Cyclic dimer blending modified PA66 material and preparation method thereof

Abstract

The invention discloses a cyclic dimer blending modified PA66 (polyamide 66) material. The invention discloses a cool-feeling functional nano-material, which is prepared from the following raw materials in parts by weight: 20 to 30 percent of cyclic dimer, 20 to 40 percent of PA66, 40 to 50 percent of PA66, 5 to 10 percent of industrial white oil, 1 to 5 percent of polypropylene, 1 to 5 percent of epoxy acrylate rubber, 1 to 5 percent of solid lubricant, 1 to 5 percent of glass bead and 1 to 5 percent of cool-feeling functional nano-powder. The tensile strength and the hooking strength of the fibers are improved by adopting polypropylene, the toughness of a blend system is greatly improved by adopting epoxy acrylate rubber, the comprehensive mechanical property of PA66 is remarkably improved by adopting a solid lubricant and glass beads, the draft multiple is improved by adopting nanoscale powder with a cool feeling function, and the breaking strength is in a rising trend. The application scene of the modified PA66 material is expanded, the market competitiveness of the material is improved, the preparation process is simple, the capacity of batch production is achieved, and the use requirements of people are met.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and specifically to a cyclic dimer blended and modified PA66 material. Background Art

[0002] Polyamide 6 (PA6) has good heat resistance, excellent acid, alkali and corrosion resistance, high tensile strength and good impact resistance. PA6 also has the characteristics of low friction coefficient, self-lubricating and good anti-wear performance. PA6 has a very common application in the automotive manufacturing industry. In recent years, plastic products have become increasingly common and their sales have increased rapidly. PA6 combines a series of excellent properties, such as: low density and light weight; easy to form and process in manufacturing, with a large space for free play in design; can isolate heat, has a large resistance and is an excellent insulator. In addition, PA6 is economical and the cost of the produced mold is low, having a great advantage in price compared with other resins. PA6 can be spun into fibers to make long fibers or short fibers.

[0003] The usage amount of PA6 short fibers accounts for about 21% of that of PA6 long fibers, and is mainly used for carpets, socks, gabardine fabrics, filter fabrics. Valentin fabrics are made by mixing and spinning PA6 short fibers with other fibers.

[0004] PA66 is a temperature-sensitive polymer material, and there is room for improvement in its self-shrinkage rate, which is between 1% and 2%. After adding glass fiber reinforcement, the shrinkage rate of PA66 can be reduced to 0.2% - 1%. The shrinkage rate is quite different in the flow direction and the direction perpendicular to the flow direction. The thermal stability and weather resistance of PA66 are better than those of PA6, while PA6 has good chemical resistance at high temperatures. Polyamide 66 has a higher melting point than polyamide 6 and can maintain strong strength and stiffness at higher temperatures. Polyamide 66 resin also has good moisture absorption after molding, which is mainly related to the groups of polyamide macromolecular chains, and the degree of water absorption is also related to the water humidity in the environment. The comprehensive mechanical properties of polyamide 66 are good, and it can be used as a modifier to achieve a toughening effect. In addition, using polyamide to modify polyamide can greatly reduce the interfacial delamination caused by incompatibility.

[0005] However, traditional PA66 has the following disadvantages:

[0006] Traditional PA66 has low toughness and low transparency, which limits its application in some fields and cannot meet people's usage requirements. Summary of the Invention

[0007] The purpose of the present invention is to provide a cyclic dimer blended and modified PA66 material to solve the problems of low toughness and low transparency of traditional PA66 as mentioned in the above background art, which limit its application in some fields and cannot meet people's usage requirements.

[0008] To achieve the above object, the present invention provides the following technical solution: A cyclic dimer blended and modified PA66 material, the raw materials by weight include: 20%-30% of cyclic dimer, 20%-40% of PA6, 40%-50% of PA66, 5%-10% of industrial white oil, 1%-5% of polypropylene, 1%-5% of epoxy acrylate rubber, 1%-5% of solid lubricant, 1%-5% of glass microspheres, and 1%-5% of cool-sensation functional nanoscale powder.

[0009] The PA6 is obtained by removing unreacted monomers and low-molecular by-products from caprolactam monomers and initiators through vacuum dehydration, followed by extrusion granulation, drying treatment, and screening to obtain polycaprolactam particles with different particle sizes.

[0010] The PA66 uses adipic acid and hexamethylenediamine as raw materials to synthesize hexamethylenediamine adipate; then it is prepared by polycondensation using hexamethylenediamine adipate as the raw material.

[0011] The solid lubricant is at least one of polytetrafluoroethylene or graphite.

[0012] The cool-sensation functional nanoscale powder is at least one of silicon carbide powder, aluminum nitride powder, or jade powder.

[0013] A preparation method of a cyclic dimer blended and modified PA66 material, comprising the following steps:

[0014] Step 1. Raw material preparation: Prepare the required raw materials PA6 and PA66 respectively;

[0015] Step 2. Raw material pretreatment: Weigh various dried raw materials according to the formula ratio, including cyclic dimer; PA6; PA66; industrial white oil; polypropylene; epoxy acrylate rubber; solid lubricant; glass microspheres; cool-sensation functional nanoscale powder;

[0016] Step 3. Raw material melting: Mix the weighed cyclic dimer, PA6, PA66, and industrial white oil evenly in a high-speed mixer, add them from the main feeder of the twin-screw extruder, and obtain an intermediate product after melting extrusion, granulation, and drying treatment;

[0017] Step 4. Product preparation: Mix the weighed polypropylene; epoxy acrylate rubber; solid lubricant; glass microspheres; cool-sensation functional nanoscale powder evenly in a high-speed mixer to obtain an auxiliary product. Add the auxiliary product from the side feeder and the intermediate product from step 3 from the main feeder of the twin-screw extruder, and obtain the product after melting extrusion, granulation, and drying treatment.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows: By using cyclic dimers, the molding time is effectively shortened; by using polypropylene, both the fiber tensile strength and the snagging strength are improved; by using epoxy acrylate rubber, the toughness of the blend system is greatly improved; by using solid lubricants and glass microspheres, the comprehensive mechanical properties of PA66 are significantly improved; by using cool-sensation functional nano-sized powders, the draw ratio is increased and the breaking strength shows an upward trend. Brief Description of the Drawings

[0019] Figure 1 This is a flowchart of the present invention. Detailed Embodiments

[0020] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.

[0021] PA6, manufacturer: Shandong Dongchen; grade: TM01;

[0022] PA66, manufacturer: Huafeng; grade: EP1106;

[0023] Cyclic dimer, manufacturer: DuPont, USA; grade: PC-2000;

[0024] Industrial white oil, manufacturer: 0em manufacturer; grade: Beishan No. 5;

[0025] Polypropylene, manufacturer: Shandong; grade: PP-H;

[0026] Epoxy acrylate rubber, manufacturer: Suining Qinglong; grade: model ar-100;

[0027] Solid lubricant, manufacturer: Jingjing brand; grade: HZN-102;

[0028] Glass microspheres, manufacturer: Langfang Aolan Glass Microspheres Co., Ltd.; grade: IM16K3M3M;

[0029] Cool-sensation functional nano-sized powder, manufacturer: Jiangxi; grade: 70 / 48;

[0030] Refer to Figure 1, the present invention discloses a cyclic dimer blended and modified PA66 material, and the raw materials by weight include: 20%-30% of cyclic dimer, 20%-40% of PA6, 40%-50% of PA66, 5%-10% of industrial white oil, 1%-5% of polypropylene, 1%-5% of epoxy acrylate rubber, 1%-5% of solid lubricant, 1%-5% of glass microspheres, and 1%-5% of cool feeling functional nanoscale powder.

[0031] PA6 is obtained by removing unreacted monomers and low molecular by-products from caprolactam monomers and initiators through vacuum dehydration, followed by extrusion granulation, drying treatment, and screening to obtain polycaprolactam particles with different particle sizes.

[0032] PA66 uses adipic acid and hexamethylenediamine as raw materials to synthesize hexamethylenediamine adipate salt; and then polycondenses using hexamethylenediamine adipate salt as the raw material.

[0033] The solid lubricant is at least one of polytetrafluoroethylene or graphite.

[0034] The cool feeling functional nanoscale powder is at least one of silicon carbide powder, aluminum nitride powder, or jade powder.

[0035] A preparation method of a cyclic dimer blended and modified PA66 material includes the following steps:

[0036] Step 1, raw material preparation: Prepare the required raw materials PA6 and PA66 respectively;

[0037] Step 2, raw material pretreatment: Weigh various dried raw materials according to the formula ratio, including cyclic dimer; PA6; PA66; industrial white oil; polypropylene; epoxy acrylate rubber; solid lubricant; glass microspheres; cool feeling functional nanoscale powder;

[0038] Step 3, raw material melting: Mix the weighed cyclic dimer, PA6, PA66, and industrial white oil evenly in a high-speed mixer, add them from the main feeder of the twin-screw extruder, and obtain an intermediate product after the processes of melt extrusion, granulation, and drying treatment;

[0039] Step 4, product preparation: Mix the weighed polypropylene; epoxy acrylate rubber; solid lubricant; glass microspheres; cool feeling functional nanoscale powder evenly in a high-speed mixer to obtain an auxiliary product, add the intermediate product in Step 3 from the main feeder of the twin-screw extruder, add the auxiliary product from the side feeder, and obtain the product after the processes of melt extrusion, granulation, and drying treatment

[0040] Example 1:

[0041] By percentage, the raw materials include 20% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 2% of polypropylene, 3% of epoxy acrylate rubber, 1% of solid lubricant, 4% of glass microspheres, and 5% of cool-sensation functional nano-sized powder;

[0042] The processing method is as follows:

[0043] (1) Dry PA6 and PA66 in a vacuum circulating oven at 150 °C for 6 h, and control the moisture content to be less than 0.3%.

[0044] (2) Mix the dried PA66 / PA6, cyclic dimer, industrial white oil evenly in a high-speed mixer according to the formula ratio, add it from the main feeder of the twin-screw extruder, and obtain an intermediate product after the processes of melt extrusion, pelletizing, and drying.

[0045] (3) Mix the weighed polypropylene, epoxy acrylate rubber, solid lubricant, glass microspheres, and cool-sensation functional nano-sized powder evenly in a high-speed mixer to obtain an auxiliary product. Add the auxiliary product from the side feeder and the intermediate product obtained in the previous step from the main feeder of the twin-screw extruder, and obtain the product after the processes of melt extrusion, pelletizing, and drying.

[0046] Among them, the aspect ratio of the twin-screw extruder is 40:1, the temperature range of the extruder is 220 °C - 300 °C, the screw speed is set at 350 rpm. The processing temperatures of each section of the twin-screw extruder are as follows: the temperature of the first zone is 200 - 220 °C, the temperature of the second zone is 220 - 280 °C, the temperature of the third zone is 220 - 280 °C, the temperature of the fourth zone is 250 - 300 °C, the temperature of the fifth zone is 250 - 300 °C, the temperature of the sixth zone is 250 - 300 °C, the temperature of the seventh zone is 260 - 320 °C, the temperature of the eighth zone is 260 - 320 °C, the temperature of the ninth zone is 260 - 320 °C, the temperature of the tenth zone is 260 - 320 °C, and the temperature of the die head is 260 - 320 °C.

[0047] Example 2:

[0048] By percentage, the raw materials include 20% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 3% of polypropylene, 2% of epoxy acrylate rubber, 2% of solid lubricant, 3% of glass microspheres, and 5% of cool-sensation functional nano-sized powder;

[0049] The processing method is the same as that of Example 1.

[0050] Example 3:

[0051] By percentage, the raw materials include 20% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 3% of polypropylene, 3% of epoxy acrylate rubber, 2% of solid lubricant, 2% of glass microspheres, and 5% of cool-sensation functional nano-sized powder;

[0052] The processing method is the same as that of Example 1.

[0053] Example 4:

[0054] By percentage, the raw materials include 20% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 1% of polypropylene, 4% of epoxy acrylate rubber, 1% of solid lubricant, 4% of glass microspheres, and 5% of cool-sensation functional nano-scale powder;

[0055] The processing method is the same as that of Example 1.

[0056] Example 5:

[0057] By percentage, the raw materials include 20% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 4% of polypropylene, 4% of epoxy acrylate rubber, 1% of solid lubricant, 1% of glass microspheres, and 5% of cool-sensation functional nano-scale powder;

[0058] The processing method is the same as that of Example 1.

[0059] Comparative Example 1:

[0060] By percentage, the raw materials include 23% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 4% of polypropylene, 1% of epoxy acrylate rubber, 1% of solid lubricant, 1% of glass microspheres, and 5% of cool-sensation functional nano-scale powder;

[0061] The processing method is the same as that of Example 1.

[0062] Comparative Example 2:

[0063] By percentage, the raw materials include 24% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 3% of polypropylene, 1% of epoxy acrylate rubber, 1% of solid lubricant, 1% of glass microspheres, and 5% of cool-sensation functional nano-scale powder;

[0064] The processing method is the same as that of Example 1.

[0065] Comparative Example 3:

[0066] By percentage, the raw materials include 25% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 2% of polypropylene, 1% of epoxy acrylate rubber, 1% of solid lubricant, 1% of glass microspheres, and 5% of cool-sensation functional nano-scale powder;

[0067] The processing method is the same as that of Example 1.

[0068] Comparative Example 4:

[0069] By percentage, the raw materials include 26% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 1% of polypropylene, 1% of epoxy acrylate rubber, 1% of solid lubricant, 1% of glass microbeads, and 5% of cool-sensation functional nano-sized powder;

[0070] The processing method is the same as that of Example 1.

[0071] Comparative Example 5:

[0072] By percentage, the raw materials include 27% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 1% of polypropylene, 1% of epoxy acrylate rubber, 1% of solid lubricant, 1% of glass microbeads, and 4% of cool-sensation functional nano-sized powder;

[0073] The processing method is the same as that of Example 1.

[0074] Comparative Example 6:

[0075] By percentage, the raw materials include 28% of cyclic dimer, 20% of PA6, 40% of PA66, 5% of industrial white oil, 1% of polypropylene, 1% of epoxy acrylate rubber, 1% of solid lubricant, 1% of glass microbeads, and 3% of cool-sensation functional nano-sized powder;

[0076] The processing method is the same as that of Example 1.

[0077] Table 1:

[0078]

[0079]

[0080] When the mass fraction of the added cyclic dimer is 0.2%, the crystallinity of the cyclic dimer-modified PA66 is 25.14%, which is close to that of pure PA66. However, the crystallization temperature is increased compared with that of pure PA66, and the crystallization peak becomes narrower. As the addition amount of the cyclic dimer increases, the fracture strength and impact strength of the modified PA66 first increase and then decrease. The mechanical properties of the modified PA66 with a mass fraction of 0.2% of the added cyclic dimer are equivalent to those of the modified PA66 with a mass fraction of 0.1% of the added nucleating agent P22. The cyclic dimer plays a nucleating role in PA66, effectively shortening the molding time;

[0081] The copolyamide PA6 / PA66 was synthesized by polymerization reaction. H-NMR, FTIR and relative viscosity tests showed that AHSalt successfully polycondensed with caprolactam in a copolymerization form to form the macromolecular chain of polyamide. The relative viscosity range of the synthesized copolyamide was 2.1 - 2.6, meeting the spinning standard. With the increase of the mass ratio of PA66 in the polymerization system, the regularity of molecular segments and the intermolecular force decreased, the proportion of the crystalline region in the structure decreased, and the stable α-crystalline form decreased. The glass transition temperature, crystallization temperature, melting point and crystallinity of PA6 / PA66 all decreased gradually. The thermal stability of PA6 / PA66 decreased slightly, but the decrease was not obvious, indicating that with the addition of PA66, the amorphous state of the polymer increased, the transparency increased, the breaking strength decreased, and the elongation at break increased significantly. The crystallization rate constant, crystallization time and crystallization activation energy of the isothermal crystallization and non-isothermal crystallization of polyamide were calculated by using the Avrami equation and the Jeziorny model respectively. The results showed that with the increase of the mass ratio of PA66, the crystallization rate decreased gradually, the crystallization time increased gradually, and the activation energy decreased gradually during the crystallization process. PA6, PA6-10%PA66 and PA6-20%PA66 were selected for melt spinning. Compared with PA66, the moisture regain of PA6 / PA66 increased, the orientation degree and crystallinity decreased, and the breaking strength showed a downward trend. In addition, the crimp strength test was carried out on the fibers prepared by the melt method. The crimp strength ratio and elongation at break retention rate of PA6 / PA66 were much higher than those of PA66. The addition of PA6 helped to improve the crimp strength of PA66 fibers and reduce the loss of toughness of PA66 fibers, indicating that PA6 / PA66 fibers are very suitable for crimped fabrics.

[0082] Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent substitution on some of the technical features. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A cyclic dimer blended modified PA66 material, characterized in that: The invention is composed of the following raw materials in percentage by weight: 20%-30% of cyclic dimer, 20%-40% of PA6, 40%-50% of PA66, 5%-10% of industrial white oil, 1%-5% of polypropylene, 1%-5% of epoxy acrylate rubber, 1%-5% of solid lubricant, 1%-5% of glass microspheres and 1%-5% of nano-powder with cooling function.

2. The cyclic dimer blended modified PA66 material according to claim 1, characterized in that: The PA6 is prepared from caprolactam monomers and initiators by vacuum dehydration to remove unreacted monomers and low molecular weight byproducts, and then subjected to extrusion granulation, drying treatment and sieving to obtain polycaprolactam particles of different particle sizes.

3. The cyclic dimer blended modified PA66 material according to claim 1, characterized in that: The PA66 is prepared by using adipic acid and hexamethylenediamine as raw materials to synthesize hexamethylenediamine adipic acid salt; and then using hexamethylenediamine adipic acid salt as raw material for polycondensation.

4. The cyclic dimer blended modified PA66 material according to claim 1, characterized in that: The solid lubricant is at least one of polytetrafluoroethylene and graphite.

5. The cyclic dimer blended modified PA66 material according to claim 1, characterized in that: The cooling function nanometer-scale powder is at least one of silicon carbide powder, aluminum nitride powder or jade powder.

6. The method for preparing the cyclic dimer blended modified PA66 material according to any one of claims 1 to 5, characterized in that: The following steps are involved: Step 1: Raw material preparation: prepare the required raw materials PA6 and PA66 respectively; Step 2, raw material pretreatment: weigh various dried raw materials according to the formula ratio, cyclic dimer; PA6; PA66; industrial white oil; polypropylene; epoxy acrylate rubber; solid lubricant; glass microbeads; cool function nano-powder; Step 3, melting of raw materials: the weighed cyclic dimer, PA6, PA66, and industrial white oil are mixed evenly in a high-speed mixer, added from the main feed of a twin-screw extruder, and subjected to melt extrusion, granulation, and drying processes to obtain an intermediate product; Step 4, preparing the product: weighing polypropylene; epoxy acrylate rubber; solid lubricant; glass micro beads; The nanometer-scale powder with cooling function is mixed evenly in a high-speed mixer to obtain an auxiliary product, and the intermediate product in step three is added from the main feed of the twin-screw extruder, and the auxiliary product is added from the side feed, and the product is obtained after melt extrusion, granulation and drying treatment processes.

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