WO2023169033A1 - 苯乙烯马来酸酐共聚物复合材料及其制备方法和应用 - Google Patents
苯乙烯马来酸酐共聚物复合材料及其制备方法和应用 Download PDFInfo
- Publication number
- WO2023169033A1 WO2023169033A1 PCT/CN2022/138881 CN2022138881W WO2023169033A1 WO 2023169033 A1 WO2023169033 A1 WO 2023169033A1 CN 2022138881 W CN2022138881 W CN 2022138881W WO 2023169033 A1 WO2023169033 A1 WO 2023169033A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- maleic anhydride
- composite material
- anhydride copolymer
- styrene maleic
- styrene
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] 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 present invention relates to the technical field of polymer materials, and more specifically, to a styrene maleic anhydride copolymer composite material and its preparation method and application.
- Automobile lightweight technology is one of the important directions for the development of the automobile industry. It is a common choice of global automobile manufacturers. It is an effective, direct and feasible way to achieve energy conservation and emission reduction. It is an inevitable measure for my country to deal with energy security, and it is also the key to the sustainable development of the automobile industry. The only way to go. There is no contradiction between automobile lightweighting and safety. Appropriate lightweighting can help improve automobile safety performance.
- the development of the automobile lightweight industry will help enhance the international competitiveness of my country's own brand cars. It is also one of the important ways to improve the independent innovation capabilities of my country's automobile industry. It is a practical need to adjust the product structure and industrialization structure. It is also conducive to improving and Developing the technical level of my country's related industries also points the way forward for the development direction of advanced automotive materials technology, and truly realizes the supply-side reform of the automotive industry.
- Composite materials are materials with new properties that are macroscopically composed of two or more materials with different properties through physical or chemical methods. Various materials complement each other in terms of performance, creating a synergistic effect, making the overall performance of composite materials better than the original component materials and meeting various different requirements.
- fiber-reinforced thermoplastic composite materials have the advantages of low density, flexible design, corrosion resistance, heat resistance, impact resistance, and vibration resistance, and are increasingly used in automobiles.
- Carbon fiber reinforced polymer matrix composite is a new type of composite material for automobiles. It has excellent toughness and tensile strength, and its density is only 1/4 of steel. It is suitable for manufacturing body panels and chassis parts. Weight loss usually reaches 50% to 65%. Its main features are: 1. It can greatly reduce the mass of the car and is especially suitable for manufacturing car body parts. Car body parts made of CFRP are 30% lighter and more than 50% lighter than car body parts made of aluminum and steel respectively, which can reduce the mass of the entire vehicle by up to 10%; 2. It shows excellent strength and stiffness during a collision . The diameter of carbon fiber is about 0.007mm, and the stress is mainly concentrated in the directional flow direction of the fiber itself.
- CFRP can reduce the weight of the automobile body by 30% to 50%, which is equivalent to 2/3 to 1/2 of the mass of the steel body structure. Taking an ordinary car as an example, the average mass is 1380kg. After CFRP, the mass will drop to 970kg, a decrease of 30%.
- due to the current high price of CFRP its application in general automobiles is limited.
- structural designers of automobile OEMs want to use as much CFRP material as possible to reduce vehicle weight, but on the other hand, they are limited by cost, so they use CFRP in the most critical parts. To achieve this goal, designers have developed a new lightweight car door panel module.
- the outer door panel is made of carbon fiber composite material, which is characterized by light weight, high strength, less complex structure, and easy to mold at a fast pace; the inner door panel is made of carbon fiber composite material.
- the door panels are made of glass fiber reinforced composite materials, which are characterized by being lightweight and moderately strong. However, they can be easily molded into inner door panels with complex structures through injection molding. The inner and outer door panels are then thermally bonded at a temperature of 120 to 130°C. The complete door module skeleton is prepared.
- the outer door panels disclosed in the prior art are made of epoxy resin modified carbon fiber composite materials.
- the prior art discloses a long glass fiber reinforced polypropylene composite material that is specially used for all-plastic tailgates and has excellent bonding effects. Its composition mainly includes 30 to 40% long glass fibers by weight, 50 ⁇ 60% modified polypropylene resin, 1 ⁇ 6% maleic anhydride graft PP-g-MAH, 0.5 ⁇ 5% antioxidant additive masterbatch, 1 ⁇ 3% epoxy additives, etc. .
- this material has fewer reaction sites for bonding with epoxy resin-modified carbon fiber composites, the matrix resin has low polarity, and the long glass fiber reinforced polypropylene composite material technology solution cannot be modified with epoxy resin.
- Carbon fiber composite materials perform effective high-strength overall bonding at temperatures of 120 to 130°C.
- the technical problem to be solved by the present invention is to overcome the defects and shortcomings of poor adhesion between existing materials and epoxy resin modified carbon fiber composite materials at a temperature of 120-130°C, and provide a styrene maleic anhydride copolymer composite Material, through the synergistic effect of styrene maleic anhydride copolymer and compatibilizer, the bonding of styrene maleic anhydride copolymer composite material and epoxy resin modified carbon fiber composite material is greatly improved at a temperature of 120 to 130°C. sex.
- Another object of the present invention is to provide a method for preparing a styrene maleic anhydride copolymer composite material.
- Another object of the present invention is to provide an application of a styrene maleic anhydride copolymer composite material in the preparation of automobile structural parts.
- Another object of the present invention is to provide an automobile door inner panel.
- a styrene maleic anhydride copolymer composite material including the following components in parts by weight:
- the compatibilizer is a polymer containing structural units with epoxy functional groups.
- the mass content of the structural units containing epoxy functional groups is 1 to 10%.
- the test method is GB/T 1677-2008.
- the styrene maleic anhydride copolymer composite material of the present invention can be combined with the epoxy resin modified carbon fiber composite material through the optimized synergy of the styrene maleic anhydride copolymer and the compatibilizer containing the epoxy ring energy group structural unit. High-strength adhesion at temperatures of 120 to 130°C.
- styrene maleic anhydride copolymer maleic anhydride is copolymerized on the styrene chain segment, which makes the material have high heat resistance.
- the styrene maleic anhydride copolymer composite material can be combined with the epoxy resin modified carbon fiber composite material. Effective thermal bonding can be performed at a temperature of 120 to 130°C without causing thermal deformation of the styrene maleic anhydride copolymer composite material.
- the structural units containing epoxy functional groups in the compatibilizer are similar in structure to the functional groups in epoxy resin modified carbon fiber composite materials.
- the structural units containing epoxy functional groups in the compatibilizer are located on the surface of the composite material and can be treated at high temperatures with the same
- the resin polymers in the functional group epoxy resin modified carbon fiber composite materials are physically compatible with each other and co-penetrate.
- an appropriate amount of compatibilizer can undergo a mild reversible cross-linking reaction with styrene maleic anhydride.
- the styrene maleic anhydride on the surface The acid anhydride copolymer polymer chain is connected with the core layer of the skin-core structural material through the compatibilizer and even with the part of the styrene maleic anhydride copolymer polymer chain on the air contact surface, making the styrene maleic anhydride copolymer composite material and
- the epoxy resin on the surface of the carbon fiber composite material becomes a whole, which greatly improves the bonding performance of the styrene maleic anhydride copolymer composite material and the epoxy resin modified carbon fiber composite material.
- the styrene maleic anhydride copolymer composite material is not only a material The surface is effectively bonded to the carbon fiber composite material, and the entire styrene maleic anhydride copolymer composite material also forms a whole with a certain chemical structure connection with the epoxy resin modified carbon fiber composite material.
- the present invention greatly improves the bonding performance of the composite material and the epoxy resin modified carbon fiber composite material through the chemical and physical combination of the styrene maleic anhydride copolymer and the compatibilizer with the epoxy resin modified carbon fiber composite material.
- the compatibilizer is added in an excessive amount, although it can significantly improve the bonding effect between the styrene maleic anhydride copolymer composite material and the epoxy resin modified carbon fiber composite material, it will significantly reduce the impact performance of the composite material.
- the mass content of the structural units containing epoxy functional groups in the compatibilizer is related to the bonding properties and impact properties of the final composite material and the epoxy resin modified carbon fiber composite material.
- the mass content is less than 1%.
- Glycidyl methacrylate and cyclic The physical bonding of epoxy resin in oxygen resin modified carbon fiber composite materials is poor, and the bonding effect between the final composite material and epoxy resin modified carbon fiber composite materials is not significantly improved; the mass content is greater than 10%, although it is effectively improved The bonding effect between composite materials and epoxy resin modified carbon fiber composite materials, but the higher mass content of structural units containing epoxy functional groups will significantly reduce the impact properties of the composite materials.
- the function of the toughening agent is to improve the impact performance of the composite material.
- the toughening agent may be a copolymer containing a styrenic impact toughening agent, vinyl aromatic structural units and ethylenically unsaturated nitrile structural units.
- the styrenic impact toughening agent is styrene-butadiene-acrylonitrile copolymer, styrene-butadiene-acrylate copolymer, methacrylate-butadiene-styrene copolymer, One or a mixture of one or more of methacrylate-acrylate-styrene copolymer, styrene-acrylate-acrylonitrile copolymer or methacrylate-acrylate copolymer.
- the acrylonitrile content may be 20% to 30%.
- the mass content of the structural units containing epoxy functional groups in the compatibilizer is 3 to 6%.
- the compatibilizer is styrene-acrylonitrile-glycidyl methacrylate.
- Styrene-acrylonitrile-glycidyl methacrylate contains styrene-acrylonitrile, which has good compatibility with the matrix resin styrene maleic anhydride, which is beneficial to improving the mechanical and heat-resistant properties of composite materials and avoiding high temperatures. Bonding deformation.
- the styrene maleic anhydride copolymer is a styrene maleic anhydride random copolymer, wherein The molar content of maleic anhydride is 18 to 26%.
- the glass fiber is alkali-free chopped glass fiber.
- Alkali-free chopped glass fiber can improve the rigidity and heat resistance of composite materials and avoid high-temperature bonding deformation.
- processing aids such as lubricants and/or antioxidants can also be added according to actual needs.
- the antioxidant may be selected from one or a mixture of hindered amines, hindered phenols or phosphites, calixarenes and thioesters.
- the lubricant can be selected from one or a mixture of amides, metal soaps and low molecular esters.
- Antioxidants can improve the antioxidant effect of styrene maleic anhydride copolymer composite materials, and lubricants can improve the lubrication effect of styrene maleic anhydride copolymer composite materials.
- the toughening agent is styrene-butadiene-acrylonitrile copolymer.
- colorants and other additives are also included according to actual performance needs.
- the colorant is 0 to 0.5 parts by weight.
- the coloring agent can be selected from carbon black and the like.
- Colorants can change the color of styrene maleic anhydride copolymer composites.
- the present invention also protects the preparation method of the above-mentioned styrene maleic anhydride copolymer composite material, which specifically includes the following steps: mix each component evenly, melt and extrudate at 220-240°C through a twin-screw extruder, granulate, and dry. The styrene maleic anhydride copolymer composite material is then obtained.
- the styrene maleic anhydride copolymer composite material prepared by the present invention has excellent bonding properties with the epoxy resin modified carbon fiber composite material and can be widely used in the preparation of plastic products.
- the present invention particularly protects the styrene maleic anhydride copolymer composite material.
- Application of maleic anhydride copolymer composites in the preparation of automotive structural parts can be car interior door panels, dashboard frames, front-end frames, sunroof frames, wind guards, rearview mirror brackets, etc., but are not limited to the above applications, which are especially suitable for preparing cars for bonding with carbon fiber composite materials. Door inner panel.
- the present invention also specifically protects an automobile door panel, which is bonded by a raw material including the styrene maleic anhydride copolymer composite material and a carbon fiber composite material.
- the car door panel is made by bonding the car inner door panel and the car outer door panel.
- the material of the car outer door panel is carbon fiber composite material.
- the styrene maleic anhydride copolymer composite material of the present invention can greatly improve the performance of the car after injection molding the car inner door panel.
- the bonding strength between the inner door panel and the carbon fiber composite outer door panel ultimately ensures that the entire car door module can pass the rigorous car crash test and perform better in the key indicator of passenger intrusion distance.
- the invention discloses a styrene maleic anhydride copolymer composite material.
- the resin base material is composed of a styrene maleic anhydride copolymer and a compatibilizer containing structural units of epoxy functional groups.
- the synergistic effect of the combination effectively improves the adhesion with epoxy resin modified carbon fiber composite materials at temperatures of 120 to 130°C.
- the bonding strength of the styrene maleic anhydride copolymer composite material and the epoxy resin modified carbon fiber composite material of the present invention can reach more than 8.5MPa, and no thermal deformation will occur at temperatures below 105°C.
- the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
- Styrene maleic anhydride copolymer 1 is styrene maleic anhydride copolymer SZ23110, the molar content of maleic anhydride is 26%, Polyscope of the Netherlands;
- Styrene maleic anhydride copolymer 2 is styrene maleic anhydride copolymer SMA-725, the molar content of maleic anhydride is 18%, China Huawen;
- Styrene maleic anhydride copolymer 3 is styrene maleic anhydride copolymer SMA-700, the molar content of maleic anhydride is 8%, China Huawen;
- Styrene maleic anhydride copolymer 4 is styrene maleic anhydride copolymer SMA-800, the molar content of maleic anhydride is 35%, China Huawen;
- the toughening agent is styrene-butadiene-acrylonitrile copolymer PA-757, which is commercially available and the same one is used in all examples and comparative examples.
- the glass fiber is alkali-free chopped glass fiber, which is commercially available and the same one is used in all examples and comparative examples;
- Compatibilizer 1 is styrene-acrylonitrile-glycidyl methacrylate SAG-005.
- the structural unit containing epoxy functional groups is glycidyl methacrylate.
- the mass content of glycidyl methacrylate is 5%, preferably Disguise;
- Compatibilizer 2 is styrene-acrylonitrile-glycidyl methacrylate SAG-002, the structural unit containing epoxy functional groups is glycidyl methacrylate, and the mass content of glycidyl methacrylate is 2%, preferably Disguise;
- Compatibilizer 3 is styrene-acrylonitrile-glycidyl methacrylate SAG-008.
- the structural unit containing epoxy functional groups is glycidyl methacrylate.
- the mass content of glycidyl methacrylate is 8%, preferably Disguise;
- Compatibilizer 4 is ethylene-methyl methacrylate-glycidyl methacrylate AX8900.
- the structural unit containing epoxy functional groups is glycidyl methacrylate.
- the mass content of glycidyl methacrylate is 8%. koma;
- Compatibilizer 5 is styrene-acrylonitrile-glycidyl methacrylate SAG-012, the structural unit containing epoxy functional groups is glycidyl methacrylate, and the mass content of glycidyl methacrylate is 12%, preferably Disguise;
- Compatibilizer 6 is styrene-acrylonitrile-glycidyl methacrylate SAG-0005.
- the structural unit containing epoxy functional groups is glycidyl methacrylate.
- the mass content of glycidyl methacrylate is 0.5%, preferably Disguise;
- Compatibilizer 7 is maleic anhydride grafted polypropylene, the grafting rate of maleic anhydride is 2%, and it is commercially available.
- the lubricant is a low molecular weight ester, which is commercially available and the same one is used in all examples and comparative examples;
- the antioxidants are hindered phenols and phosphites.
- the ratio of hindered phenols and phosphites is 1:1. They are commercially available and the same ones are used in all examples and comparative examples;
- a styrene maleic anhydride copolymer composite material including the following components in parts by weight: styrene maleic anhydride copolymer; toughener; filler; compatibilizer; lubricant and antioxidant;
- the preparation method of styrene maleic anhydride copolymer composite material is as follows:
- a styrene maleic anhydride copolymer composite material in which the specific contents of each component are as shown in Table 2 below.
- the preparation method of the styrene maleic anhydride copolymer composite material is the same as in Example 1 and will not be described again here.
- Tensile strength tested according to ISO527-2019 standard, tensile speed is 50mm/min;
- Flexural modulus tested according to ISO178-2019 standard, speed 2mm/min, span 64mm;
- Izod notch impact strength tested according to ISO180/1eA-2000 standard;
- Heat distortion temperature Tested in accordance with ISO 75-2-2013, with a load of 1.82MPa.
- Bonding performance The carbon fiber composite material spline is thermally bonded with the glass fiber reinforced styrene maleic anhydride copolymer spline, the bonding time is 5 hours, the bonding temperature is 120°C, according to GB/T 7124-2008 The bonding strength test was performed at a test temperature of 23°C, a clamp spacing of 115mm, and a tensile speed of 50mm/min.
- Example 1 and Comparative Example 1 that without adding a compatibilizer, the bonding performance of the material and the epoxy resin modified carbon fiber composite material decreases by 75%, because the compatibilizer is the polymerization of structural units containing epoxy functional groups.
- a compatibilizer with a certain functionality to the material, on the one hand, it can physically accommodate and co-penetrate with the resin polymer in the epoxy resin modified carbon fiber composite material with the same functional group at high temperature; on the other hand, an appropriate amount of compatibilizer can A slight reversible cross-linking reaction occurs with styrene maleic anhydride, and the polymer chains of the styrene maleic anhydride copolymer on the surface are connected to the core layer and even part of the styrene maleic anhydride copolymer polymer chains on the lower surface through the compatibilizer. Together, the styrene maleic anhydride copolymer composite material becomes a whole, which greatly improves the bonding performance of the styrene male
- Example 1 and Comparative Example 2 It can be seen from Example 1 and Comparative Example 2 that the amount of compatibilizer added is too small, and the bonding strength of the styrene maleic anhydride copolymer composite material and the epoxy resin modified carbon fiber composite material is limited, indicating that the compatibilizer is The overall micro-crosslinking effect of styrene maleic anhydride copolymer cannot be ignored. Only by forming an overall bond can it be possible to greatly improve the bonding performance.
- Example 1 and Comparative Example 3 It can be seen from Example 1 and Comparative Example 3 that the amount of compatibilizer added is too large. Although the mechanical strength, modulus and bonding strength of the material are well maintained, the impact performance drops significantly. Although the material in Comparative Example 3 Styrene maleic anhydride copolymer can still be used in the bonding field of carbon fiber composite materials, but it cannot be used in automobile parts that require high impact performance. Otherwise, during automobile impact experiments, a large number of sharp fragments will be produced and cause injuries to personnel. Casualties, unable to meet the five-star collision rating requirements.
- Example 1 and Comparative Example 4 It can be seen from Example 1 and Comparative Example 4 that the mass content of structural units containing epoxy functional groups in the compatibilizer is too large. Although the mechanical strength, modulus and bonding strength of the material are well maintained, due to the local functional groups If the content is too high, excessive cross-linking will easily occur and the impact performance will be significantly reduced. It cannot be applied to automotive parts that have both carbon fiber composite bonding requirements and high impact performance requirements.
- Example 1 and Comparative Example 5 It can be seen from Example 1 and Comparative Example 5 that the mass content of the structural units containing epoxy functional groups in the compatibilizer is too small to form an overall micro-crosslink with the styrene maleic anhydride copolymer, and the improvement in bonding performance is limited. .
- Example 1 and Comparative Example 6 the bonding strength is only 2.7MPa. This is because the grafting rate of maleic anhydride is generally only 0.8 to 2%. Therefore, even if a larger amount of maleic anhydride graft is added, however, there are only one thousandth of the chemical reaction sites available for bonding, so the bonding strength is very low; moreover, polyolefin is a non-polar material and has poor physical bonding anchor points with epoxy resin. Styrene maleic anhydride has poor compatibility with toughening agents. During mechanical property testing, the maleic anhydride-grafted PP position formed a stress defect, resulting in a significant reduction in overall performance.
- Example 1 and Comparative Example 7 that after replacing glass fiber with talc powder, although the bonding performance remains good, the inorganic filler is a flake filler, and compared with the needle-shaped filler glass fiber, its overall enhancement The increase in stiffness and even the balance of stiffness and toughness are far inferior to those of glass fiber. Therefore, the overall mechanical properties of Comparative Example 7, including heat resistance, have dropped significantly, which is significantly different from Example 1.
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)
- Laminated Bodies (AREA)
Abstract
苯乙烯马来酸酐共聚物复合材料及其制备方法和应用，属于高分子材料技术领域。苯乙烯马来酸酐共聚物复合材料按重量份数计，包括以下组分：苯乙烯马来酸酐共聚物10～60份；增韧剂20～50份；玻璃纤维20～50份；相容剂0.3～8份；其中，所述相容剂为含有环氧官能团的结构单元的聚合物，含有环氧官能团的结构单元的质量含量为1～10％，测试方法为GB/T 1677-2008。苯乙烯马来酸酐共聚物复合材料通过苯乙烯马来酸酐共聚物和相容剂的优化协同作用即可实现与环氧树脂改性碳纤维复合材料在120～130℃的温度下的粘结性。
Description
本发明涉及高分子材料技术领域，更具体地，涉及一种苯乙烯马来酸酐共聚物复合材料及其制备方法和应用。
汽车轻量化技术是汽车产业发展的重要方向之一，是全球汽车厂商的共同选择，是实现节能减排的有效直接可行的途径，是我国应对能源安全的必然措施，也是汽车产业可持续发展的必经之路。汽车轻量化与安全性之间并不矛盾，合适的轻量化有助于汽车安全性能的提升。汽车轻量化产业的发展有助于提升我国自主品牌汽车的国际竞争力，也是提高我国汽车工业自主创新能力的重要途径之一，是调整产品结构和产业化结构的切实需要，还有利于提升和发展我国相关工业的技术水平，同时也为汽车先进材料技术的发展方向指明了前进的道路，真正意义上实现汽车行业的供给侧改革。
车身“以塑代钢”技术已成为车身轻量化的主要手段之一。众所周知，车身用钢的密度为7.85g/cm
3，工程塑料的密度一般为1.1～1.4g/cm
3，车身“以塑代钢”就是通过采用密度更低的工程塑料，尤其是复合材料替代传统的车身金属零部件，结合CAE(是用计算机辅助求解复杂工程和产品结构强度、刚度、屈曲稳定性、动力响应、热传导、三维多体接触、弹塑性等力学性能)分析手段，确保汽车综合性能指标的前提下，优化结构设计，实现车身轻量化。复合材料是由两种或两种以上不同性质的材料，通过物理或化学方法在宏观上组成具有新性能的材料。各种材料在性能上互相取长补短，产生协同效应，使复合材料的综合性能优于原组成材料而满足各种不同的要求。特别是纤维增强热塑性复合材料具有密度小、设计灵活、耐腐蚀、耐热、耐冲击、抗振等优点，在汽车上的应用范围越来越广泛。
碳纤维增强聚合物基复合材料(CFRP)是一种新型的汽车用复合材料，具有绝佳的韧性和抗拉强度，且密度只有钢的1/4，适用于制造车身覆盖件和底盘零部件，减重幅度通常可达50％～65％。其主要特点有：一、可大幅度减轻汽车质量，特别适合制造车体部件。用CFRP制成的车体部件，其质量比铝材和钢材制作的车体部件分别轻30％和50％以上，可减轻整车质量达10％；二、碰撞时表现出 优异的强度和刚度。碳纤维直径约为0.007mm，受力主要集中在纤维本身的定向流方向，因此可选择合理的排列，将纤维彼此层叠构建，从而优化CFRP的特色功能和特性，将其调整到预期的强度和承载性能；三、可制成高度整合的超大型车体部件，为车体设计和制造提供了巨大优势，固定和支承等功能可直接整合于部件本体之中。即使复杂的结构件或整车模块，均可用同一模具一体化制作，从而减少车体所需部件的数量。
CFRP的应用可使汽车车身减轻30％～50％，相当于钢制车身结构质量的2/3～1/2。以普通车为例，平均质量为1380kg，CFRP化之后，质量将下降到970kg，下降了30％。但由于目前CFRP价格昂贵，使它在一般汽车中的应用受到限制。汽车主机厂的结构设计师们一方面为了汽车轻量化希望尽可能多的应用CFRP材料，另一方面又受限于成本，因此将CFRP用在最关键的部位。为达成这一目标，设计师们开发了一种全新的轻量化汽车门板模块，其外门板由碳纤维复合材料制成，其特点是轻质高强，且复杂结构较少，易于快节拍成型；内门板则由玻纤增强复合材料制备，其特点是轻质强度适中，但可以通过注塑成型，易于成型具有复杂结构的内门板，再将内外门板在120～130℃的温度下热粘合，从而制备出完整的门模块骨架。
现有技术公开的外门板是由环氧树脂改性碳纤维复合材料制备而成。为了制备汽车内门板，现有技术公开了一种全塑尾门专用、粘接效果优异的长玻璃纤维增强聚丙烯复合材料，其组成主要包括重量百分比计的30～40％长玻璃纤维，50～60％的改性聚丙烯树脂，1～6％的马来酸酐接枝物PP-g-MAH，0.5～5％的抗氧化助剂母粒，1～3％的环氧类助剂等。然而，该材料能够与环氧树脂改性碳纤维复合材料可供粘接的反应位点较少，基体树脂极性低，采用的长玻璃纤维增强聚丙烯复合材料技术方案无法与环氧树脂改性碳纤维复合材料在120～130℃的温度下进行有效的高强度整体粘接。
发明内容
本发明要解决的技术问题是克服现有材料与环氧树脂改性碳纤维复合材料在120～130℃的温度下的粘接性不佳缺陷和不足，提供一种苯乙烯马来酸酐共聚物复合材料，通过苯乙烯马来酸酐共聚物和相容剂的协同作用，大幅提升了苯乙烯马来酸酐共聚物复合材料与环氧树脂改性碳纤维复合材料在120～130℃的温度下的粘结性。
本发明的再一目的在于提供一种苯乙烯马来酸酐共聚物复合材料的制备方法。
本发明的另一目的在于提供一种苯乙烯马来酸酐共聚物复合材料在制备汽车结构件中的应用。
本发明的又一目的在于提供一种汽车门内板。
本发明上述目的通过以下技术方案实现：
一种苯乙烯马来酸酐共聚物复合材料，按重量份数计，包括以下组分：
其中，所述相容剂为含有环氧官能团的结构单元的聚合物，含有环氧官能团的结构单元的质量含量为1～10％，测试方法为GB/T 1677-2008。
其中需要说明的是：
本发明的苯乙烯马来酸酐共聚物复合材料通过苯乙烯马来酸酐共聚物和含有环氧环能团结构单元的相容剂的优化协同作用即可实现与环氧树脂改性碳纤维复合材料在120～130℃的温度下的高强度粘结性。
本发明的苯乙烯马来酸酐共聚物复合材料各组分的作用机理具体如下：
苯乙烯马来酸酐共聚物中，马来酸酐共聚在苯乙烯链段上，使得材料具有较高的耐热性能，苯乙烯马来酸酐共聚物复合材料可以与环氧树脂改性碳纤维复合材料在120～130℃的温度下进行有效热粘接，且不会造成苯乙烯马来酸酐共聚物复合材料的热变形。而且，苯乙烯马来酸酐共聚物中的马来酸酐吸收空气中的水后，能够与环氧树脂改性碳纤维复合材料中的环氧树脂进行快速的化学反应结合，从而提高了苯乙烯马来酸酐共聚物复合材料与环氧树脂改性碳纤维复合材料的粘接性能。
相容剂中含有环氧官能团的结构单元与环氧树脂改性碳纤维复合材料中的官能团的结构相近，相容剂中含有环氧官能团的结构单元位于复合材料的表面可以在高温下与具有相同官能团的环氧树脂改性碳纤维复合材料中的树脂高分子进行物理互容共穿，另一方面适量的相容剂可以与苯乙烯马来酸酐发生轻度可逆交联反应，表面的苯乙烯马来酸酐共聚物高分子链通过相容剂与皮芯结构材料的 芯层甚至与空气接触表面的部分苯乙烯马来酸酐共聚物高分子链连接在一起，使苯乙烯马来酸酐共聚物复合材料和碳纤维复合材料表面的环氧树脂成为一个整体，大幅提高了苯乙烯马来酸酐共聚物复合材料与环氧树脂改性碳纤维复合材料的粘接性能，苯乙烯马来酸酐共聚物复合材料不仅在材料的表面跟碳纤维复合材料进行有效粘接，而且整个苯乙烯马来酸酐共聚物复合材料也与环氧树脂改性碳纤维复合材料形成有一定化学结构连接的整体。
本发明通过苯乙烯马来酸酐共聚物和相容剂与环氧树脂改性碳纤维复合材料的化学结合和物理结合相互协同大幅提高复合材料与环氧树脂改性碳纤维复合材料的粘接性能。
相容剂的添加量过少，苯乙烯马来酸酐共聚物复合材料与环氧树脂改性碳纤维复合材料的粘接效果提升有限。
相容剂的添加量过大，虽然能够显著提高苯乙烯马来酸酐共聚物复合材料与环氧树脂改性碳纤维复合材料的粘接效果，但是会显著降低复合材料的冲击性能。
相容剂中含有环氧官能团的结构单元的质量含量与最终复合材料与环氧树脂改性碳纤维复合材料的粘接性能和冲击性能有关，质量含量小于1％，甲基丙烯酸缩水甘油酯与环氧树脂改性碳纤维复合材料中的环氧树脂的物理结合性较差，对最终复合材料与环氧树脂改性碳纤维复合材料的粘接效果改善不显著；质量含量大于10％，虽然有效提高了复合材料与环氧树脂改性碳纤维复合材料的粘接效果，但是含有环氧官能团的结构单元的质量含量较高，会显著降低复合材料的冲击性能。
增韧剂的作用为是提升复合材料的冲击性能。增韧剂可以为含有苯乙烯类抗冲增韧剂和乙烯基芳族结构单元和烯属不饱和腈结构单元共聚物。
其中所述苯乙烯类抗冲增韧剂为苯乙烯-丁二烯-丙烯腈共聚物、苯乙烯-丁二烯-丙烯酸酯共聚物、甲基丙烯酸酯-丁二烯-苯乙烯共聚物、甲基丙烯酸酯-丙烯酸酯-苯乙烯共聚物、苯乙烯-丙烯酸酯-丙烯腈共聚物或甲基丙烯酸酯-丙烯酸酯共聚物中一种或几种的混合物。
其中所述乙烯基芳族结构单元和烯属不饱和腈结构单元共聚物中，丙烯腈含量可以为20％～30％。
优选地，环氧树脂粘接性优异的苯乙烯马来酸酐共聚物复合材料中，
按重量份数计，包括以下组分：
为了进一步提升复合材料与环氧树脂改性碳纤维复合材料的粘接性能和冲击性能，优选地，所述相容剂中，含有环氧官能团的结构单元的质量含量为3～6％。
优选地，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-甲基丙烯酸缩水甘油酯中含有苯乙烯-丙烯腈，同基体树脂苯乙烯马来酸酐具有很好的相容性，有利于提高复合材料的力学和耐热性能，避免高温粘接变形。
为了进一步提高复合材料与环氧树脂改性碳纤维复合材料的热变形温度、粘接性能和冲击性能，优选地，所述苯乙烯马来酸酐共聚物为苯乙烯马来酸酐无规共聚物，其中马来酸酐的摩尔含量为18～26％。
优选地，所述玻璃纤维为无碱短切玻璃纤维。
无碱短切玻璃纤维能够提高复合材料的刚性和耐热性能，避免高温粘接变形。
在实际应用中，根据实际需求，还可以添加润滑剂和/或抗氧剂等加工助剂。
抗氧剂可选自受阻胺类、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的混合物。
润滑剂可选自酰胺类、金属皂类和低分子酯类中的一种或几种的混合物。
抗氧剂可提升苯乙烯马来酸酐共聚物复合材料的抗氧化效果，润滑剂可提升苯乙烯马来酸酐共聚物复合材料的润滑效果。
优选地，所述增韧剂为苯乙烯-丁二烯-丙烯腈共聚物。
在实际应用中，根据实际性能需要，还包括着色剂等助剂。
其中，以重量份数计，着色剂0～0.5份。
着色剂可选自炭黑等。
着色剂可改变苯乙烯马来酸酐共聚物复合材料的颜色。
本发明还保护上述苯乙烯马来酸酐共聚物复合材料的制备方法，具体包括如下步骤：将各组分混合均匀，通过双螺杆挤出机在220～240℃下熔融挤出、造粒， 干燥后即得所述苯乙烯马来酸酐共聚物复合材料。
本发明制备得到的苯乙烯马来酸酐共聚物复合材料具有很好的与环氧树脂改性碳纤维复合材料的粘接优异性，可以广泛应用于塑料制品的制备，本发明尤其保护所述苯乙烯马来酸酐共聚物复合材料在制备汽车结构件中的应用。汽车结构件可以为汽车内门板，仪表板骨架、前端框架、天窗框架、护风圈、后视镜支架等，但不限于上述应用，其中特别适用于制备用于与碳纤维复合材料粘接的汽车门内板。
本发明还具体保护一种汽车门板，所述汽车门板由包括所述苯乙烯马来酸酐共聚物复合材料的原料和碳纤维复合材料粘接而成。
汽车门板由汽车内门板和汽车外门板粘接而成，汽车外门板的材料为碳纤维复合材料，本发明的所述苯乙烯马来酸酐共聚物复合材料在注塑汽车内门板后，能够大幅提升汽车内门板同碳纤维复合材料外门板的粘接强度，最终保证整个汽车门模块得以通过严苛的汽车碰撞实验，在乘客侵入距离这一关键指标上有更好的表现。
与现有技术相比，本发明的有益效果是：
本发明公开了一种苯乙烯马来酸酐共聚物复合材料，其树脂基材由苯乙烯马来酸酐共聚物和含有环氧官能团的结构单元的相容剂组成，通过与增韧剂和玻璃纤维等组合协同作用，有效改善了与环氧树脂改性碳纤维复合材料在120～130℃的温度下的粘结性。
本发明的苯乙烯马来酸酐共聚物复合材料与环氧树脂改性碳纤维复合材料的粘接强度可达到8.5MPa以上，在105℃以下的温度时都不会发生热变形。
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。
苯乙烯马来酸酐共聚物1为苯乙烯马来酸酐共聚物SZ23110，马来酸酐的摩尔含量为26％，荷兰Polyscope；
苯乙烯马来酸酐共聚物2为苯乙烯马来酸酐共聚物SMA-725，马来酸酐的摩尔含量为18％，中国华雯；
苯乙烯马来酸酐共聚物3为苯乙烯马来酸酐共聚物SMA-700，马来酸酐的 摩尔含量为8％，中国华雯；
苯乙烯马来酸酐共聚物4为苯乙烯马来酸酐共聚物SMA-800，马来酸酐的摩尔含量为35％，中国华雯；
增韧剂为苯乙烯-丁二烯-丙烯腈共聚物PA-757，市售可得且所有实施例和对比例用的是同一种。
玻璃纤维为无碱短切玻璃纤维，市售可得且所有实施例和对比例用的是同一种；
滑石粉，市售可得；
相容剂1为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-005，含有环氧官能团的结构单元为甲基丙烯酸缩水甘油酯，甲基丙烯酸缩水甘油酯的质量含量为5％，佳易容；
相容剂2为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-002，含有环氧官能团的结构单元为甲基丙烯酸缩水甘油酯，甲基丙烯酸缩水甘油酯的质量含量为2％，佳易容；
相容剂3为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-008，含有环氧官能团的结构单元为甲基丙烯酸缩水甘油酯，甲基丙烯酸缩水甘油酯的质量含量为8％，佳易容；
相容剂4为乙烯-甲基丙烯酸甲酯-甲基丙烯酸缩水甘油酯AX8900，含有环氧官能团的结构单元为甲基丙烯酸缩水甘油酯，甲基丙烯酸缩水甘油酯的质量含量为8％，阿科玛；
相容剂5为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-012，含有环氧官能团的结构单元为甲基丙烯酸缩水甘油酯，甲基丙烯酸缩水甘油酯的质量含量为12％，佳易容；
相容剂6为苯乙烯-丙烯腈-甲基丙烯酸缩水甘油酯SAG-0005，含有环氧官能团的结构单元为甲基丙烯酸缩水甘油酯，甲基丙烯酸缩水甘油酯的质量含量为0.5％，佳易容；
相容剂7为马来酸酐接枝聚丙烯，马来酸酐的接枝率为2％，市售可得。
润滑剂为低分子酯类，市售可得且所有实施例和对比例用的是同一种；
抗氧剂为受阻酚类和亚磷酸酯类，受阻酚类和亚磷酸酯类的比为1：1，市售可得且所有实施例和对比例用的是同一种；
实施例1～11
一种苯乙烯马来酸酐共聚物复合材料，按重量份数计，包括以下组分：苯乙烯马来酸酐共聚物；增韧剂；填料；相容剂；润滑剂和抗氧剂；
其中各组分的具体含量如下表1所示。
表1 各实施例的苯乙烯马来酸酐共聚物复合材料组成(以重量份数计)
| 1 | 2 | 3 | 4 | 5 | |
| 苯乙烯马来酸酐共聚物1 | 25 | 10 | 60 | 20 | 40 |
| 增韧剂 | 40 | 50 | 20 | 40 | 35 |
| 玻璃纤维 | 30 | 50 | 20 | 40 | 25 |
| 相容剂1 | 5 | 0.3 | 8 | 1 | 5 |
| 润滑剂 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 抗氧剂 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
续表1
| 6 | 7 | 8 | 9 | 10 | 11 | |
| 苯乙烯马来酸酐共聚物1 | 25 | 25 | 25 | |||
| 苯乙烯马来酸酐共聚物2 | 25 | |||||
| 苯乙烯马来酸酐共聚物3 | 25 | |||||
| 苯乙烯马来酸酐共聚物4 | 25 | |||||
| 增韧剂 | 40 | 40 | 40 | 40 | 40 | 40 |
| 玻璃纤维 | 30 | 30 | 30 | 30 | 30 | 30 |
| 相容剂1 | 5 | 5 | 5 | |||
| 相容剂2 | 5 | |||||
| 相容剂3 | 5 | |||||
| 相容剂4 | 5 | |||||
| 润滑剂 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 抗氧剂 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
苯乙烯马来酸酐共聚物复合材料的制备方法如下：
将各组分混合均匀，再投入螺杆挤出机中在230℃进行挤出造粒，其中短切玻璃纤维侧喂进入双螺杆挤出机，最终得到苯乙烯马来酸酐共聚物复合材料； 其中，双螺杆挤出机的螺杆转速为400r/min。
对比例1～7
一种苯乙烯马来酸酐共聚物复合材料，其中各组分的具体含量如下表2所示。
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | |
| 苯乙烯马来酸酐共聚物1 | 25 | 25 | 25 | 25 | 25 | 25 | 25 |
| 增韧剂1 | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| 玻璃纤维 | 30 | 30 | 30 | 30 | 30 | 30 | |
| 滑石粉 | 30 | ||||||
| 相容剂1 | / | 0.1 | 10 | 5 | |||
| 相容剂5 | 5 | ||||||
| 相容剂6 | 5 | ||||||
| 相容剂7 | 10 | ||||||
| 润滑剂 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| 抗氧剂 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
苯乙烯马来酸酐共聚物复合材料的制备方法与实施例1相同，这里不再赘述。
各项性能测试方法：
(1)力学性能：使用震雄注塑机注塑各类标准样条和样板。
拉伸强度：按照ISO527-2019标准测试，拉伸速度为50mm/min；
弯曲模量：按照ISO178-2019标准测试，速度2mm/min，跨距64mm；
Izod缺口冲击强度：按照ISO180/1eA-2000标准测试；
热变形温度：按照ISO 75-2-2013，负荷为1.82MPa标准测试。
(2)粘接性能：将碳纤维复合材料样条同玻纤增强苯乙烯马来酸酐共聚物样条进行热粘接，粘接时间5小时，粘接温度120℃，按GB/T 7124-2008进行粘接强度测试，测试温度23℃，夹具间距为115mm，拉伸速度为50mm/min。
各实施例的性能检测结果如下表3所示。
续表3
各对比例的性能检测结果如下表4所示。
从实施例1和对比例1可以看出，不加相容剂，材料与环氧树脂改性碳纤维复合材料的粘接性能下降75％，由于相容剂为含有环氧官能团的结构单元的聚合物，加入一定官能度的相容剂，一方面可以在高温下与具有相同官能团的环氧树脂改性碳纤维复合材料中的树脂高分子进行物理互容共穿，另一方面适量的相容剂可以与苯乙烯马来酸酐发生轻度可逆交联反应，表面的苯乙烯马来酸酐共聚物高分子链通过相容剂与芯层甚至下表面的部分苯乙烯马来酸酐共聚物高分子链连接在一起，使苯乙烯马来酸酐共聚物复合材料成为一个整体，大幅提高了苯乙 烯马来酸酐共聚物复合材料与环氧树脂改性碳纤维复合材料的粘接性能。
从实施例1和对比例2可以看出，相容剂的加入量过少，苯乙烯马来酸酐共聚复合材料与环氧树脂改性碳纤维复合材料的粘接强度提升有限，说明相容剂对苯乙烯马来酸酐共聚物的整体微交联作用不可忽视，只有形成整体的粘接才有可能大幅度提高粘接性能。
从实施例1和对比例3可以看出，相容剂的加入量过大，虽然材料力学强度、模量和粘接强度都有很好的保持，但冲击性能下降显著，虽然对比例3的苯乙烯马来酸酐共聚物依然可以应用在碳纤维复合材料的粘接领域，但无法应用在对冲击性能要求较高的汽车零部件上，否则在进行汽车撞击实验中，产生大量的尖锐碎片引起人员伤亡，无法达到五星碰撞等级要求。
从实施例1和对比例4可以看出，相容剂中含有环氧官能团的结构单元的质量含量过大，虽然材料力学强度、模量和粘接强度有很好的保持，但由于局部官能团含量过高，导致易发生过度交联，使冲击性能下降显著，无法应用在既有碳纤维复合材料粘接要求，又有很高抗冲性能要求的汽车零部件上。
从实施例1和对比例5可以看出，相容剂中含有环氧官能团的结构单元的质量含量过小，无法与苯乙烯马来酸酐共聚物形成整体的微交联，粘接性能提升有限。
从实施例1和对比例6可以看出，粘接强度只有2.7MPa，这是因为马来酸酐的接枝率一般仅为0.8～2％，因此即使添加较大量的马来酸酐接枝物，但是可供粘接的化学反应位点仅有千分之一，因此粘接强度很低；而且，聚烯烃为非极性材料，与环氧树脂形成物理结合锚点也很差，与整体的苯乙烯马来酸酐和增韧剂相容性很差，在进行力学性能测试时，马来酸酐接枝PP位置形成受力缺陷，导致整体性能降低显著。
从实施例1和对比例7可以看出，将玻纤更换为滑石粉后，虽然粘接性能保持较好，但无机填料为片状填料，与针状填料玻纤相比，其整体的增强增刚，甚至刚韧平衡上远不如玻璃纤维，因此对比例7整体的力学性能包括耐热性能均有较大幅度的下降，与实施例1差距明显。
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)
- 一种苯乙烯马来酸酐共聚物复合材料，其特征在于，按重量份数计，包括以下组分：
其中，所述相容剂为含有环氧官能团的结构单元的聚合物，含有环氧官能团的结构单元的质量含量为1～10％，测试方法为GB/T 1677-2008。 - 如权利要求1所述苯乙烯马来酸酐共聚物复合材料，其特征在于，按重量份数计，包括以下组分：
- 如权利要求1所述苯乙烯马来酸酐共聚物复合材料，其特征在于，所述相容剂为含有甲基丙烯酸缩水甘油酯的聚合物。
- 如权利要求3所述苯乙烯马来酸酐共聚物复合材料，其特征在于，所述相容剂中，含有环氧官能团的结构单元的质量含量为3～6％。
- 如权利要求4所述苯乙烯马来酸酐共聚物复合材料，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。
- 如权利要求1所述苯乙烯马来酸酐共聚物复合材料，其特征在于，所述苯乙烯马来酸酐共聚物为苯乙烯马来酸酐无规共聚物，其中马来酸酐的摩尔含量为18～26％。
- 如权利要求1所述苯乙烯马来酸酐共聚物复合材料，其特征在于，所述玻璃纤维为无碱短切玻璃纤维。
- 权利要求1～7任一项所述苯乙烯马来酸酐共聚物复合材料的制备方法，其特征在于，将各组分混合均匀，通过双螺杆挤出机在220～240℃熔融挤出、造粒，干燥后即得所述苯乙烯马来酸酐共聚物复合材料。
- 一种权利要求1～7任意一项所述苯乙烯马来酸酐共聚物复合材料在制备 汽车结构件中的应用。
- 一种汽车门板，其特征在于，所述汽车门板由包括权利要求1～7任意一项所述苯乙烯马来酸酐共聚物复合材料的原料和碳纤维复合材料粘接而成。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210233826.7 | 2022-03-09 | ||
| CN202210233826.7A CN114621553B (zh) | 2022-03-09 | 2022-03-09 | 一种苯乙烯马来酸酐共聚物复合材料及其制备方法和应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023169033A1 true WO2023169033A1 (zh) | 2023-09-14 |
Family
ID=81900336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2022/138881 WO2023169033A1 (zh) | 2022-03-09 | 2022-12-14 | 苯乙烯马来酸酐共聚物复合材料及其制备方法和应用 |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114621553B (zh) |
| WO (1) | WO2023169033A1 (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020115748A1 (en) * | 2000-12-20 | 2002-08-22 | Cheil Industries Inc. | Glass fiber reinforced styrenic thermoplastic composites containing an aminosilane coupling agent |
| WO2006056758A2 (en) * | 2004-11-23 | 2006-06-01 | Nova Chemicals (International) S.A. | Rubber modified thermoplastic resin |
| CN101555341A (zh) * | 2009-05-25 | 2009-10-14 | 国家复合改性聚合物材料工程技术研究中心 | 一种高强玻纤增强abs复合材料及其制备方法 |
| CN102408524A (zh) * | 2011-11-21 | 2012-04-11 | 福建师范大学 | 一种多单体熔融接枝丙烯腈-丁二烯-苯乙烯共聚物及其制备方法 |
| CN112662107A (zh) * | 2020-12-22 | 2021-04-16 | 金发科技股份有限公司 | 一种玻纤增强苯乙烯马来酸酐共聚物组合物及其制备方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272376C (zh) * | 2002-03-21 | 2006-08-30 | 同济大学 | 一种增韧增强改性苯乙烯－马来酸酐无规共聚物 |
| CN1490352A (zh) * | 2002-10-16 | 2004-04-21 | 中国石油化工股份有限公司 | 含苯乙烯－马来酸酐无规共聚物的组合物 |
| CN1245447C (zh) * | 2003-09-03 | 2006-03-15 | 中国石油化工股份有限公司 | 玻璃纤维增强热塑性聚合物的组合物 |
| CN102617973B (zh) * | 2012-03-19 | 2014-04-16 | 上海锦湖日丽塑料有限公司 | 高熔体强度的汽车尾翼专用组合物及其制备方法 |
-
2022
- 2022-03-09 CN CN202210233826.7A patent/CN114621553B/zh active Active
- 2022-12-14 WO PCT/CN2022/138881 patent/WO2023169033A1/zh unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020115748A1 (en) * | 2000-12-20 | 2002-08-22 | Cheil Industries Inc. | Glass fiber reinforced styrenic thermoplastic composites containing an aminosilane coupling agent |
| WO2006056758A2 (en) * | 2004-11-23 | 2006-06-01 | Nova Chemicals (International) S.A. | Rubber modified thermoplastic resin |
| CN101555341A (zh) * | 2009-05-25 | 2009-10-14 | 国家复合改性聚合物材料工程技术研究中心 | 一种高强玻纤增强abs复合材料及其制备方法 |
| CN102408524A (zh) * | 2011-11-21 | 2012-04-11 | 福建师范大学 | 一种多单体熔融接枝丙烯腈-丁二烯-苯乙烯共聚物及其制备方法 |
| CN112662107A (zh) * | 2020-12-22 | 2021-04-16 | 金发科技股份有限公司 | 一种玻纤增强苯乙烯马来酸酐共聚物组合物及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114621553A (zh) | 2022-06-14 |
| CN114621553B (zh) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110776742B (zh) | 一种高填充低翘曲电池模组端板用的聚苯硫醚复合材料及其制备方法 | |
| CN100509953C (zh) | 一种聚对苯二甲酸丁二醇酯复合材料及其制备方法 | |
| US8299144B2 (en) | TPO nanocomposites and methods of use | |
| CN103044764A (zh) | 一种高韧性长玻璃纤维增强聚丙烯复合材料及其制备方法 | |
| CN111978640A (zh) | 一种石墨烯改性保险杠用聚丙烯复合材料及其制备方法 | |
| CN113603964B (zh) | 一种用于汽车内饰的低voc玻纤增强聚丙烯复合材料及其制备方法 | |
| CN106009246A (zh) | 一种有机纤维增强聚丙烯复合材料及其lft-d成型工艺 | |
| WO2023024939A1 (zh) | 一种微发泡聚丙烯组合物及其制备方法和应用 | |
| CN104861287A (zh) | 一种汽车仪表台用晶须改性pp复合材料及其制备方法 | |
| CN102367311B (zh) | 一种低比重汽车保险杆用聚丙烯复合材料及其制备方法 | |
| CN106189136A (zh) | 一种改性聚乳酸复合材料及其制造方法和应用 | |
| CN111978641A (zh) | 一种高模量、高流动、高抗冲玻纤增强聚丙烯复合材料及其制备方法 | |
| KR102452003B1 (ko) | 레이저 융착용 폴리프로필렌 수지 조성물 및 이를 포함하는 운송 수단용 성형품 | |
| CN103665570B (zh) | 一种超低温韧性聚丙烯组合物及其制备方法 | |
| KR101154303B1 (ko) | 탄소섬유 복합재 조성물 및 이를 이용한 성형품 | |
| WO2023169033A1 (zh) | 苯乙烯马来酸酐共聚物复合材料及其制备方法和应用 | |
| WO2024056043A1 (zh) | 一种聚碳酸酯合金及其制备方法和应用 | |
| US10533086B2 (en) | Polypropylene resin composition and molded product thereof | |
| JP2017186492A (ja) | 炭素繊維強化・改質ポリプロピレン系樹脂の発泡成形体の製造方法 | |
| KR101257820B1 (ko) | 폴리올레핀 복합소재 조성물 | |
| CN108530754A (zh) | 一种用于汽车保险杠薄壁注塑件的聚丙烯塑料及制备方法 | |
| CN108034218A (zh) | 一种用于新能源汽车尾翼的abs材料及其制备方法 | |
| CN114539664A (zh) | 一种低线性膨胀系数、易粘接的全塑尾门外板材料及其制备方法 | |
| CN105820440A (zh) | 一种高性能pp/epdm热塑性弹性体及其制备方法 | |
| US20240017453A1 (en) | Ultra-low density conductive thermoplastic composite material for painted components |
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: 22930654 Country of ref document: EP Kind code of ref document: A1 |