的一种或几种。本发明通过晶须纤维与ACS、PBAT体系的协同增效作用，使得ACS/PBAT合金在不损耗其高耐候性、韧性的情况下，具有极低的收缩率和较高的弯曲模量，有助于使合金与注塑模具实现共模，减少重新开模所需的费用，提高工业应用价值。

Description

一种晶须纤维改性的ACS/PBAT合金及其制备方法和应用 技术领域
本发明涉及工程塑料技术领域，更具体的，涉及一种晶须纤维改性的ACS/PBAT合金及其制备方法和应用。
背景技术
聚己二酸对苯二甲酸丁二酯(PBAT)是己二酸丁二醇酯和对苯二甲酸丁二醇酯的共聚物，兼具PBA和PBT的特性。PBAT含有柔性的脂肪链和刚性的芳香链因而具有高韧性和耐高温性。但是由于PBAT中酯键的存在，PBAT易发生水解，而耐候性较差。ACS树脂是氯化聚乙烯橡胶增韧丙烯腈-苯乙烯共聚物，因氯化聚乙烯橡胶不含有双键结构，ACS树脂中双键含量极少，因而具有较好的耐候性。通过将ACS树脂与PBAT树脂复配，可以有效改善PBAT的耐候性。
PBAT树脂为结晶材料，具有较大的收缩率，ACS树脂为非晶材料，ACS、PBAT二者的收缩率有非常大的差异。复配的ACS/PBAT合金体系的收缩率，不仅受到ACS树脂、PBAT树脂各自收缩率的影响，也与两种树脂基体的相容性、结晶程度等息息相关。对于如电视机前框、后壳等对于尺寸非常敏感的场合，需要材料具有较低的收缩率，才能在注塑过程中实现共模，减少重新开模所需的费用，提高工业应用价值。因而在不影响其性能的情况下，改善ACS/PBAT合金的收缩率具有重要的应用价值。
中国专利CN108659476A公开了一种低收缩率3D打印材料，包括PBAT树脂、无机晶须材料、无机矿物、淀粉、增塑剂等组分，通过无机晶须材料和无机矿物降低了3D打印材料的收缩率。但该低收缩率3D打印材料为PBAT树脂基体，并非ACS/PBAT体系，无法预期ACS/PBAT体系的收缩率是否仍能保持较低水平。
因此，需要开发出一种较低收缩率的ACS/PBAT合金。
发明内容
本发明为克服上述现有技术所述的缺陷，提供一种ACS/PBAT合金，该ACS/PBAT合金使用晶须纤维改性，具有极低的收缩率。
本发明的另一目的在于提供上述ACS/PBAT合金的制备方法。
本发明的另一目的在于提供上述ACS/PBAT合金的应用。
为解决上述技术问题，本发明采用的技术方案是：
一种晶须纤维改性的ACS/PBAT合金，包括如下重量份的组分：
氯化聚乙烯-丙烯腈-苯乙烯共聚物(ACS树脂)40～80份，
聚己二酸对苯二甲酸丁二酯(PBAT树脂)10～30份，
相容剂3～8份，
成核剂0.1～1份，
晶须纤维10～30份；
所述晶须纤维为硫酸钙晶须、硫酸镁晶须或碳酸钙晶须中的一种或几种。
晶须纤维是由高纯度单晶生长而成的微纳米级的短纤维，其机械强度等于邻接原子间力产生的强度，晶须纤维的高度取向结构使其具有高强度、高模量和高伸长率。发明人研究发现，将本申请的硫酸钙晶须、硫酸镁晶须或碳酸钙晶须引入ACS/PBAT合金体系中，一方面，使晶须纤维沿流动方向分布于树脂基体中，另一方面，硫酸钙晶须、硫酸镁晶须和碳酸钙晶须具有优良的热稳定性，在ACS/PBAT合金注塑成型过程中，能够承受较高温度下性能不劣化，从而极大程度的降低ACS/PBAT基体的收缩率。与此同时，所述晶须纤维的加入也使得ACS/PBAT合金的弯曲模量大幅度提高。
通过晶须纤维与ACS、PBAT体系的互相协同增效作用，使得ACS/PBAT、合金在不损耗其高耐候性、韧性的情况下，具有极低的收缩率和较高的弯曲模量。
优选地，所述ACS/PBAT合金包括如下重量份的组分：ACS树脂为60～80重量份，PBAT树脂为10～20重量份，晶须纤维为20～30重量份，相容剂3～8份，成核剂0.1～1份。
优选地，所述晶须纤维为硫酸钙晶须和碳酸钙晶须的混合物。
发明人研究发现，当晶须纤维为硫酸钙晶须和碳酸钙晶须的混合物时，所述ACS/PBAT合金具有更低的收缩率和更高的弯曲模量。
更优选地，所述硫酸钙晶须和碳酸钙晶须的重量比为(1～9)：3。
优选地，所述晶须纤维的直径≤3μm，长度为30～70μm。
晶须纤维的直径较低，可以有效避免晶须纤维的加入对ACS/PBAT合金韧性的影响。晶须纤维的长度较长，相应的，长径比较大，有利于降低ACS/PBAT合金的收缩率、提高弯曲模量。
优选地，所述PBAT树脂的特性粘度为2.0～2.8dl/g。
优选地，所述ACS树脂的特性粘度为3.0～3.8dl/g。
PBAT树脂、ACS树脂的特性粘度均按照GB/T1632-2008标准方法检测。
若PBAT树脂的特性粘度过高或过低，则ACS/PBAT合金加工过程中ACS树脂与PBAT树脂粘度不匹配，相态结构不稳定，制得的ACS/PBAT合金综合力学性能较差。
所述成核剂为塑料中常用的成核剂。优选地，所述成核剂优选为纳米蒙脱土和/或纳米滑石粉。
优选地，所述相容剂优选为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯、苯乙烯-丙烯腈-马来酸酐共聚物、乙烯-丙烯酸酯-缩水甘油酯共聚物、乙烯-缩水甘油酯或乙烯-丙烯酸正丁酯-缩水甘油酯共聚物中的一种或几种。
优选地，所述ACS/PBAT合金还包括0～4重量份的其他助剂。
所述其他助剂包括抗氧剂0～2重量份、润滑剂0～2重量份。
优选地，所述抗氧剂优选为受阻酚类抗氧剂或亚磷酸脂类抗氧剂中的一种或几种。可选地，所述抗氧剂为抗氧剂1010、抗氧剂168。
优选地，所述润滑剂为乙烯基双硬脂酰胺、聚硅氧烷、硬脂酸钙、硬脂酸镁、硬脂酸锌、PE蜡、PP蜡或乙撑双硬脂酰胺中的一种或几种。
本发明还保护上述晶须纤维改性的ACS/PBAT合金的制备方法，包括如下步骤：
S1.将ACS树脂、PBAT树脂、相容剂、成核剂混合得到第一预混料，将部分晶须纤维与第一预混料混合，得到第二预混料；
S2.将第二预混料加至挤出机主喂料口，将剩余的晶须纤维加至挤出机侧喂料口；
S3.经混合熔融、挤出造粒，得到所述晶须纤维改性的ACS/PBAT合金。
优选地，所述挤出机为双螺杆挤出机，双螺杆挤出机的一至二区温度为120～190℃，三至五区温度为200～30℃，五至十区温度为200～230℃，螺杆转速为350～450rpm。
本发明还保护上述晶须纤维改性的ACS/PBAT合金在制备大尺寸电视机、显示器壳体中的应用。
与现有技术相比，本发明的有益效果是：
本发明开发了一种晶须纤维改性的ACS/PBAT合金，通过晶须纤维与ACS、PBAT体系的互相协同增效作用，使得ACS/PBAT合金在不损耗其高耐候性、韧性的情况下，具有极低的收缩率和较高的弯曲模量，有助于使合金与注塑模具实现共模，减少重新开模所需的费用，提高工业应用价值。
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。
实施例及对比例中的原料均可通过市售得到，具体如下：
Figure PCTCN2021138632-appb-000001
除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方 法和设备。
实施例1～18
实施例1～18的ACS/PBAT合金中各组分的含量如表1所示。
其制备方法为：
S1.将ACS树脂、PBAT树脂、相容剂、成核剂混合得到第一预混料，将部分晶须纤维与第一预混料混合，得到第二预混料；
S2.将第二预混料加至双螺杆挤出机主喂料口，将剩余的晶须纤维加至双螺杆挤出机侧喂料口；
S3.经混合熔融、挤出造粒，得到ACS/PBAT合金。
其中双螺杆挤出机的一至二区温度为120～190℃，三至五区温度为200～30℃，五至十区温度为200～230℃，螺杆转速为350～450rpm。
表1实施例1～18的ACS/PBAT合金的组分含量(重量份)
Figure PCTCN2021138632-appb-000002
表1续实施例1～18的ACS/PBAT合金的组分含量(重量份)
Figure PCTCN2021138632-appb-000003
Figure PCTCN2021138632-appb-000004
对比例1～7
对比例1～7的合金材料中各组分的含量如表2所示。
其制备方法为：
S1.根据表2的含量将ACS树脂(如有)、PBAT树脂(如有)、相容剂、成核剂混合得到第一预混料，将部分晶须纤维(如有)与第一预混料混合，得到第二预混料；
S2.将第二预混料加至双螺杆挤出机主喂料口，将剩余的晶须纤维(如有)加至双螺杆挤出机侧喂料口；
S3.经混合熔融、挤出造粒，得到ACS/PBAT合金。
其中双螺杆挤出机的一至二区温度为120～190℃，三至五区温度为200～30℃，五至十区温度为200～230℃，螺杆转速为350～450rpm。
表2对比例1～7的合金材料的组分含量(重量份)
Figure PCTCN2021138632-appb-000005
性能测试
对上述实施例及对比例制备的合金进行性能测试。
具体测试方法如下：
弯曲模量：按照ISO 178-2010标准进行测试，弯曲速率为2mm/min；
缺口冲击强度：按照ISO 180-2001标准进行测试，缺口类型为A型，单位为kJ/m 2。
收缩率：据GB/T 17037.4-2003标准，在常温下使用二次元仪器进行测试。
缺口冲击强度：根据GB/T 1843-2008标准方法检测。
实施例1～18的测试结果见表3；对比例1～7的测试结果见表4。
表3实施例1～18的测试结果
Figure PCTCN2021138632-appb-000006
根据表3的测试结果，本发明各实施例制备的ACS/PBAT合金弯曲模量均≥1800MPa，收缩率均≤0.7％，缺口冲击强度均≥14kJ/m 2。
由实施例1～5可以看出，ACS树脂的特性粘度为3.0～3.8dl/g，PBAT树脂的特性粘度为2.0～2.8dl/g时，ACS/PBAT体系中ACS树脂与PBAT树脂粘度更匹配，相态结构更稳定，制得的ACS/PBAT合金综合力学性能更优。
由实施例1、实施例6～11可以看出，在硫酸钙晶须、硫酸镁晶须、碳酸钙晶须这三种晶须纤维中，硫酸钙晶须和碳酸钙晶须的混合物能为ACS/PBAT合金提供更高的弯曲模量和缺口冲击强度，以及更低的收缩率。更优选地，硫酸钙晶须和碳酸钙晶须的质量比为(1～9)：3。
由实施例1、实施例12～13、实施例14～15，可以看出PBAT树脂的含量增加，一方面提高了ACS/PBAT合金的韧性，但另一方面也影响了ACS/PBAT合金的收缩率变大；晶须纤维的含量增加，一方面提高了ACS/PBAT合金的弯曲模量和收缩率，另一方面也使得材料韧性变差。综合考虑收缩率、韧性与弯曲模量，优选ACS树脂为60～80重量份，PBAT树脂为10～20重量份，晶须纤维为20～30重量份。
表4对比例1～7的测试结果
  1 2 3 4 5 6 7
弯曲模量(MPa) 1300 1550 2250 1800 3040 2500 1120
收缩率(％) 0.78 0.81 0.58 0.83 0.32 0.42 0.94
缺口冲击强度 27 21 7 24 6 9 25
(kJ/m 2)              
对比例1中，PBAT树脂含量过多，使得ACS/PBAT合金收缩率过大，且弯曲模量仅为1300MPa；对比例2中晶须纤维替换为了非晶须形貌的纳米碳酸钙，制得的ACS/PBAT合金收缩率较高，弯曲模量过低，不能满足实际需求；对比例3中晶须纤维替换为了钛酸钾晶须，ACS/PBAT合金虽具有良好收缩率，但韧性变差，缺口冲击强度仅为7kJ/m 2；对比例4～5中，本发明技术方案中的晶须纤维未添加或含量过高，无法获得兼具良好韧性、弯曲模量和低收缩率的ACS/PBAT合金。
对比例6中，使用ACS树脂搭配晶须纤维、相容剂和成核剂，不含PBAT树脂，材料收缩率低但韧性较差；对比例7中，使用PBAT树脂搭配晶须纤维、相容剂和成核剂，不含ACS树脂，材料收缩率极高，达到0.94％，难以应用于工业大规模生产中实现共模。
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. 一种晶须纤维改性的ACS/PBAT合金，其特征在于，包括如下重量份的组分：
    ACS树脂40～80份，PBAT树脂10～30份，相容剂3～8份，成核剂0.1～1份，晶须纤维10～30份；
    所述晶须纤维为硫酸钙晶须、硫酸镁晶须或碳酸钙晶须中的一种或几种。
  2. 根据权利要求1所述ACS/PBAT合金，其特征在于，包括如下重量份的组分：
    ACS树脂为60～80重量份，PBAT树脂为10～20重量份，晶须纤维为20～30重量份，相容剂3～8份，成核剂0.1～1份。
  3. 根据权利要求1所述ACS/PBAT合金，其特征在于，所述晶须纤维为硫酸钙晶须和碳酸钙晶须的混合物。
  4. 根据权利要求1所述ACS/PBAT合金，其特征在于，所述PBAT树脂的特性粘度为2.0dl/g～2.8dl/g。
  5. 根据权利要求1所述ACS/PBAT合金，其特征在于，所述ACS树脂的特性粘度为3.0～3.8dl/g。
  6. 根据权利要求1所述ACS/PBAT合金，其特征在于，所述晶须纤维的直径≤3μm，长度为30～70μm。
  7. 根据权利要求1所述ACS/PBAT合金，其特征在于，所述相容剂为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯、苯乙烯-丙烯腈-马来酸酐共聚物、乙烯-丙烯酸酯-缩水甘油酯共聚物、乙烯-缩水甘油酯或乙烯-丙烯酸正丁酯-缩水甘油酯共聚物中的一种或几种。
  8. 根据权利要求1所述ACS/PBAT合金，其特征在于，所述成核剂为纳米蒙脱土和/或纳米滑石粉。
  9. 权利要求1～8任一项所述ACS/PBAT合金的制备方法，其特征在于，包括如下步骤：
    S1.将ACS树脂、PBAT树脂、相容剂、成核剂混合得到第一预混料，将部分晶须纤维与第一预混料混合，得到第二预混料；
    S2.将第二预混料加至挤出机主喂料口，将剩余的晶须纤维加至挤出机侧喂料口；
    S3.经混合熔融、挤出造粒，得到所述晶须纤维改性的ACS/PBAT合金。
  10. 权利要求1～8任一项所述ACS/PBAT合金在制备大尺寸电视机、显示器壳体中的应用。
PCT/CN2021/138632 2020-12-22 2021-12-16 一种晶须纤维改性的acs/pbat合金及其制备方法和应用 Ceased WO2022135249A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011530846.8A CN112724576B (zh) 2020-12-22 2020-12-22 一种晶须纤维改性的acs/pbat合金及其制备方法和应用
CN202011530846.8 2020-12-22

Publications (1)

Publication Number Publication Date
WO2022135249A1 true WO2022135249A1 (zh) 2022-06-30

Family

ID=75604050

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/138632 Ceased WO2022135249A1 (zh) 2020-12-22 2021-12-16 一种晶须纤维改性的acs/pbat合金及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN112724576B (zh)
WO (1) WO2022135249A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112724576B (zh) * 2020-12-22 2022-09-02 金发科技股份有限公司 一种晶须纤维改性的acs/pbat合金及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199339A (zh) * 2015-10-19 2015-12-30 福建师范大学 一种用于3D打印的PBS/PBAT/CNTs材料及其制备方法
US20200189251A1 (en) * 2017-08-29 2020-06-18 Breakwall Technology Llc Electromagnetic Reduction Materials, Methods, and Devices
CN111944291A (zh) * 2020-09-03 2020-11-17 浙江海诺尔生物材料有限公司 一种聚乳酸树脂组合物及其制备方法
CN112724576A (zh) * 2020-12-22 2021-04-30 金发科技股份有限公司 一种晶须纤维改性的acs/pbat合金及其制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101402767A (zh) * 2008-11-10 2009-04-08 上海金发科技发展有限公司 一种丙烯腈-苯乙烯共聚物/聚对苯二甲酸乙二醇酯合金材料及其制备方法
CN104098876B (zh) * 2013-04-09 2016-10-12 合肥杰事杰新材料股份有限公司 一种耐候性pbt/aes合金及其制备方法
CN105968606B (zh) * 2016-06-17 2019-03-19 金发科技股份有限公司 一种自增强异型材及其制备方法和应用
JP2019038918A (ja) * 2017-08-24 2019-03-14 東レ株式会社 ポリブチレンテレフタレート樹脂組成物およびそれからなる成形品
CN108659476B (zh) * 2018-05-21 2020-09-04 广州医科大学 一种低收缩率3d打印材料及其制备方法与应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199339A (zh) * 2015-10-19 2015-12-30 福建师范大学 一种用于3D打印的PBS/PBAT/CNTs材料及其制备方法
US20200189251A1 (en) * 2017-08-29 2020-06-18 Breakwall Technology Llc Electromagnetic Reduction Materials, Methods, and Devices
CN111944291A (zh) * 2020-09-03 2020-11-17 浙江海诺尔生物材料有限公司 一种聚乳酸树脂组合物及其制备方法
CN112724576A (zh) * 2020-12-22 2021-04-30 金发科技股份有限公司 一种晶须纤维改性的acs/pbat合金及其制备方法和应用

Also Published As

Publication number Publication date
CN112724576B (zh) 2022-09-02
CN112724576A (zh) 2021-04-30

Similar Documents

Publication Publication Date Title
US8486313B2 (en) Flame retarding thermoplastic alloy and its preparation method
WO2022110673A1 (zh) 一种减震阻尼有卤阻燃增强pbt材料及其制备方法
WO2018107969A1 (zh) 一种pc/abs组合物及其制备方法和应用
CN103059543B (zh) 一种汽车内饰件用抗冲击改性聚碳酸酯塑料及其制备方法
CN114835975B (zh) 一种低翘曲玻纤增强聚丙烯复合材料及其制备方法和应用
CN108467544B (zh) 一种高强、高刚且透明改性聚丙烯复合材料及其制备方法
CN111154246B (zh) 玻璃纤维增强聚碳酸酯组合物及其制备方法和用途
CN105542375A (zh) 一种可用于薄壁化零件注塑的高性能聚丙烯复合材料及其制备方法
CN116063796A (zh) 一种汽车立柱用耐刮擦、耐析出、耐光老化玻纤增强聚丙烯复合材料及其制备方法
CN113563667A (zh) 复配填充保险杠用轻量化改性聚丙烯复合材料及其制备方法
CN108342057B (zh) 无卤阻燃pc/pbt合金及其产品
CN115433450A (zh) 一种良外观玻矿复合增强pc合金组合物及其制备方法和应用
WO2022135249A1 (zh) 一种晶须纤维改性的acs/pbat合金及其制备方法和应用
CN111763383B (zh) 一种良触感玻纤增强聚丙烯复合物及其制备方法
US5367013A (en) Process for producing reinforced crystalline engineering plastic composition
CN107418197B (zh) 一种导热尼龙工程塑料及其制备方法
CN103073822A (zh) 一种汽车内饰件用抗冲击改性pvc树脂及其制备方法
CN105086134A (zh) 医用高分子材料及其制备方法
CN108342056A (zh) Pc/pbt合金及其产品
CN108329647B (zh) 低内应力、高抗冲abs组合物及其制备方法和应用
CN111484679A (zh) 一种高刚、高韧、高流动聚丙烯复合材料及其制备方法
CN112662053A (zh) 一种低密度高性能车保险杠用改性聚丙烯复合材料及其制备方法
CN104788804A (zh) 聚丙烯树脂组合物及其产品
CN113980383A (zh) 一种高透光低温韧性的聚丙烯组合物及其制备方法和应用
US10550255B2 (en) Polyolefine resin composition, polyolefine master batch, method of manufacturing polyolefine master batch, and article formed of the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21909245

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21909245

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 01/02/2024).

122 Ep: pct application non-entry in european phase

Ref document number: 21909245

Country of ref document: EP

Kind code of ref document: A1