CN102796258A

Movatterモバイル変換

Info

Publication number: CN102796258A
Application number: CN2012102596119A
Authority: CN
Inventors: 龙盛如; 张美林; 杨杰; 瞿兰; 张刚; 王孝军
Original assignee: Sichuan University
Current assignee: Sichuan University
Priority date: 2012-07-25
Filing date: 2012-07-25
Publication date: 2012-11-28

Abstract

Translated fromChinese

本发明公开了一种原位增强半芳香聚酰胺复合材料的制备方法，其特点是按重量份计，将半芳香聚酰胺预聚体1000～5000份、催化剂1～50份、增强纤维500～5000份和分子量调节剂1～10份加入反应挤出机，在温度290～330℃、螺杆转速20～200rpm和真空度0.04～0.09MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料。The invention discloses a method for preparing an in-situ reinforced semi-aromatic polyamide composite material. Add 5000 parts and 1-10 parts of molecular weight regulator into the reaction extruder, and react and extrude at a temperature of 290-330 ° C, a screw speed of 20-200 rpm and a vacuum of 0.04-0.09 MPa; the extruded product is drawn, cooled, and pelletized and drying to obtain in-situ reinforced semi-aromatic polyamide composites.

Description

Translated fromChinese

一种原位增强半芳香聚酰胺复合材料的制备方法A kind of preparation method of in-situ reinforced semi-aromatic polyamide composite material

技术领域technical field

本发明涉及一种原位增强半芳香聚酰胺复合材料的制备方法，属于高分子材料技术领域。The invention relates to a preparation method of an in-situ reinforced semi-aromatic polyamide composite material, belonging to the technical field of polymer materials.

背景技术Background technique

半芳香聚酰胺是一类耐高温、耐腐蚀和易加工的高分子材料，主要用于电子电器和汽车工业等领域。工业应用往往需要加入纤维进行增强，如玻璃纤维增强聚对苯二甲酰己二胺（PA6T）和聚对苯二甲酰壬二胺（PA9T）。Semi-aromatic polyamide is a kind of polymer material with high temperature resistance, corrosion resistance and easy processing. It is mainly used in the fields of electronic appliances and automobile industry. Industrial applications often require the addition of fibers for reinforcement, such as glass fiber reinforced polyhexamethylene terephthalamide (PA6T) and polynonanediamide terephthalamide (PA9T).

目前纤维增强半芳香聚酰胺复合材料主要采用纯树脂和增强纤维挤出造粒得到，但树脂合成工艺复杂，且树脂合成和纤维添加分开进行，能量综合利用率低。本发明的前期工作已公开发明专利CN102532528A以二元羧酸、二元胺、尼龙盐和氨基酸等为原料，先固相缩聚制得一定分子量的聚合物，再通过反应挤出进一步提高分子量获得高分子量的半芳香聚酰胺。在此基础上，本发明采用低分子量的半芳香聚酰胺预聚体和增强纤维直接反应挤出制备原位增强半芳香聚酰胺复合材料，所得复合材料可采用注射、模压和挤出等方式加工成型。At present, fiber-reinforced semi-aromatic polyamide composites are mainly obtained by extrusion and granulation of pure resin and reinforced fiber, but the resin synthesis process is complicated, and the resin synthesis and fiber addition are carried out separately, and the comprehensive energy utilization rate is low. The previous work of the present invention has published the invention patent CN102532528A, using dicarboxylic acid, diamine, nylon salt and amino acid as raw materials, first solid-state polycondensation to obtain a polymer with a certain molecular weight, and then further increasing the molecular weight to obtain a high molecular weight by reaction extrusion. Molecular weight semi-aromatic polyamide. On this basis, the present invention uses low-molecular-weight semi-aromatic polyamide prepolymers and reinforcing fibers to directly react and extrude to prepare in-situ reinforced semi-aromatic polyamide composite materials, and the obtained composite materials can be processed by injection, molding and extrusion. forming.

发明内容Contents of the invention

本发明的目的是针对现有技术的不足而提供一种原位增强半芳香聚酰胺复合材料的制备方法，其特点是以半芳香聚酰胺预聚体为原料，在催化剂和分子量调节剂的作用下，并加入增强纤维，反应挤出制备原位增强半芳香聚酰胺复合材料。此方法具有可连续操作和收率高的优点，所得复合材料具有易加工、力学强度高和耐高温的优点。The purpose of the present invention is to provide a kind of preparation method of in-situ reinforced semi-aromatic polyamide composite material in view of the deficiencies in the prior art, and its characteristic is to use semi-aromatic polyamide prepolymer as raw material, in the role of catalyst and molecular weight regulator Next, adding reinforcing fibers, reactive extrusion prepared in-situ reinforced semi-aromatic polyamide composites. The method has the advantages of continuous operation and high yield, and the obtained composite material has the advantages of easy processing, high mechanical strength and high temperature resistance.

本发明的目的由以下技术措施实现，其中所述原料份数除特殊说明外，均为重量份数。The object of the present invention is achieved by the following technical measures, wherein the parts of raw materials are parts by weight unless otherwise specified.

原位增强半芳香聚酰胺复合材料制备方法包括以下步骤：The preparation method of the in-situ reinforced semi-aromatic polyamide composite material comprises the following steps:

（1）将半芳香聚酰胺预聚体1000～5000份、催化剂1～50份、增强纤维500～5000份和分子量调节剂1～10份加入反应挤出机，在温度290～330℃、螺杆转速20～200rpm和真空度0.04～0.09MPa下反应挤出,得到挤出物；(1) Add 1000-5000 parts of semi-aromatic polyamide prepolymer, 1-50 parts of catalyst, 500-5000 parts of reinforcing fiber and 1-10 parts of molecular weight regulator into the reaction extruder, and at a temperature of 290-330 ° C, the screw Reaction extrusion at a rotation speed of 20-200rpm and a vacuum degree of 0.04-0.09MPa to obtain extrudates;

（2）将上述挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料。(2) The in-situ reinforced semi-aromatic polyamide composite material is obtained after the above-mentioned extrudate is drawn, cooled, pelletized and dried.

半芳香聚酰胺预聚体的结构式为：The structural formula of semi-aromatic polyamide prepolymer is:

其中m＝2～20，O＜x+v≤l，x≠O

中的至少一种；Where m=2～20, O<x+v≤l, x≠O

at least one of;

R₁＝-(CH₂)₂-、 -(CH₂)₄-、 -(CH₂)₆-、 -(CH₂)₉-和——(CH₂)₁₀-中的至少一种；R₁ ＝-(CH₂ )₂ -, -(CH₂ )₄ -, -(CH₂ )₆ -, -(CH₂ )₉ - and -(CH₂ )₁₀ - at least one of;

R₂＝-(CH₂)₄-和/或-(CH₂)₈-；R₂ = -(CH₂ )₄ - and/or -(CH₂ )₈ -;

R₃＝-(CH₂)₅-、 -(CH₂)₆-、 -(CH₂)₇-、 -(CH₂)₈-、-(CH₂)₉-、-(CH₂)₁₀-和-(CH₂)₁₁-中的至少一种。R₃ =-(CH₂ )₅ -, -(CH₂ )₆ -, -(CH₂ )₇ -, -(CH₂ )₈ -, -(CH₂ )₉ -, -(CH₂ )₁₀ - and at least one of -(CH₂ )₁₁ -.

催化剂为磷酸、焦磷酸、多聚磷酸、亚磷酸、磷酸钠、三磷酸钠、亚磷酸钠、次磷酸钠、丙酸和丁酸中的到少一种。The catalyst is at least one of phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, sodium phosphate, sodium triphosphate, sodium phosphite, sodium hypophosphite, propionic acid and butyric acid.

增强纤维为玻璃纤维、碳纤维、石英纤维、玄武岩纤维、芳纶纤维和金属纤维中的至少一种。The reinforcing fiber is at least one of glass fiber, carbon fiber, quartz fiber, basalt fiber, aramid fiber and metal fiber.

分子量调节剂为苯甲酸、对甲基苯甲酸、间甲基苯甲酸、邻甲基苯甲酸、1-萘甲酸、2-萘甲酸、月桂酸、软脂酸、硬脂酸、邻苯二甲酸酐或2,3-吡啶二甲酸酐中的任一种。Molecular weight regulators are benzoic acid, p-toluic acid, m-toluic acid, o-toluic acid, 1-naphthoic acid, 2-naphthoic acid, lauric acid, palmitic acid, stearic acid, phthalic acid Any of acid anhydride or 2,3-pyridine dicarboxylic anhydride.

半芳香聚酰胺预聚体和催化剂的加入口为反应挤出机的主喂料口。The inlet of semi-aromatic polyamide prepolymer and catalyst is the main feeding inlet of the reaction extruder.

增强纤维的加入口为反应挤出机的主喂料口和/或辅喂料口。The inlet for reinforcing fiber is the main feed port and/or auxiliary feed port of the reaction extruder.

分子量调节剂的加入口为反应挤出机的辅喂料口。The inlet of the molecular weight regulator is the auxiliary feeding inlet of the reaction extruder.

性能测试：Performance Testing:

原位增强半芳香聚酰胺复合材料注射成标准样条，采用岛津公司AGS-J型电子万能材料试验机测试力学性能。In-situ reinforced semi-aromatic polyamide composites were injected into standard specimens, and the mechanical properties were tested by Shimadzu AGS-J electronic universal material testing machine.

本发明具有如下优点：The present invention has the following advantages:

1．采用半芳香聚酰胺预聚体和增强纤维反应挤出的方法，省去树脂合成工艺，直接生产原位增强半芳香聚酰胺复合材料。1. The method of reactive extrusion of semi-aromatic polyamide prepolymer and reinforcing fiber is adopted, the resin synthesis process is omitted, and the in-situ reinforced semi-aromatic polyamide composite material is directly produced.

2．增强纤维的加入和树脂的生成同步进行，纤维与树脂界面结合好，复合材料的力学强度高。2. The addition of reinforcing fiber and the generation of resin are carried out simultaneously, the interface between fiber and resin is well combined, and the mechanical strength of the composite material is high.

3．半芳香聚酰胺预聚体和增强纤维的种类丰富，可以生产多种原位增强半芳香聚酰胺复合材料。3. There are many types of semi-aromatic polyamide prepolymers and reinforcing fibers, which can produce a variety of in-situ reinforced semi-aromatic polyamide composites.

4．原位增强半芳香聚酰胺复合材料的制备方法，反应挤出时间短，具有节能环保的优点。4. The preparation method of in-situ reinforced semi-aromatic polyamide composite material has short reaction extrusion time and has the advantages of energy saving and environmental protection.

5．原位增强半芳香聚酰胺复合材料的制备方法，实验重复性好，工艺稳定，产品收率高。5. The preparation method of in-situ reinforced semi-aromatic polyamide composite material has good experiment repeatability, stable process and high product yield.

具体实施方式Detailed ways

下面通过实施例对本发明进行具体的描述，有必要在此指出的是本实施例只用于对本发明进行进一步说明，不能理解为对本发明包括范围的限制，该领域的技术熟练人员可以根据上述本发明的内容作出一些非本质的改进和调整。The present invention is specifically described below through the examples, it is necessary to point out that the present examples are only used to further illustrate the present invention, and can not be interpreted as limiting the scope of the present invention, those skilled in the art can according to the above-mentioned The content of the invention makes some non-essential improvements and adjustments.

实施例1Example 1

将半芳香聚酰胺预聚体（由对苯二甲酸:己二酸:己二胺=83:73:116的重量比制备）5000g和磷酸50g从反应挤出机的主喂料口加入，玻璃纤维5000g和苯甲酸10g从辅喂料口加入，在温度320℃、螺杆转速150rpm和真空度0.04MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率96%，拉伸强度153MPa，弯曲强度248MPa，无缺口冲击强度83kJ/m²。Add 5000g of semi-aromatic polyamide prepolymer (prepared by the weight ratio of terephthalic acid: adipic acid: hexamethylenediamine = 83:73:116) and 50g of phosphoric acid from the main feeding port of the reaction extruder, glass Add 5000g of fiber and 10g of benzoic acid from the auxiliary feeding port, and react and extrude at a temperature of 320°C, a screw speed of 150rpm and a vacuum of 0.04MPa; the extrudate is drawn, cooled, pelletized and dried to obtain in-situ enhanced semi-aromatic Polyamide composite material, yield 96%, tensile strength 153MPa, flexural strength 248MPa, unnotched impact strength 83kJ/m² .

实施例2Example 2

将半芳香聚酰胺预聚体（由对苯二甲酸己二胺盐:己内酰胺=141:59的重量比制备）1000g和焦磷酸1g从反应挤出机的主喂料口加入，碳纤维500g和对甲基苯甲酸1g从辅喂料口加入，在温度290℃、螺杆转速20rpm和真空度0.09MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率94%，拉伸强度137MPa，弯曲强度241MPa，无缺口冲击强度76kJ/m²。Add 1000g of semi-aromatic polyamide prepolymer (prepared by the weight ratio of hexamethylenediamine terephthalate:caprolactam=141:59) and 1g of pyrophosphoric acid from the main feeding port of the reaction extruder, 500g of carbon fiber and Add 1 g of methyl benzoic acid from the auxiliary feeding port, and react and extrude at a temperature of 290 ° C, a screw speed of 20 rpm, and a vacuum of 0.09 MPa; Amide composite material, the yield is 94%, the tensile strength is 137MPa, the bending strength is 241MPa, and the unnotched impact strength is 76kJ/m² .

实施例3Example 3

将半芳香聚酰胺预聚体（由4,4’-(4-硫醚苯甲酸)-三苯基氧化膦:癸二胺:环庚内酰胺=582:172:46的重量比制备）3500g、多聚磷酸20g和碳纤维1000g从反应挤出机的主喂料口加入，玻璃纤维2000g和间甲基苯甲酸8g从辅喂料口加入，在温度330℃、螺杆转速200rpm和真空度0.07MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率93%，拉伸强度168MPa，弯曲强度257MPa，无缺口冲击强度75kJ/m²。Semi-aromatic polyamide prepolymer (prepared by weight ratio of 4,4'-(4-thioetherbenzoic acid)-triphenylphosphine oxide:decanediamine:cycloenantholactam=582:172:46) 3500g , 20g of polyphosphoric acid and 1000g of carbon fiber are added from the main feeding port of the reaction extruder, 2000g of glass fiber and 8g of m-toluic acid are added from the auxiliary feeding port, at a temperature of 330°C, a screw speed of 200rpm and a vacuum of 0.07MPa Down reaction extrusion; the extrudate is drawn, cooled, pelletized and dried to obtain an in-situ reinforced semi-aromatic polyamide composite material with a yield of 93%, a tensile strength of 168MPa, a flexural strength of 257MPa, and an unnotched impact strength of 75kJ/m² .

实施例4Example 4

将半芳香聚酰胺预聚体（由间苯二甲酸乙二胺盐:己二酸己二胺盐=120:180的重量比制备）1500g和亚磷酸10g从反应挤出机的主喂料口加入，石英纤维500g和邻甲基苯甲酸5g从辅喂料口加入，在温度300℃、螺杆转速100rpm和真空度0.08MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率91%，拉伸强度94MPa，弯曲强度172MPa，无缺口冲击强度51kJ/m²。Put 1500g of semi-aromatic polyamide prepolymer (prepared by the weight ratio of ethylenediamine isophthalate: hexamethylenediamine adipate = 120:180) and 10g of phosphorous acid from the main feeding port of the reaction extruder Add, 500g of quartz fiber and 5g of o-toluic acid are added from the auxiliary feeding port, and the reaction is extruded at a temperature of 300°C, a screw speed of 100rpm and a vacuum of 0.08MPa; the extrudate is drawn, cooled, pelletized and dried The in-situ reinforced semi-aromatic polyamide composite material was obtained, with a yield of 91%, a tensile strength of 94MPa, a bending strength of 172MPa, and an unnotched impact strength of 51kJ/m² .

实施例5Example 5

将半芳香聚酰胺预聚体（由二苯硫醚二甲酰氯:癸二酰氯:丁二胺=311:358:220的重量比制备）4000g、磷酸钠35g和玄武岩纤维1500g从反应挤出机的主喂料口加入，玄武岩纤维2000g和1-萘甲酸10g从辅喂料口加入，在温度310℃、螺杆转速90rpm和真空度0.06MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率92%，拉伸强度149MPa，弯曲强度220MPa，无缺口冲击强度87kJ/m²。4000g of semi-aromatic polyamide prepolymer (prepared by the weight ratio of diphenyl sulfide diformyl chloride: sebacoyl chloride: butanediamine = 311:358:220), 35g of sodium phosphate and 1500g of basalt fiber from the reaction extruder 2000g of basalt fiber and 10g of 1-naphthoic acid were added from the auxiliary feeding port, and reacted and extruded at a temperature of 310°C, a screw speed of 90rpm and a vacuum of 0.06MPa; the extruded product was drawn, cooled, cut After pelleting and drying, an in-situ reinforced semi-aromatic polyamide composite material was obtained, with a yield of 92%, a tensile strength of 149MPa, a bending strength of 220MPa, and an unnotched impact strength of 87kJ/m² .

实施例6Example 6

将半芳香聚酰胺预聚体（由二苯醚二甲酸:壬二胺:8-氨基辛酸=258:158:84的重量比制备）2000g和三磷酸钠5g、磷酸钠10g从反应挤出机的主喂料口加入，芳纶纤维1000g和2-萘甲酸3g从辅喂料口加入，在温度300℃、螺杆转速60rpm和真空度0.09MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率95%，拉伸强度128MPa，弯曲强度213MPa，无缺口冲击强度78kJ/m²。Put 2000g of semi-aromatic polyamide prepolymer (prepared by the weight ratio of diphenyl ether dicarboxylic acid:nonanediamine:8-aminocaprylic acid=258:158:84), 5g of sodium triphosphate, and 10g of sodium phosphate from the reaction extruder 1000g of aramid fiber and 3g of 2-naphthoic acid are added from the auxiliary feeding port, and reacted and extruded at a temperature of 300°C, a screw speed of 60rpm and a vacuum of 0.09MPa; the extruded product is drawn, cooled, After pelletizing and drying, an in-situ reinforced semi-aromatic polyamide composite material was obtained, with a yield of 95%, a tensile strength of 128MPa, a bending strength of 213MPa, and an unnotched impact strength of 78kJ/m² .

实施例7Example 7

将半芳香聚酰胺预聚体（由二苯甲酮二甲酸:癸二胺:9-氨基壬酸:己内酰胺=270:172:158:50的重量比制备）3500g、亚磷酸钠35g和玻璃纤维2000g从反应挤出机的主喂料口加入，金属纤维100g和月桂酸8g从辅喂料口加入，在温度305℃、螺杆转速120rpm和真空度0.08MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率93%，拉伸强度178MPa，弯曲强度260MPa，无缺口冲击强度95kJ/m²。Semi-aromatic polyamide prepolymer (prepared by the weight ratio of benzophenone dicarboxylic acid:decanediamine:9-aminononanoic acid:caprolactam=270:172:158:50) 3500g, sodium phosphite 35g and glass fiber Add 2000g from the main feeding port of the reaction extruder, add 100g of metal fiber and 8g of lauric acid from the auxiliary feeding port, and react and extrude at a temperature of 305°C, a screw speed of 120rpm and a vacuum of 0.08MPa; the extruded product is drawn , cooling, pelletizing and drying to obtain an in-situ reinforced semi-aromatic polyamide composite material with a yield of 93%, a tensile strength of 178MPa, a bending strength of 260MPa and an unnotched impact strength of 95kJ/m² .

实施例8Example 8

将半芳香聚酰胺预聚体（由二苯砜二甲酸:乙二胺:己二胺:10-氨基癸酸=306:30:53:334的重量比制备）3200g和次磷酸钠30g从反应挤出机的主喂料口加入，玻璃纤维1800g和软脂酸7g从辅喂料口加入，在温度325℃、螺杆转速170rpm和真空度0.09MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率93%，拉伸强度167MPa，弯曲强度232MPa，无缺口冲击强度82kJ/m²。Semi-aromatic polyamide prepolymer (prepared by the weight ratio of diphenylsulfonedicarboxylic acid: ethylenediamine: hexamethylenediamine: 10-aminodecanoic acid = 306:30:53:334) 3200g and sodium hypophosphite 30g from the reaction Add in the main feeding port of the extruder, add 1800g of glass fiber and 7g of palmitic acid from the auxiliary feeding port, and react and extrude at a temperature of 325°C, a screw speed of 170rpm and a vacuum of 0.09MPa; the extruded product is drawn and cooled , pelletizing and drying to obtain in-situ reinforced semi-aromatic polyamide composite material with a yield of 93%, a tensile strength of 167MPa, a bending strength of 232MPa and an unnotched impact strength of 82kJ/m² .

实施例9Example 9

将半芳香聚酰胺预聚体（由4,4’-(4-硫醚苯甲酸)-二苯甲酮:丁二胺:11-氨基十一碳酸=243:44:163的重量比制备）4500g和丙酸40g从反应挤出机的主喂料口加入，玻璃纤维2500g和硬脂酸10g从辅喂料口加入，在温度320℃、螺杆转速160rpm和真空度0.05MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率92%，拉伸强度123MPa，弯曲强度216MPa，无缺口冲击强度75kJ/m²。Semi-aromatic polyamide prepolymer (prepared by weight ratio of 4,4'-(4-thioetherbenzoic acid)-benzophenone:butylene diamine:11-aminoundecanoic acid=243:44:163) Add 4500g and 40g of propionic acid from the main feeding port of the reaction extruder, add 2500g of glass fiber and 10g of stearic acid from the auxiliary feeding port, and react and extrude at a temperature of 320°C, a screw speed of 160rpm and a vacuum of 0.05MPa; The extrudate was drawn, cooled, pelletized and dried to obtain an in-situ reinforced semi-aromatic polyamide composite material with a yield of 92%, a tensile strength of 123MPa, a bending strength of 216MPa and an unnotched impact strength of 75kJ/m² .

实施例10Example 10

将半芳香聚酰胺预聚体（由4,4’-(4-硫醚苯甲酸)-二苯砜:4,4’-(4-硫醚苯甲酸)-二苯甲酮:己二酸:己二胺=26:219:146:174的重量比制备）2400g和丁酸20g从反应挤出机的主喂料口加入，金属纤维500g和邻苯二甲酸酐6g从辅喂料口加入，在温度295℃、螺杆转速70rpm和真空度0.07MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率94%，拉伸强度94MPa，弯曲强度187MPa，无缺口冲击强度53kJ/m²。The semi-aromatic polyamide prepolymer (by 4,4'-(4-thioether benzoic acid)-diphenyl sulfone:4,4'-(4-thioether benzoic acid)-benzophenone:adipic acid :hexamethylenediamine=26:219:146:174 weight ratio preparation) 2400g and butyric acid 20g are added from the main feeding port of the reaction extruder, metal fiber 500g and phthalic anhydride 6g are added from the auxiliary feeding port , reaction extrusion at a temperature of 295 ° C, a screw speed of 70 rpm and a vacuum of 0.07 MPa; the extrudate was drawn, cooled, pelletized and dried to obtain an in-situ reinforced semi-aromatic polyamide composite material, with a yield of 94%, stretching The strength is 94MPa, the bending strength is 187MPa, and the unnotched impact strength is 53kJ/m² .

实施例11Example 11

将半芳香聚酰胺预聚体（由4,4’-(4-氧苯甲酸)-二苯甲酮:癸二酸:癸二胺=227:101:172的重量比制备）3900g、磷酸20g和多聚磷酸15g从反应挤出机的主喂料口加入，碳纤维2600g和2,3-吡啶二甲酸酐7g从辅喂料口加入，在温度330℃、螺杆转速150rpm和真空度0.07MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率95%，拉伸强度164MPa，弯曲强度239MPa，无缺口冲击强度86kJ/m²。Semi-aromatic polyamide prepolymer (prepared by weight ratio of 4,4'-(4-oxybenzoic acid)-benzophenone:sebacic acid:decanediamine=227:101:172) 3900g, phosphoric acid 20g Add 15g of polyphosphoric acid from the main feeding port of the reaction extruder, add 2600g of carbon fiber and 7g of 2,3-pyridine dicarboxylic anhydride from the auxiliary feeding port, at a temperature of 330°C, a screw speed of 150rpm and a vacuum of 0.07MPa Reactive extrusion; the extrudate is drawn, cooled, pelletized and dried to obtain an in-situ reinforced semi-aromatic polyamide composite material with a yield of 95%, a tensile strength of 164MPa, a flexural strength of 239MPa, and an unnotched impact strength of 86kJ/m² .

实施例12Example 12

将半芳香聚酰胺预聚体（由4,4’-(4-氧苯甲酸)-二苯砜:己二酸:壬二胺=245:73:158的重量比制备）4800g、三磷酸钠47g和石英纤维1200g从反应挤出机的主喂料口加入，玻璃纤维2500g和邻甲基苯甲酸10g从辅喂料口加入，在温度325℃、螺杆转速170rpm和真空度0.08MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率91%，拉伸强度171MPa，弯曲强度268MPa，无缺口冲击强度77kJ/m²。Semi-aromatic polyamide prepolymer (prepared by weight ratio of 4,4'-(4-oxybenzoic acid)-diphenylsulfone: adipic acid: nonanediamine = 245:73:158) 4800g, sodium triphosphate 47g and 1200g of quartz fiber are added from the main feeding port of the reaction extruder, 2500g of glass fiber and 10g of o-toluic acid are added from the auxiliary feeding port, and the extruder is extruded at a temperature of 325°C, a screw speed of 170rpm and a vacuum of 0.08MPa. Extrusion; the extrudate was drawn, cooled, pelletized and dried to obtain an in-situ reinforced semi-aromatic polyamide composite material with a yield of 91%, a tensile strength of 171MPa, a bending strength of 268MPa and an unnotched impact strength of 77kJ/m² .

实施例13Example 13

将半芳香聚酰胺预聚体（由三苯基氧化膦二甲酸:癸二胺:己内酰胺=183:86:81的重量比制备）3400g、亚磷酸35g和玄武岩纤维2100g从反应挤出机的主喂料口加入，金属纤维500g和2-萘甲酸7g从辅喂料口加入，在温度320℃、螺杆转速100rpm和真空度0.06MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率94%，拉伸强度137MPa，弯曲强度249MPa，无缺口冲击强度62kJ/m²。3400g of semi-aromatic polyamide prepolymer (prepared by the weight ratio of triphenylphosphine oxide dicarboxylic acid: decyl diamine: caprolactam = 183:86:81), 35g of phosphorous acid and 2100g of basalt fiber from the main body of the reaction extruder Add in the feed port, add 500g of metal fiber and 7g of 2-naphthoic acid from the auxiliary feed port, and react and extrude at a temperature of 320°C, a screw speed of 100rpm and a vacuum of 0.06MPa; the extrudate is drawn, cooled, pelletized and After drying, an in-situ reinforced semi-aromatic polyamide composite material was obtained, with a yield of 94%, a tensile strength of 137MPa, a bending strength of 249MPa, and an unnotched impact strength of 62kJ/m² .

实施例14Example 14

将半芳香聚酰胺预聚体（由4,4’-(4-氧苯甲酸)-三苯基氧化膦:丁二胺:环庚内酰胺=275:44:171的重量比制备）2700g、丙酸8g、磷酸20g和玻璃纤维1500g从反应挤出机的主喂料口加入，碳纤维800g和苯甲酸8g从辅喂料口加入，在温度315℃、螺杆转速140rpm和真空度0.05MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率92%，拉伸强度173MPa，弯曲强度266MPa，无缺口冲击强度84kJ/m²。Semi-aromatic polyamide prepolymer (prepared by weight ratio of 4,4'-(4-oxybenzoic acid)-triphenylphosphine oxide:butylene diamine:cycloenantholactam=275:44:171) 2700g, Add 8g of propionic acid, 20g of phosphoric acid and 1500g of glass fiber from the main feeding port of the reaction extruder, add 800g of carbon fiber and 8g of benzoic acid from the auxiliary feeding port, and react at a temperature of 315°C, a screw speed of 140rpm and a vacuum of 0.05MPa Extrusion; the extrudate was drawn, cooled, pelletized and dried to obtain in-situ reinforced semi-aromatic polyamide composite material with a yield of 92%, a tensile strength of 173MPa, a bending strength of 266MPa and an unnotched impact strength of 84kJ/m² .

实施例15Example 15

将半芳香聚酰胺预聚体（由对苯二甲酸己二胺盐:己二酸己二胺盐:己内酰胺=846:524:113的重量比制备）2100g、亚磷酸钠18g和石英纤维800g从反应挤出机的主喂料口加入，玄武岩纤维1200g和硬脂酸5g从辅喂料口加入，在温度310℃、螺杆转速160rpm和真空度0.06MPa下反应挤出；挤出物经牵引、冷却、切粒和干燥后获得原位增强半芳香聚酰胺复合材料，产率95%，拉伸强度158MPa，弯曲强度243MPa，无缺口冲击强度76kJ/m²。Semi-aromatic polyamide prepolymer (prepared by hexamethylenediamine terephthalate: hexamethylene adipate: caprolactam = 846:524:113 weight ratio) 2100g, sodium phosphite 18g and quartz fiber 800g from The main feeding port of the reaction extruder is added, 1200g of basalt fiber and 5g of stearic acid are added from the auxiliary feeding port, and the reaction is extruded at a temperature of 310°C, a screw speed of 160rpm and a vacuum of 0.06MPa; the extruded product is drawn, After cooling, pelletizing and drying, an in-situ reinforced semi-aromatic polyamide composite material was obtained, with a yield of 95%, a tensile strength of 158MPa, a bending strength of 243MPa, and an unnotched impact strength of 76kJ/m² .

Claims

1. an original position strengthens the preparation method of semi-aromatic polyamide matrix material, it is characterized in that this method may further comprise the steps:

(1) by weight; 1000～5000 parts of semi-aromatic polyamide performed polymers, 1～50 part of catalyzer, 500～5000 parts of fortifying fibres and molecular weight regulator are added extruder for 1～10 part; Under 290～330 ℃ of temperature, screw speed 20～200rpm and vacuum tightness 0.04～0.09MPa, react and extrude, obtain extrudate;

(2) above-mentioned extrudate is obtained original position after traction, cooling, pelletizing and drying and strengthen the semi-aromatic polyamide matrix material.

2. strengthen the preparation method of semi-aromatic polyamide matrix material according to the said original position of claim 1, it is characterized in that the structural formula of semi-aromatic polyamide performed polymer is:

M=2～20 wherein; 0＜x+y≤1, at least a in x ≠ 0;

R₁=-(CH₂)₂-,-(CH₂)₄-,-(CH₂)₆-,-(CH₂)₉-with-(CH₂)₁₀-at least a;

R₂=-(CH₂)₄-and/or-(CH₂)₈-;

R₃=-(CH₂)₅-,-(CH₂)₆-,-(CH₂)₇-,-(CH₂)₈-,-(CH₂)₉-,-(CH₂)₁₀-with-(CH₂)₁₁-at least a.

3. strengthen the preparation method of semi-aromatic polyamide matrix material according to the said original position of claim 1, it is characterized in that catalyzer is at least a in phosphoric acid, tetra-sodium, polyphosphoric acid, phosphorous acid, sodium phosphate, Tri sodium Phosphate, sodium phosphite, sodium hypophosphite, propionic acid and the butyric acid.

4. strengthen the preparation method of semi-aromatic polyamide matrix material according to the said original position of claim 1, it is characterized in that fortifying fibre is at least a in spun glass, thomel, silica fiber, basalt fibre, aramid fiber and the steel fiber.

5. strengthen the preparation method of semi-aromatic polyamide matrix material according to the said original position of claim 1; It is characterized in that molecular weight regulator is phenylformic acid, p-methylbenzoic acid, m-methyl benzoic acid, o-toluic acid, 1-naphthoic acid, 2-naphthoic acid, LAURIC ACID 99 MIN, Palmiticacid, Triple Pressed Stearic Acid, Tetra hydro Phthalic anhydride or 2, any in the 3-dinicotinic acid acid anhydride.

6. strengthen the preparation method of semi-aromatic polyamide matrix material according to claim 1 or 2 or 3 said original positions, it is characterized in that the inlet that adds of semi-aromatic polyamide performed polymer and catalyzer is the main spout of extruder.

7. strengthen the preparation method of semi-aromatic polyamide matrix material according to claim 1 or 4 said original positions, it is characterized in that the inlet that adds of fortifying fibre is the main spout of extruder and/or auxilliary spout.

8. strengthen the preparation method of semi-aromatic polyamide matrix material according to claim 1 or 5 said original positions, it is characterized in that the inlet that adds of molecular weight regulator is the auxilliary spout of extruder.