CN113136101B - Nylon composite material for realizing high strength by using composite compatilizer and preparation method thereof - Google Patents

Nylon composite material for realizing high strength by using composite compatilizer and preparation method thereof Download PDF

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CN113136101B
CN113136101B CN202110446110.0A CN202110446110A CN113136101B CN 113136101 B CN113136101 B CN 113136101B CN 202110446110 A CN202110446110 A CN 202110446110A CN 113136101 B CN113136101 B CN 113136101B
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nylon
compatibilizer
polyphenylene sulfide
composite material
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CN113136101A (en
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张伟
吴玉成
徐星驰
孙圳
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Jiangsu Lihan Technology Co ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/08Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2207/04Thermoplastic elastomer

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Abstract

The invention discloses a nylon composite material for realizing high strength by using a composite compatilizer and a preparation method thereof, belonging to the technical field of modification of high polymer materials. The composite material comprises nylon, a composite compatilizer and polyphenylene sulfide, wherein the mass ratio of the nylon to the polyphenylene sulfide is (2.1-5.6): 1; the nylon and the polyphenylene sulfide are compatible through a composite compatilizer; the composite compatilizer is a composite graft obtained by melt grafting reaction of polyphenylene sulfide, thermoplastic elastomer X and a grafting monomer, and the polyphenylene sulfide and the thermoplastic elastomer X in the composite graft are connected through chemical bonds. The added polyphenylene sulfide resin can greatly improve the rigidity and hydrophobicity of the nylon material, the compatibility of the polyphenylene sulfide and the nylon can be effectively improved by adding the composite compatilizer, and the hydrophobicity and strength of the composite material are effectively improved from the aspect of improving the compatibility of the polyphenylene sulfide and the nylon.

Description

一种利用复合相容剂实现高强度的尼龙复合材料及其制备 方法A kind of nylon composite material and its preparation using composite compatibilizer to realize high strength method

技术领域technical field

本发明属于高分子材料改性技术领域,更具体地说,涉及一种利用复合相容剂实现高强度的尼龙复合材料及其制备方法。The invention belongs to the technical field of polymer material modification, and more specifically relates to a high-strength nylon composite material using a composite compatibilizer and a preparation method thereof.

背景技术Background technique

随着笔记本电脑轻量化的发展,超薄已成为其发展主流。这不仅需要对笔记本电脑的产品结构重新进行设计,更需要因其结构的变化对材料进行优化。这其中就涉及到键盘。With the development of lightweight notebook computers, ultra-thin has become the mainstream of its development. This not only needs to redesign the product structure of the notebook computer, but also needs to optimize the material because of its structural changes. This involves the keyboard.

键盘上有很多字母或符号按键,而在按键下存在着支撑骨架。在未进行超薄化设计之前,支撑骨架是由聚甲醛(POM)材料生产制造。在支撑骨架超薄化设计之后,其厚度已降至0.6mm左右。但由于POM材料强度的问题,超薄化设计之后,POM已无法满足其使用要求。设计师将材料优化为强度更高的玻纤增强尼龙66材料。但由于尼龙66树脂分子结构中含有亲水性的酰胺基团,具有很强的吸水性,在高温高湿环境下玻纤增强尼龙66材料也无法通过产品验证,即使将玻纤含量提高到50%或以上。There are many letter or symbol keys on the keyboard, and there is a support frame under the keys. Before the ultra-thin design, the supporting frame is made of polyoxymethylene (POM) material. After the ultra-thin design of the support frame, its thickness has been reduced to about 0.6mm. However, due to the strength of the POM material, after the ultra-thin design, the POM can no longer meet its use requirements. The designer optimized the material to be a stronger glass fiber reinforced nylon 66 material. However, due to the hydrophilic amide group in the molecular structure of nylon 66 resin, which has strong water absorption, the glass fiber reinforced nylon 66 material cannot pass the product verification under high temperature and high humidity environment, even if the glass fiber content is increased to 50 %or above.

经检索,中国发明专利CN111040442A公开了一种晶须增强疏水性尼龙66复合材料及制备方法;其具体公开了通过将具有疏水性的聚四氟乙烯牢固附着在硫酸钙晶须表面,以此作为填料分散于尼龙66,聚四氟乙烯的疏水性赋予尼龙66良好的疏水效果,同时,聚四氟乙烯牢固包覆在硫酸钙晶须表面,受硫酸钙晶须纤维特性的网络分散,不会出现聚四氟乙烯离析的问题,而且硫酸钙晶须能够有效增加尼龙66的强度。可见该复合材料是通过填充附着了聚四氟乙烯的硫酸钙晶须,利用填充物的疏水性来提升尼龙复合材料的疏水性;但是该复合材料仅使用常规的马来酸酐接枝POE作为相容剂,因此其强度较低可能是由于聚四氟乙烯和尼龙66之间的相容性未得到有效地解决,导致聚四氟乙烯包裹的高强度硫酸钙晶须与尼龙66之间的相容性较差,而在材料组分之间相容性较差的情况下,制备出的复合材料强度等力学性能会明显不足。After retrieval, the Chinese invention patent CN111040442A discloses a whisker-reinforced hydrophobic nylon 66 composite material and its preparation method; it specifically discloses that by firmly attaching hydrophobic polytetrafluoroethylene to the surface of calcium sulfate whiskers, as The filler is dispersed in nylon 66, and the hydrophobicity of polytetrafluoroethylene endows nylon 66 with a good hydrophobic effect. There is a problem of PTFE segregation, and calcium sulfate whiskers can effectively increase the strength of nylon 66. It can be seen that the composite material is filled with calcium sulfate whiskers attached to polytetrafluoroethylene, and the hydrophobicity of the filler is used to improve the hydrophobicity of the nylon composite material; but the composite material only uses conventional maleic anhydride grafted POE as the phase. Compatibilizer, so its lower strength may be due to the fact that the compatibility between PTFE and nylon 66 has not been effectively resolved, resulting in the phase between the high-strength calcium sulfate whiskers wrapped in PTFE and nylon 66. The compatibility is poor, and in the case of poor compatibility between material components, the strength and other mechanical properties of the prepared composite material will be obviously insufficient.

基于以上原因,目前亟需对玻纤增强尼龙66材料进行改进,设计一种高疏水高强度的尼龙复合材料,以满足其在高温高湿环境下的强度要求。Based on the above reasons, there is an urgent need to improve the glass fiber reinforced nylon 66 material and design a high hydrophobic and high strength nylon composite material to meet its strength requirements in high temperature and high humidity environments.

发明内容Contents of the invention

1.要解决的问题1. The problem to be solved

针对现有技术中尼龙复合材料高温高湿环境下的吸水性较强、强度降低的问题,本发明提供一种利用复合相容剂实现高强度的尼龙复合材料及其制备方法;通过将PPS与热塑性弹性体复合接枝极性单体,较好地改善了尼龙与PPS之间的相容性,从而有效提升尼龙复合材料的疏水性和强度,解决了其高温高湿环境下的吸水性较强、强度降低的问题。Aiming at the problem of strong water absorption and reduced strength of nylon composite materials in the prior art under high-temperature and high-humidity environments, the present invention provides a nylon composite material that uses a composite compatibilizer to achieve high strength and a preparation method thereof; by combining PPS with The thermoplastic elastomer composite grafted polar monomers can better improve the compatibility between nylon and PPS, thereby effectively improving the hydrophobicity and strength of nylon composite materials, and solving the problem of poor water absorption in high-temperature and high-humidity environments. Strong, low-strength problems.

2.技术方案2. Technical solution

为了解决上述问题,本发明所采用的技术方案如下:In order to solve the above problems, the technical scheme adopted in the present invention is as follows:

本发明的一种利用复合相容剂实现高强度的尼龙复合材料,包括尼龙、复合相容剂和聚苯硫醚,尼龙和聚苯硫醚的质量比为(2.1~5.6):1;所述尼龙和聚苯硫醚通过复合相容剂进行相容;所述复合相容剂是将聚苯硫醚、热塑性弹性体X和接枝单体通过熔融接枝反应获得的复合接枝物,该复合接枝物中的聚苯硫醚和热塑性弹性体X之间通过化学键相连。A kind of nylon composite material utilizing composite compatibilizer to realize high strength of the present invention comprises nylon, composite compatibilizer and polyphenylene sulfide, and the mass ratio of nylon and polyphenylene sulfide is (2.1~5.6): 1; Said nylon and polyphenylene sulfide are compatible through a composite compatibilizer; said composite compatibilizer is a composite graft obtained by melting polyphenylene sulfide, thermoplastic elastomer X and graft monomer, The polyphenylene sulfide and the thermoplastic elastomer X in the composite graft are connected by chemical bonds.

优选地,所述接枝单体包括MAH,本发明中的MAH是指马来酸酐;所述复合相容剂在复合材料中的占比为3wt%~6wt%,其包括PPS-X-g-MAH和/或X-PPS-g-MAH和/或MAH-g-X-PPS-g-MAH。Preferably, the graft monomer includes MAH, and MAH in the present invention refers to maleic anhydride; the proportion of the composite compatibilizer in the composite material is 3wt% to 6wt%, which includes PPS-X-g-MAH and/or X-PPS-g-MAH and/or MAH-g-X-PPS-g-MAH.

优选地,所述尼龙包括尼龙66,尼龙66为中粘尼龙66和/或低粘尼龙66;所述聚苯硫醚的分子量为40000~50000。Preferably, the nylon includes nylon 66, and nylon 66 is medium-viscosity nylon 66 and/or low-viscosity nylon 66; the molecular weight of the polyphenylene sulfide is 40,000-50,000.

优选地,所述复合相容剂中的聚苯硫醚和热塑性弹性体X质量比为(1.4~5.5):1;该质量比下的聚苯硫醚和热塑性弹性体X能够与尼龙复合材料中的尼龙和聚苯硫醚成分相匹配,能够获得相容性较高的尼龙复合材料,使其体现出优异的疏水性和强度。Preferably, the mass ratio of polyphenylene sulfide and thermoplastic elastomer X in the composite compatibilizer is (1.4-5.5): 1; polyphenylene sulfide and thermoplastic elastomer X in this mass ratio can be combined with nylon composite material The nylon and polyphenylene sulfide components in the compound match, and a nylon composite material with high compatibility can be obtained, which makes it exhibit excellent hydrophobicity and strength.

优选地,所述热塑性弹性体X包括SBS和/或POE和/或EPDM和/或SEBS。Preferably, the thermoplastic elastomer X comprises SBS and/or POE and/or EPDM and/or SEBS.

优选地,还包括经过偶联剂处理的玻璃纤维,玻璃纤维与尼龙的质量比为(1.16~1.73):1。Preferably, glass fibers treated with a coupling agent are also included, and the mass ratio of glass fibers to nylon is (1.16-1.73):1.

本发明的一种利用复合相容剂实现高强度的尼龙复合材料制备方法,所述复合材料为本发明中所述的复合材料,先制备出复合相容剂,再将尼龙、复合相容剂和聚苯硫醚混合经双螺杆挤出机熔融挤出制得。A kind of preparation method of nylon composite material utilizing composite compatibilizer to realize high strength of the present invention, described composite material is the composite material described in the present invention, first prepares composite compatibilizer, then nylon, composite compatibilizer It is mixed with polyphenylene sulfide and produced by melt extrusion with twin-screw extruder.

优选地,具体制备步骤为:Preferably, the specific preparation steps are:

(1)制备复合相容剂:将占比为15wt%~85wt%的PPS,15wt%~85wt%的热塑性弹性体,0.1wt%~0.3wt%的引发剂和1wt%~3wt%的接枝单体在混料机中混合均匀,再倒入双螺杆挤出机熔融挤出后切粒干燥制得复合相容剂,其中所述的双螺杆挤出机的各区加工温度为250℃~295℃;(1) Preparation of composite compatibilizer: PPS accounting for 15wt% to 85wt%, thermoplastic elastomer of 15wt% to 85wt%, initiator of 0.1wt% to 0.3wt%, and grafting of 1wt% to 3wt% The monomers are mixed evenly in a mixer, and then poured into a twin-screw extruder to melt and extrude, and then pelletized and dried to obtain a composite compatibilizer. The processing temperature of each zone of the twin-screw extruder is 250 ° C to 295 ° C ℃;

(2)制备复合材料:将占比为31.9wt%~38.6wt%的尼龙66,7wt%~15wt%的PPS树脂,3wt%~6wt%的复合相容剂,45wt%~55wt%的玻璃纤维,0.1wt%~0.3wt%的抗氧剂和0.3wt%~0.8wt%的润滑剂在混料机中混合均匀,再倒入双螺杆挤出机熔融挤出后切粒干燥制得复合相容剂,其中所述的双螺杆挤出机的各区加工温度为255℃~295℃。(2) Preparation of composite materials: Nylon 66 accounting for 31.9wt% to 38.6wt%, 7wt% to 15wt% of PPS resin, 3wt% to 6wt% of composite compatibilizer, and 45wt% to 55wt% of glass fiber , 0.1wt% to 0.3wt% of antioxidant and 0.3wt% to 0.8wt% of lubricant are mixed uniformly in a mixer, then poured into a twin-screw extruder to melt and extrude, and then pelletized and dried to obtain a composite phase Compatible agent, wherein the processing temperature of each zone of the twin-screw extruder is 255°C to 295°C.

优选地,所述(1)步骤中的引发剂包括过氧化二异丙苯或2,5-二甲基-2,5-二(叔丁基过氧化)己烷;和/或所述(2)步骤中的玻璃纤维单丝直径为10μm~13μm;所述抗氧剂为抗氧剂1098与抗氧剂S-9228的混合物,其质量比值为(1~2):1;所述润滑剂为硅酮类化合物或酰胺类化合物。Preferably, the initiator in the (1) step includes dicumyl peroxide or 2,5-dimethyl-2,5-bis(tert-butyl peroxy)hexane; and/or the ( 2) The diameter of the glass fiber monofilament in the step is 10 μm to 13 μm; the antioxidant is a mixture of antioxidant 1098 and antioxidant S-9228, and its mass ratio is (1 to 2): 1; the lubricating The agent is a silicone compound or an amide compound.

优选地,所述双螺杆挤出机的各区加工温度控制包括一区至九区的加工温度控制,所述的一区至九区的加工温度控制分别为255℃、280℃、290℃、295℃、290℃、285℃、280℃、280℃和275℃;所述双螺杆挤出机的机头温度为270℃。Preferably, the processing temperature control of each zone of the twin-screw extruder includes the processing temperature control of the first zone to the ninth zone, and the processing temperature control of the first zone to the ninth zone is 255°C, 280°C, 290°C, 295°C, respectively. °C, 290 °C, 285 °C, 280 °C, 280 °C and 275 °C; the head temperature of the twin-screw extruder is 270 °C.

3.有益效果3. Beneficial effect

相比于现有技术,本发明的有益效果为:Compared with the prior art, the beneficial effects of the present invention are:

(1)本发明的一种利用复合相容剂实现高强度的尼龙复合材料,包括尼龙、复合相容剂和聚苯硫醚,尼龙和聚苯硫醚的质量比为(2.1~5.6):1;所述尼龙和聚苯硫醚通过复合相容剂进行相容;所述复合相容剂是将聚苯硫醚、热塑性弹性体X和接枝单体通过熔融接枝反应获得的复合接枝物,该复合接枝物中的聚苯硫醚和热塑性弹性体X之间通过化学键相连。通过上述设置,在尼龙材料里所添加的聚苯硫醚树脂,因其分子结构里只含有苯环和硫原子,并没有因吸水而造成材料刚性下降的酰胺基团,因此从分子结构方面分析,聚苯硫醚树脂本身并不吸水;另外,聚苯硫醚因其分子结构中芳香族苯环的存大,其刚性远比脂肪族尼龙中碳碳链(C-C)高的多;此外,部分聚苯硫醚的添加,也降低了尼龙在整个材料中的占比,因此添加聚苯硫醚树脂可大幅度改善尼龙材料的刚性和疏水性;进一步地,由于尼龙和聚苯硫醚之间的相容性较差,本发明通过将聚苯硫醚、热塑性弹性体X和接枝单体混合熔融接枝反应制备上述复合相容剂,在该熔融接枝反应中,聚苯硫醚和热塑性弹性体X之间既可以通过化学键的方式相结合,聚苯硫醚或热塑性弹性体X也可以与接枝单体进行接枝反应,从而形成聚苯硫醚、热塑性弹性体X和接枝单体复合接枝的复合接枝物,从提升聚苯硫醚与尼龙相容性的角度有效地提升了复合材料的疏水性和强度。(1) A kind of nylon composite material utilizing composite compatibilizer of the present invention to realize high strength comprises nylon, composite compatibilizer and polyphenylene sulfide, and the mass ratio of nylon and polyphenylene sulfide is (2.1~5.6): 1; the nylon and polyphenylene sulfide are compatible through a composite compatibilizer; the composite compatibilizer is a composite graft obtained by melting and grafting polyphenylene sulfide, thermoplastic elastomer X and graft monomer The polyphenylene sulfide and the thermoplastic elastomer X in the composite graft are connected by chemical bonds. Through the above settings, the polyphenylene sulfide resin added to the nylon material only contains benzene rings and sulfur atoms in its molecular structure, and there is no amide group that reduces the rigidity of the material due to water absorption, so it is analyzed from the molecular structure. , the polyphenylene sulfide resin itself does not absorb water; in addition, because of the large aromatic benzene ring in the molecular structure of polyphenylene sulfide, its rigidity is much higher than that of the carbon-carbon chain (C-C) in aliphatic nylon; in addition, The addition of some polyphenylene sulfide also reduces the proportion of nylon in the entire material, so the addition of polyphenylene sulfide resin can greatly improve the rigidity and hydrophobicity of nylon materials; further, due to the relationship between nylon and polyphenylene sulfide The compatibility among them is poor, the present invention prepares above-mentioned composite compatibilizer by mixing polyphenylene sulfide, thermoplastic elastomer X and grafting monomer melt graft reaction, in this melt graft reaction, polyphenylene sulfide It can be combined with thermoplastic elastomer X through chemical bonds, and polyphenylene sulfide or thermoplastic elastomer X can also undergo grafting reaction with graft monomer to form polyphenylene sulfide, thermoplastic elastomer X and graft The composite graft of graft monomer composite graft effectively improves the hydrophobicity and strength of the composite material from the perspective of improving the compatibility of polyphenylene sulfide and nylon.

(2)本发明的一种利用复合相容剂实现高强度的尼龙复合材料,所述接枝单体包括MAH;所述复合相容剂在复合材料中的占比为3wt%~6wt%,其包括PPS-X-g-MAH和/或X-PPS-g-MAH和/或MAH-g-X-PPS-g-MAH;还包括经过偶联剂处理的玻璃纤维,玻璃纤维与尼龙的质量比为(1.16~1.73):1;本发明所选用的复合相容剂为PPS树脂和热塑性弹性体X混合后同时接枝的复合接枝物,其与普通单一组分接枝反应不同,在该接枝反应过程中形成了PPS-X-g-MAH、X-PPS-g-MAH和MAH-g-X-PPS-g-MAH,这不仅可以改善尼龙和聚苯硫醚树脂之间的相容性,同时MAH还可以和玻璃纤维表面的偶联剂发生反应,进一步提高尼龙、PPS和玻璃纤维之间的粘结力,从而提高尼龙复合材料的机械强度和刚性;这主要是由于引发剂受热分解生成自由基,从而夺取热塑性弹性体X和PPS分子链上的氢原子,分别形成大分子自由基,该自由基一方面可以与MAH结合,形成接枝反应;另一方面,热塑性弹性体自由基与PPS自由基之间也可以发生反应,以化学键的形式进行结合,从而形成上述复合接枝物。(2) A kind of nylon composite material utilizing composite compatibilizer of the present invention to realize high strength, described graft monomer comprises MAH; The proportion of described composite compatibilizer in composite material is 3wt%~6wt%, It includes PPS-X-g-MAH and/or X-PPS-g-MAH and/or MAH-g-X-PPS-g-MAH; It also includes glass fiber treated with coupling agent, and the mass ratio of glass fiber to nylon is ( 1.16~1.73): 1; The selected composite compatibilizer of the present invention is the composite graft that grafts simultaneously after PPS resin and thermoplastic elastomer X mix, and it is different with common single-component grafting reaction, in this grafting During the reaction, PPS-X-g-MAH, X-PPS-g-MAH and MAH-g-X-PPS-g-MAH were formed, which not only improved the compatibility between nylon and polyphenylene sulfide resin, but also MAH It can react with the coupling agent on the surface of glass fiber to further improve the bonding force between nylon, PPS and glass fiber, thereby improving the mechanical strength and rigidity of nylon composite materials; this is mainly due to the thermal decomposition of the initiator to generate free radicals, In this way, the hydrogen atoms on the thermoplastic elastomer X and PPS molecular chains are captured to form macromolecular free radicals, which can combine with MAH on the one hand to form a grafting reaction; on the other hand, the thermoplastic elastomer free radicals and PPS free radicals Reactions can also occur between them, and they can be combined in the form of chemical bonds to form the above-mentioned composite grafts.

具体实施方式detailed description

本说明书中的比例、大小等,均仅用以配合说明书所揭示的内容,以供熟悉此技术的人士了解与阅读,并非用以限定本发明可实施的限定条件,故不具技术上的实质意义,任何结构的修饰、比例关系的改变或大小的调整,在不影响本发明所能产生的功效及所能达成的目的下,均应仍落在本发明所揭示的技术内容得以涵盖的范围内。同时,本说明书中所引用的如“上”、“下”、“左”、“右”、“中间”等用语,亦仅为便于叙述的明了,而非用以限定可实施的范围,其相对关系的改变或调整,在无实质变更技术内容下,当亦视为本发明可实施的范畴;除此之外,本发明的各个实施例之间并不是相互独立的,而是可以进行组合的。The proportions, sizes, etc. in this specification are only used to cooperate with the content disclosed in the specification for the understanding and reading of those who are familiar with this technology, and are not used to limit the conditions for the implementation of the present invention, so they have no technical significance , any modification of the structure, change of the proportional relationship or adjustment of the size shall still fall within the scope covered by the technical content disclosed in the present invention without affecting the effect and purpose of the present invention. . At the same time, terms such as "upper", "lower", "left", "right", and "middle" quoted in this specification are only for the convenience of description and are not used to limit the scope of implementation. The change or adjustment of the relative relationship shall also be regarded as the applicable scope of the present invention without substantially changing the technical content; in addition, the various embodiments of the present invention are not independent of each other, but can be combined of.

下面结合具体实施例对本发明进一步进行描述。The present invention will be further described below in conjunction with specific embodiments.

实施例1Example 1

本实施例提供一种利用复合相容剂实现高强度的尼龙复合材料,以质量百分比计,其原料由以下成分组成:36.6wt%尼龙66树脂、15wt%PPS树脂、3wt%复合相容剂、45wt%玻璃纤维、0.1wt%抗氧剂、0.3wt%润滑剂;其中相容剂以质量百分比计,其原料由以下组分组成:13.9wt%PPS树脂、85wt%热塑性弹性体、0.1wt%引发剂、1wt%接枝单体。所述的尼龙66为中粘尼龙66;所述的PPS树脂分子量为40000~50000;所述的玻璃纤维单丝直径为13微米;所述的抗氧剂为抗氧剂1098与抗氧剂S-9228的混合物,其质量比值为1:1;所述的润滑剂为硅酮粉;所述的热塑性弹性体为SBS,因此本实施例的复合相容剂包括PPS-SBS-g-MAH、SBS-PPS-g-MAH和MAH-g-SBS-PPS-g-MAH;所述的引发剂为过氧化二异丙苯;所述的接枝单体为马来酸酐。This embodiment provides a nylon composite material that uses a composite compatibilizer to achieve high strength. In terms of mass percentage, its raw materials are composed of the following components: 36.6wt% nylon 66 resin, 15wt% PPS resin, 3wt% composite compatibilizer, 45wt% glass fiber, 0.1wt% antioxidant, 0.3wt% lubricant; wherein the compatibilizer is calculated by mass percentage, and its raw material is composed of the following components: 13.9wt% PPS resin, 85wt% thermoplastic elastomer, 0.1wt% Initiator, 1 wt% grafting monomer. The nylon 66 is medium-viscosity nylon 66; the molecular weight of the PPS resin is 40,000 to 50,000; the diameter of the glass fiber monofilament is 13 microns; the antioxidant is antioxidant 1098 and antioxidant S -9228 mixture, its mass ratio is 1:1; the lubricant is silicone powder; the thermoplastic elastomer is SBS, so the composite compatibilizer of the present embodiment includes PPS-SBS-g-MAH, SBS-PPS-g-MAH and MAH-g-SBS-PPS-g-MAH; the initiator is dicumyl peroxide; the graft monomer is maleic anhydride.

本实施例还提供一种利用复合相容剂实现高强度的尼龙复合材料制备方法:将干燥好的尼龙66、PPS树脂、复合相容剂、抗氧剂、润滑剂按所述的质量百分比的比例要求在混料机中预先混合均匀,制得预混料;随后将预混料倒入主加料斗,侧喂料口再辅以一定质量百分比的玻纤经双螺杆挤出机熔融挤出后切粒干燥,最终制成一种玻纤增强尼龙66复合材料;所述的双螺杆挤出机的各区加工温度控制包括一区至九区的加工温度控制,所述的一区至九区的加工温度控制分别为255℃、280℃、290℃、295℃、290℃、285℃、280℃、280℃和275℃;所述双螺杆挤出机的机头温度为270℃。This embodiment also provides a method for preparing a nylon composite material that utilizes a composite compatibilizer to achieve high strength: dry nylon 66, PPS resin, composite compatibilizer, antioxidant, lubricant in the stated mass percentage The ratio requires pre-mixing in the mixer to make a premix; then pour the premix into the main hopper, and the side feeding port is supplemented with a certain mass percentage of glass fiber to be melted and extruded by a twin-screw extruder After cutting and drying, a glass fiber reinforced nylon 66 composite material is finally made; the processing temperature control of each zone of the twin-screw extruder includes the processing temperature control of the first zone to the ninth zone, and the first zone to the ninth zone The processing temperature controls are 255°C, 280°C, 290°C, 295°C, 290°C, 285°C, 280°C, 280°C and 275°C respectively; the head temperature of the twin-screw extruder is 270°C.

实施例2Example 2

本实施例提供一种利用复合相容剂实现高强度的尼龙复合材料,以质量百分比计,其原料由以下成分组成:34.3wt%尼龙66树脂、10wt%PPS树脂、5wt%复合相容剂、50wt%玻璃纤维、0.2wt%抗氧剂、0.5wt%润滑剂;其中复合相容剂以质量百分比计,其原料由以下组分组成:57.8wt%PPS树脂、40wt%热塑性弹性体、0.2wt%引发剂、2wt%接枝单体。所述的尼龙66为低粘尼龙66;所述的PPS树脂分子量为40000~50000;所述的玻璃纤维单丝直径为10微米;所述的抗氧剂为抗氧剂1098与抗氧剂S-9228的混合物,其质量比值为1:1;所述的润滑剂为TAF;所述的热塑性弹性体为POE,因此本实施例的复合相容剂包括PPS-POE-g-MAH、POE-PPS-g-MAH和MAH-g-POE-PPS-g-MAH;所述的引发剂为过氧化二异丙苯;所述的接枝单体为马来酸酐。This embodiment provides a nylon composite material that uses a composite compatibilizer to achieve high strength. In terms of mass percentage, its raw materials are composed of the following components: 34.3wt% nylon 66 resin, 10wt% PPS resin, 5wt% composite compatibilizer, 50wt% glass fiber, 0.2wt% antioxidant, 0.5wt% lubricant; wherein the composite compatibilizer is calculated by mass percentage, and its raw material is composed of the following components: 57.8wt% PPS resin, 40wt% thermoplastic elastomer, 0.2wt% % initiator, 2wt% grafting monomer. The nylon 66 is low-viscosity nylon 66; the molecular weight of the PPS resin is 40,000 to 50,000; the diameter of the glass fiber monofilament is 10 microns; the antioxidant is antioxidant 1098 and antioxidant S -9228 mixture, its mass ratio is 1:1; the lubricant is TAF; the thermoplastic elastomer is POE, so the composite compatibilizer of this embodiment includes PPS-POE-g-MAH, POE- PPS-g-MAH and MAH-g-POE-PPS-g-MAH; the initiator is dicumyl peroxide; the graft monomer is maleic anhydride.

本实施例还提供一种利用复合相容剂实现高强度的尼龙复合材料制备方法:将干燥好的尼龙66、PPS树脂、复合相容剂、抗氧剂、润滑剂按所述的质量百分比的比例要求在混料机中预先混合均匀,制得预混料;随后将预混料倒入主加料斗,侧喂料口再辅以一定质量百分比的玻纤经双螺杆挤出机熔融挤出后切粒干燥,最终制成一种玻纤增强尼龙66复合材料;所述的双螺杆挤出机的各区加工温度控制包括一区至九区的加工温度控制,所述的一区至九区的加工温度控制分别为255℃、280℃、290℃、295℃、290℃、285℃、280℃、280℃和275℃;所述双螺杆挤出机的机头温度为270℃。This embodiment also provides a method for preparing a nylon composite material that utilizes a composite compatibilizer to achieve high strength: dry nylon 66, PPS resin, composite compatibilizer, antioxidant, lubricant in the stated mass percentage The ratio requires pre-mixing in the mixer to make a premix; then pour the premix into the main hopper, and the side feeding port is supplemented with a certain mass percentage of glass fiber to be melted and extruded by a twin-screw extruder After cutting and drying, a glass fiber reinforced nylon 66 composite material is finally made; the processing temperature control of each zone of the twin-screw extruder includes the processing temperature control of the first zone to the ninth zone, and the first zone to the ninth zone The processing temperature controls are 255°C, 280°C, 290°C, 295°C, 290°C, 285°C, 280°C, 280°C and 275°C respectively; the head temperature of the twin-screw extruder is 270°C.

实施例3Example 3

本实施例提供一种利用复合相容剂实现高强度的尼龙复合材料,以质量百分比计,其原料由以下成分组成:31.9wt%尼龙66树脂、7wt%PPS树脂、5wt%复合相容剂、55wt%玻璃纤维、0.3wt%抗氧剂、0.8wt%润滑剂;其中复合相容剂以质量百分比计,其原料由以下组分组成:81.7wt%PPS树脂、15wt%热塑性弹性体、0.3wt%引发剂、3wt%接枝单体。所述的尼龙66为中粘尼龙66;所述的PPS树脂分子量为40000~50000;所述的玻璃纤维单丝直径为13微米;所述的抗氧剂为抗氧剂1098与抗氧剂S-9228的混合物,其质量比值为1:1;所述的润滑剂为硅酮粉;所述的热塑性弹性体为EPDM,因此本实施例的复合相容剂包括PPS-EPDM-g-MAH、EPDM-PPS-g-MAH和MAH-g-EPDM-PPS-g-MAH;所述的引发剂为过氧化二异丙苯;所述的接枝单体为马来酸酐。This embodiment provides a nylon composite material that uses a composite compatibilizer to achieve high strength. In terms of mass percentage, its raw materials are composed of the following components: 31.9wt% nylon 66 resin, 7wt% PPS resin, 5wt% composite compatibilizer, 55wt% glass fiber, 0.3wt% antioxidant, 0.8wt% lubricant; wherein the composite compatibilizer is calculated by mass percentage, and its raw material is composed of the following components: 81.7wt% PPS resin, 15wt% thermoplastic elastomer, 0.3wt% % initiator, 3wt% grafting monomer. The nylon 66 is medium-viscosity nylon 66; the molecular weight of the PPS resin is 40,000 to 50,000; the diameter of the glass fiber monofilament is 13 microns; the antioxidant is antioxidant 1098 and antioxidant S -9228 mixture, its mass ratio is 1:1; the lubricant is silicone powder; the thermoplastic elastomer is EPDM, so the composite compatibilizer of the present embodiment includes PPS-EPDM-g-MAH, EPDM-PPS-g-MAH and MAH-g-EPDM-PPS-g-MAH; the initiator is dicumyl peroxide; the graft monomer is maleic anhydride.

本实施例还提供一种利用复合相容剂实现高强度的尼龙复合材料制备方法:将干燥好的尼龙66、PPS树脂、复合相容剂、抗氧剂、润滑剂按所述的质量百分比的比例要求在混料机中预先混合均匀,制得预混料;随后将预混料倒入主加料斗,侧喂料口再辅以一定质量百分比的玻纤经双螺杆挤出机熔融挤出后切粒干燥,最终制成一种玻纤增强尼龙66复合材料;所述的双螺杆挤出机的各区加工温度控制包括一区至九区的加工温度控制,所述的一区至九区的加工温度控制分别为255℃、280℃、290℃、295℃、290℃、285℃、280℃、280℃和275℃;所述双螺杆挤出机的机头温度为270℃。This embodiment also provides a method for preparing a nylon composite material that utilizes a composite compatibilizer to achieve high strength: dry nylon 66, PPS resin, composite compatibilizer, antioxidant, lubricant in the stated mass percentage The ratio requires pre-mixing in the mixer to make a premix; then pour the premix into the main hopper, and the side feeding port is supplemented with a certain mass percentage of glass fiber to be melted and extruded by a twin-screw extruder After cutting and drying, a glass fiber reinforced nylon 66 composite material is finally made; the processing temperature control of each zone of the twin-screw extruder includes the processing temperature control of the first zone to the ninth zone, and the first zone to the ninth zone The processing temperature controls are 255°C, 280°C, 290°C, 295°C, 290°C, 285°C, 280°C, 280°C and 275°C respectively; the head temperature of the twin-screw extruder is 270°C.

实施例4Example 4

本实施例提供一种利用复合相容剂实现高强度的尼龙复合材料,以质量百分比计,其原料由以下成分组成:38.6wt%尼龙66树脂、10wt%PPS树脂、6wt%复合相容剂、45wt%玻璃纤维、0.1wt%抗氧剂、0.3wt%润滑剂;其中复合相容剂以质量百分比计,其原料由以下组分组成:68.9wt%PPS树脂、30wt%热塑性弹性体、0.1wt%引发剂、1wt%接枝单体。所述的尼龙66为中粘尼龙66;所述的PPS树脂分子量为40000~50000;所述的玻璃纤维单丝直径为13微米;所述的抗氧剂为抗氧剂1098与抗氧剂S-9228的混合物,其质量比值为1:1;所述的润滑剂为硅酮粉;所述的热塑性弹性体为SEBS,因此本实施例的复合相容剂包括PPS-SEBS-g-MAH、SEBS-PPS-g-MAH和MAH-g-SEBS-PPS-g-MAH;所述的引发剂为2,5-二甲基-2,5-二(叔丁基过氧化)己烷;所述的接枝单体为马来酸酐。This embodiment provides a nylon composite material that uses a composite compatibilizer to achieve high strength. In terms of mass percentage, its raw materials are composed of the following components: 38.6wt% nylon 66 resin, 10wt% PPS resin, 6wt% composite compatibilizer, 45wt% glass fiber, 0.1wt% antioxidant, 0.3wt% lubricant; wherein the composite compatibilizer is calculated by mass percentage, and its raw material is composed of the following components: 68.9wt% PPS resin, 30wt% thermoplastic elastomer, 0.1wt% % initiator, 1 wt% grafting monomer. The nylon 66 is medium-viscosity nylon 66; the molecular weight of the PPS resin is 40,000 to 50,000; the diameter of the glass fiber monofilament is 13 microns; the antioxidant is antioxidant 1098 and antioxidant S -9228 mixture, its mass ratio is 1:1; the lubricant is silicone powder; the thermoplastic elastomer is SEBS, so the composite compatibilizer of the present embodiment includes PPS-SEBS-g-MAH, SEBS-PPS-g-MAH and MAH-g-SEBS-PPS-g-MAH; The initiator is 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane; the The graft monomer described is maleic anhydride.

本实施例还提供一种利用复合相容剂实现高强度的尼龙复合材料制备方法:将干燥好的尼龙66、PPS树脂、复合相容剂、抗氧剂、润滑剂按所述的质量百分比的比例要求在混料机中预先混合均匀,制得预混料;随后将预混料倒入主加料斗,侧喂料口再辅以一定质量百分比的玻纤经双螺杆挤出机熔融挤出后切粒干燥,最终制成一种玻纤增强尼龙66复合材料;所述的双螺杆挤出机的各区加工温度控制包括一区至九区的加工温度控制,所述的一区至九区的加工温度控制分别为255℃、280℃、290℃、295℃、290℃、285℃、280℃、280℃和275℃;所述双螺杆挤出机的机头温度为270℃。This embodiment also provides a method for preparing a nylon composite material that utilizes a composite compatibilizer to achieve high strength: dry nylon 66, PPS resin, composite compatibilizer, antioxidant, lubricant in the stated mass percentage The ratio requires pre-mixing in the mixer to make a premix; then pour the premix into the main hopper, and the side feeding port is supplemented with a certain mass percentage of glass fiber to be melted and extruded by a twin-screw extruder After cutting and drying, a glass fiber reinforced nylon 66 composite material is finally made; the processing temperature control of each zone of the twin-screw extruder includes the processing temperature control of the first zone to the ninth zone, and the first zone to the ninth zone The processing temperature controls are 255°C, 280°C, 290°C, 295°C, 290°C, 285°C, 280°C, 280°C and 275°C respectively; the head temperature of the twin-screw extruder is 270°C.

实施例5Example 5

本实施例提供一种利用复合相容剂实现高强度的尼龙复合材料,以质量百分比计,其原料由以下成分组成:33.3wt%尼龙66树脂、12wt%PPS树脂、4wt%复合相容剂、50wt%玻璃纤维、0.2wt%抗氧剂、0.5wt%润滑剂;其中复合相容剂以质量百分比计,其原料由以下组分组成:37.8wt%PPS树脂、60wt%热塑性弹性体、0.2wt%引发剂、2wt%接枝单体。所述的尼龙66为中粘尼龙66;所述的PPS树脂分子量为40000~50000;所述的玻璃纤维单丝直径为13微米;所述的抗氧剂为抗氧剂1098与抗氧剂S-9228的混合物,其质量比值为2:1;所述的润滑剂为硅酮粉;所述的热塑性弹性体为SEBS,因此本实施例的复合相容剂包括PPS-SEBS-g-MAH、SEBS-PPS-g-MAH和MAH-g-SEBS-PPS-g-MAH;所述的引发剂为过氧化二异丙苯;所述的接枝单体为马来酸酐。This embodiment provides a nylon composite material that uses a composite compatibilizer to achieve high strength. In terms of mass percentage, its raw materials are composed of the following components: 33.3wt% nylon 66 resin, 12wt% PPS resin, 4wt% composite compatibilizer, 50wt% glass fiber, 0.2wt% antioxidant, 0.5wt% lubricant; wherein the composite compatibilizer is calculated by mass percentage, and its raw material is composed of the following components: 37.8wt% PPS resin, 60wt% thermoplastic elastomer, 0.2wt% % initiator, 2wt% grafting monomer. The nylon 66 is medium-viscosity nylon 66; the molecular weight of the PPS resin is 40,000 to 50,000; the diameter of the glass fiber monofilament is 13 microns; the antioxidant is antioxidant 1098 and antioxidant S The mixture of -9228, its mass ratio is 2:1; Described lubricant is silicone powder; Described thermoplastic elastomer is SEBS, therefore the composite compatibilizer of the present embodiment comprises PPS-SEBS-g-MAH, SEBS-PPS-g-MAH and MAH-g-SEBS-PPS-g-MAH; the initiator is dicumyl peroxide; the graft monomer is maleic anhydride.

本实施例还提供一种利用复合相容剂实现高强度的尼龙复合材料制备方法:将干燥好的尼龙66、PPS树脂、复合相容剂、抗氧剂、润滑剂按所述的质量百分比的比例要求在混料机中预先混合均匀,制得预混料;随后将预混料倒入主加料斗,侧喂料口再辅以一定质量百分比的玻纤经双螺杆挤出机熔融挤出后切粒干燥,最终制成一种玻纤增强尼龙66复合材料;所述的双螺杆挤出机的各区加工温度控制包括一区至九区的加工温度控制,所述的一区至九区的加工温度控制分别为255℃、280℃、290℃、295℃、290℃、285℃、280℃、280℃和275℃;所述双螺杆挤出机的机头温度为270℃。This embodiment also provides a method for preparing a nylon composite material that utilizes a composite compatibilizer to achieve high strength: dry nylon 66, PPS resin, composite compatibilizer, antioxidant, lubricant in the stated mass percentage The ratio requires pre-mixing in the mixer to make a premix; then pour the premix into the main hopper, and the side feeding port is supplemented with a certain mass percentage of glass fiber to be melted and extruded by a twin-screw extruder After cutting and drying, a glass fiber reinforced nylon 66 composite material is finally made; the processing temperature control of each zone of the twin-screw extruder includes the processing temperature control of the first zone to the ninth zone, and the first zone to the ninth zone The processing temperature controls are 255°C, 280°C, 290°C, 295°C, 290°C, 285°C, 280°C, 280°C and 275°C respectively; the head temperature of the twin-screw extruder is 270°C.

对比例1Comparative example 1

本对比例提供一种玻纤增强尼龙66材料,以质量百分比计,其原料由以下成分组成:44.7wt%尼龙66树脂、55wt%玻璃纤维、0.2wt%抗氧剂、0.5wt%润滑剂。所述的尼龙66为中粘尼龙66;所述的玻璃纤维单丝直径为13微米;所述的抗氧剂为抗氧剂1098与抗氧剂S-9228的混合物,其质量比值为1:1;所述的润滑剂为硅酮粉;This comparative example provides a glass fiber reinforced nylon 66 material, the raw material of which is composed of the following components in terms of mass percentage: 44.7wt% nylon 66 resin, 55wt% glass fiber, 0.2wt% antioxidant, 0.5wt% lubricant. The nylon 66 is medium-viscosity nylon 66; the diameter of the glass fiber monofilament is 13 microns; the antioxidant is a mixture of antioxidant 1098 and antioxidant S-9228, and its mass ratio is 1: 1; the lubricant is silicone powder;

其制备方法为:将干燥好的尼龙66、抗氧剂、润滑剂按所述的质量百分比的比例要求在混料机中预先混合均匀,制得预混料;随后将预混料倒入主加料斗,侧喂料口再辅以一定质量百分比的玻纤经双螺杆挤出机熔融挤出后切粒干燥,最终制成一种玻纤增强尼龙66材料;所述的双螺杆挤出机的各区加工温度控制包括一区至九区的加工温度控制,所述的一区至九区的加工温度控制分别为250℃、260℃、270℃、275℃、270℃、270℃、265℃、265℃和260℃;所述的双螺杆挤出机的机头温度为255℃。The preparation method is as follows: pre-mix the dried nylon 66, antioxidant and lubricant in a mixer according to the ratio of the mass percentage to obtain a premix; then pour the premix into the main The feeding hopper, the side feeding port and supplemented with a certain mass percentage of glass fiber are melted and extruded by a twin-screw extruder, and then pelletized and dried to finally make a glass fiber-reinforced nylon 66 material; the twin-screw extruder The processing temperature control of each zone includes the processing temperature control of the first zone to the ninth zone, and the processing temperature control of the first zone to the ninth zone is 250°C, 260°C, 270°C, 275°C, 270°C, 270°C, 265°C , 265°C and 260°C; the head temperature of the twin-screw extruder is 255°C.

对比例2Comparative example 2

本对比例提供一种玻纤增强尼龙66材料,该材料与实施例3基本相同,其区别在于:本对比例使用的相容剂并非复合相容剂,而是EPDM-g-MAH。This comparative example provides a glass fiber reinforced nylon 66 material, which is basically the same as that of Example 3, the difference being that the compatibilizer used in this comparative example is not a composite compatibilizer, but EPDM-g-MAH.

本发明分别将实施例1~5以及对比例1~2所制备的尼龙复合材料进行了各项性能测试:拉伸强度、弯曲强度、弯曲模量、悬臂梁缺口冲击强度和产品合格认证,具体测试结果如表1所示。其中产品合格认证的测试方法为:将各类材料制成厚度为0.6mm的按键支撑骨架,再将其安装在键盘上,依次对键盘进行震动实验、高温试验和低温试验,完成测试后观察键盘按键操作是否异常,无异常即为合格。震动实验:-40℃下震动5小时加+60℃下震动5小时,重复24个循环;高温试验:温度60℃、湿度60%条件下放置2小时,再在温度85℃下放置2小时,最后室温下放置30分钟;低温试验:0℃条件下放置2小时,-20℃条件下放置2小时,室温条件下放置30分钟;对所测试样品组装进行按键操作。In the present invention, the nylon composite materials prepared in Examples 1 to 5 and Comparative Examples 1 to 2 have been tested for various properties: tensile strength, flexural strength, flexural modulus, Izod notched impact strength and product qualification certification, specifically The test results are shown in Table 1. Among them, the test method for product qualification certification is as follows: make various materials into a key support frame with a thickness of 0.6mm, and then install it on the keyboard, and then carry out vibration test, high temperature test and low temperature test on the keyboard in turn, and observe the keyboard after the test Whether the button operation is abnormal, if there is no abnormality, it is qualified. Vibration test: vibration at -40°C for 5 hours plus +60°C for 5 hours, repeat 24 cycles; high temperature test: place at 60°C and humidity 60% for 2 hours, then place at 85°C for 2 hours, Finally, place it at room temperature for 30 minutes; low temperature test: place it at 0°C for 2 hours, at -20°C for 2 hours, and at room temperature for 30 minutes; press the button to assemble the tested sample.

表1、实施例1~5和对比例1、2制备的尼龙复合材料各项性能测试Table 1, various performance tests of the nylon composite materials prepared in Examples 1 to 5 and Comparative Examples 1 and 2

Figure BDA0003036923650000081
Figure BDA0003036923650000081

通过将实施例1~5与对比例1和2进行比较可以看到,在缺少本发明的复合相容剂和PPS作用下,制得的尼龙复合材料明显不合格,其中对比例2使用了单一的相容剂还会使得复合材料的拉伸强度、弯曲强度和弯曲模量大幅下降,这一点从背景技术中CN111040442A公开的复合材料与本发明进行对比也可看出;另外,从实施例2和实施例3可以看出,在保证产品合格的情况下,其拉伸强度、弯曲强度、弯曲模量、悬臂梁缺口冲击强度均处于一个较高的水平,这是由于实施例2和实施例3的复合相容剂中聚苯硫醚和热塑性弹性体X之间具有一个合适的质量比,该合适的质量比为本发明中所述的(1.4~5.5):1,因此能够获得相容性较高的尼龙复合材料,从而使得尼龙复合材料体现出优异的力学性能。综上所述,对于本发明的尼龙复合材料,通过添加适当份数的PPS树脂及复合相容剂可以有效解决尼龙复合材料在高温高湿环境下因吸水造成材料刚性下降的问题,尤其对于键盘材料等薄壁制品,在低温和震动环境下依然能够保持较高的疏水性和强度,进一步拓展了本发明的尼龙复合材料的应用。By comparing Examples 1 to 5 with Comparative Examples 1 and 2, it can be seen that under the action of lacking the composite compatibilizer and PPS of the present invention, the nylon composite material obtained is obviously unqualified, and wherein Comparative Example 2 uses a single The compatibilizer also can make the tensile strength of composite material, flexural strength and flexural modulus drop significantly, and this point also can be seen from the composite material disclosed by CN111040442A in background technology and the present invention; In addition, from embodiment 2 As can be seen from Example 3, under the condition of ensuring that the product is qualified, its tensile strength, flexural strength, flexural modulus, Izod notched impact strength are all at a relatively high level, and this is due to Example 2 and Example There is an appropriate mass ratio between polyphenylene sulfide and thermoplastic elastomer X in the composite compatibilizer of 3, and the appropriate mass ratio is (1.4-5.5): 1 described in the present invention, so compatibilization can be obtained Nylon composite materials with high resistance, so that nylon composite materials show excellent mechanical properties. In summary, for the nylon composite material of the present invention, by adding an appropriate number of PPS resins and composite compatibilizers, the problem that the rigidity of the nylon composite material decreases due to water absorption in a high-temperature and high-humidity environment can be effectively solved, especially for keyboards. Thin-walled products such as materials can still maintain high hydrophobicity and strength under low temperature and vibration environments, which further expands the application of the nylon composite material of the present invention.

在上文中结合具体的示例性实施例详细描述了本发明。但是,应当理解,可在不脱离由所附权利要求限定的本发明的范围的情况下进行各种修改和变型。详细的描述应仅被认为是说明性的,而不是限制性的,如果存在任何这样的修改和变型,那么它们都将落入在此描述的本发明的范围内。此外,背景技术旨在为了说明本技术的研发现状和意义,并不旨在限制本发明或本申请和本发明的应用领域。The present invention has been described in detail above with reference to specific exemplary embodiments. However, it should be understood that various modifications and changes can be made without departing from the scope of the present invention as defined in the appended claims. The detailed description should be regarded as illustrative only, not restrictive, and if there are any such modifications and variations, they are intended to fall within the scope of the invention as described herein. In addition, the background art is intended to illustrate the research and development status and significance of the present technology, and is not intended to limit the present invention or the application and the application field of the present invention.

更具体地,尽管在此已经描述了本发明的示例性实施例,但是本发明并不局限于这些实施例,而是包括本领域技术人员根据前面的详细描述可认识到的经过修改、省略、例如各个实施例之间的组合、适应性改变和/或替换的任何和全部实施例。权利要求中的限定可根据权利要求中使用的语言而进行广泛的解释,且不限于在前述详细描述中或在实施该申请期间描述的示例,这些示例应被认为是非排他性的。在任何方法或过程权利要求中列举的任何步骤可以以任何顺序执行并且不限于权利要求中提出的顺序。因此,本发明的范围应当仅由所附权利要求及其合法等同物来确定,而不是由上文给出的说明和示例来确定。More specifically, although exemplary embodiments of the present invention have been described herein, the present invention is not limited to these embodiments but includes modifications, omissions, Any and all embodiments such as combinations, adaptations, and/or substitutions between the various embodiments. The definitions in the claims are to be interpreted broadly according to the language used in the claims and not limited to the examples described in the foregoing detailed description or during the prosecution of this application, which examples should be considered non-exclusive. Any steps recited in any method or process claims may be performed in any order and are not limited to the order presented in the claims. Accordingly, the scope of the present invention should be determined only by the appended claims and their legal equivalents, rather than by the description and examples given above.

Claims (7)

1.一种利用复合相容剂实现高强度的尼龙复合材料,其特征在于,所述复合材料由31.9wt%~38.6wt%的尼龙,7wt%~15wt%的聚苯硫醚,3wt%~6wt%的复合相容剂,45wt%~55wt%的经过偶联剂处理的玻璃纤维,0.1wt%~0.3wt%的抗氧剂和0.3wt%~0.8wt%的润滑剂构成,所述尼龙和聚苯硫醚通过复合相容剂进行相容;所述复合相容剂由57.8wt%~81.7wt%的聚苯硫醚,15wt%~40wt%的热塑性弹性体X,0.1wt%~0.3wt%的引发剂和1wt%~3wt%的接枝单体构成,并且所述复合相容剂是将聚苯硫醚、热塑性弹性体X和接枝单体通过熔融接枝反应获得的复合接枝物,该复合接枝物中的聚苯硫醚和热塑性弹性体X之间通过化学键相连,其中所述热塑性弹性体X为SBS、POE、EPDM或SEBS,所述接枝单体为MAH。1. A nylon composite material utilizing composite compatibilizer to realize high strength is characterized in that, said composite material is made of 31.9wt%~38.6wt% nylon, 7wt%~15wt% polyphenylene sulfide, 3wt%~ 6wt% composite compatibilizer, 45wt%~55wt% glass fiber treated with coupling agent, 0.1wt%~0.3wt% antioxidant and 0.3wt%~0.8wt% lubricant, the nylon Compatible with polyphenylene sulfide through a composite compatibilizer; the composite compatibilizer consists of 57.8wt%~81.7wt% polyphenylene sulfide, 15wt%~40wt% thermoplastic elastomer X, 0.1wt%~0.3 wt% initiator and 1wt%~3wt% graft monomer, and the composite compatibilizer is a composite graft obtained by melt grafting reaction of polyphenylene sulfide, thermoplastic elastomer X and graft monomer The polyphenylene sulfide in the composite graft is connected with the thermoplastic elastomer X through a chemical bond, wherein the thermoplastic elastomer X is SBS, POE, EPDM or SEBS, and the graft monomer is MAH. 2.根据权利要求1所述的一种利用复合相容剂实现高强度的尼龙复合材料,其特征在于,所述复合相容剂包括PPS-X-g-MAH和/或X-PPS-g-MAH和/或MAH-g-X-PPS-g-MAH。2. A kind of nylon composite material utilizing composite compatibilizer to realize high strength according to claim 1, characterized in that, said composite compatibilizer comprises PPS-X-g-MAH and/or X-PPS-g-MAH and/or MAH-g-X-PPS-g-MAH. 3.根据权利要求1所述的一种利用复合相容剂实现高强度的尼龙复合材料,其特征在于,所述尼龙包括尼龙66,所述聚苯硫醚的分子量为40000~50000。3. A nylon composite material utilizing a composite compatibilizer to achieve high strength according to claim 1, wherein the nylon comprises nylon 66, and the molecular weight of the polyphenylene sulfide is 40,000 to 50,000. 4.一种利用复合相容剂实现高强度的尼龙复合材料制备方法,所述复合材料为权利要求1~3任一项所述的复合材料,其特征在于,先制备出复合相容剂,再将尼龙、复合相容剂、聚苯硫醚和经过偶联剂处理的玻璃纤维混合经双螺杆挤出机熔融挤出制得。4. a method for preparing a nylon composite material utilizing a composite compatibilizer to realize high strength, the composite material is the composite material according to any one of claims 1 to 3, wherein the composite compatibilizer is first prepared, It is prepared by mixing nylon, compound compatibilizer, polyphenylene sulfide and glass fiber treated with coupling agent through twin-screw extruder. 5.根据权利要求4所述的一种利用复合相容剂实现高强度的尼龙复合材料制备方法,其特征在于,具体制备步骤为:5. a kind of nylon composite material preparation method utilizing composite compatibilizer to realize high strength according to claim 4, is characterized in that, concrete preparation steps are: (1)制备复合相容剂:将占比为57.8wt%~81.7wt%的PPS,15wt%~40wt%的热塑性弹性体,0.1wt%~0.3wt%的引发剂和1wt%~3wt%的接枝单体在混料机中混合均匀,再倒入双螺杆挤出机熔融挤出后切粒干燥制得复合相容剂,其中所述的双螺杆挤出机的各区加工温度为250℃~295℃;(1) Preparation of composite compatibilizer: PPS with a proportion of 57.8wt%~81.7wt%, thermoplastic elastomer at 15wt%~40wt%, initiator at 0.1wt%~0.3wt%, and 1wt%~3wt% The grafted monomers are mixed evenly in a mixer, poured into a twin-screw extruder, melted and extruded, and then pelletized and dried to obtain a composite compatibilizer, wherein the processing temperature of each zone of the twin-screw extruder is 250°C ~295°C; (2)制备复合材料:将占比为31.9wt%~38.6wt%的尼龙66,7wt%~15wt%的PPS树脂,3wt%~6wt%的复合相容剂,45wt%~55wt%的玻璃纤维,0.1wt%~0.3wt%的抗氧剂和0.3wt%~0.8wt%的润滑剂在混料机中混合均匀,再倒入双螺杆挤出机熔融挤出后切粒干燥制得复合相容剂,其中所述的双螺杆挤出机的各区加工温度为255℃~295℃。(2) Preparation of composite materials: 31.9wt%~38.6wt% nylon 66, 7wt%~15wt% PPS resin, 3wt%~6wt% composite compatibilizer, 45wt%~55wt% glass fiber , 0.1wt%~0.3wt% of antioxidant and 0.3wt%~0.8wt% of lubricant are mixed evenly in the mixer, and then poured into the twin-screw extruder to melt and extrude, then pelletized and dried to obtain the composite phase Compatible agent, wherein the processing temperature of each zone of the twin-screw extruder is 255 ° C ~ 295 ° C. 6.根据权利要求5所述的一种利用复合相容剂实现高强度的尼龙复合材料制备方法,其特征在于,所述(1)步骤中的引发剂包括过氧化二异丙苯或2,5-二甲基-2,5-二(叔丁基过氧化)己烷;6. A method for preparing a high-strength nylon composite material using a composite compatibilizer according to claim 5, wherein the initiator in the step (1) includes dicumyl peroxide or 2, 5-Dimethyl-2,5-bis(tert-butylperoxy)hexane; 所述(2)步骤中的玻璃纤维单丝直径为10μm~13μm;所述抗氧剂为抗氧剂1098与抗氧剂S-9228的混合物,其质量比值为(1~2):1;所述润滑剂为硅酮类化合物或酰胺类化合物。The diameter of the glass fiber monofilament in the step (2) is 10 μm-13 μm; the antioxidant is a mixture of antioxidant 1098 and antioxidant S-9228, and the mass ratio thereof is (1-2):1; The lubricant is a silicone compound or an amide compound. 7.根据权利要求5所述的一种利用复合相容剂实现高强度的尼龙复合材料制备方法,其特征在于,所述双螺杆挤出机的各区加工温度控制包括一区至九区的加工温度控制,所述的一区至九区的加工温度控制分别为255℃、280℃、290℃、295℃、290℃、285℃、280℃、280℃和275℃;所述双螺杆挤出机的机头温度为270℃。7. A method for preparing a high-strength nylon composite material utilizing a composite compatibilizer according to claim 5, wherein the processing temperature control in each zone of the twin-screw extruder includes the processing of one zone to nine zones Temperature control, the processing temperature control of the first zone to the ninth zone is 255°C, 280°C, 290°C, 295°C, 290°C, 285°C, 280°C, 280°C and 275°C; the twin-screw extrusion The head temperature of the machine is 270°C.
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Denomination of invention: A high-strength nylon composite material and its preparation method using composite compatibilizers

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