CN110551389A - low-cost, high-fluidity and wear-resistant PA6 material and preparation method thereof - Google Patents
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
The invention discloses a low-cost, high-fluidity and wear-resistant PA6 material and a preparation method thereof, wherein the preparation method comprises the following steps: 50-90 parts of polyamide 6 (nylon 6 and PA6), 5-30 parts of toughening agent, 2-10 parts of LLDPE resin, 0.1-1 part of compatilizer, 0.2-1 part of lubricant and 0.2-0.4 part of antioxidant. The invention solves the problems of large water absorption, large shrinkage, poor dimensional stability and the like of PA6 and better solves the industrial problems of poor mechanical property, processability, appearance quality and the like by adopting the scheme, and the prepared material can be widely applied to products such as automobile parts, mechanical parts, electronic and electric products, engineering accessories and the like.
Description
Technical Field
The invention relates to the field of material finishing, in particular to a low-cost, high-fluidity and wear-resistant PA6 material and a preparation method thereof.
Background
PA6, also called nylon 6, is semitransparent or opaque milky-white particles, has the characteristics of thermoplasticity, light weight, good toughness, chemical resistance, good durability and the like, has good wear resistance and self-lubrication, and is generally used for products such as automobile parts, mechanical parts, electronic and electrical products, engineering accessories and the like. Because PA6 is very easy to absorb water, has large shrinkage rate and low impact strength, various modifiers are generally required to balance the influence of crystallization speed and hygroscopicity.
The linear low-density polyethylene resin LLDPE resin is non-toxic, tasteless and odorless milky white particles, has higher softening temperature and melting temperature, has the advantages of high strength, good toughness, high rigidity, good heat resistance and cold resistance, and the like, also has good environmental stress crack resistance, impact strength, tearing strength and other properties, can resist acid, alkali, organic solvents and the like, and can be widely used in the fields of industry, agriculture, medicine, sanitation, daily necessities and the like.
ultra-high molecular weight polyethylene (UPE) is wear resistant, impact resistant, corrosion resistant, self lubricating, and absorbs impact energy-these five properties are the best among the existing plastics. The UPE wear-resistant plastic crown is 8 times that of common carbon steel, the impact strength is 6 times that of ABS, the self-lubricating property is equivalent to polytetrafluoroethylene, the corrosion resistance is strong, the chemical technical performance is high, the non-adhesiveness is good, the surface of a product is not easy to attach to other materials, the product is sanitary, non-toxic and low-temperature resistant, and has ductility under liquid nitrogen, and the defects are that: the tackiness was poor and the fluidity was poor.
Researchers have employed various methods by which carbon dioxide generated by a chemical blowing agent acts as a supercritical fluid through the application of a supercritical blowing agent. At the processing temperature of the thermoplastic, the carbon dioxide can dissolve any polymer melt such as UPE resin, LLDPE, PET, PA6 and the like, and greatly reduce the viscosity of the polymer melt, thereby playing the effects of a compatilizer, a flow modifier and the like. The defects of PA6 can be improved by combining the characteristics of good hydrophobicity, chemical resistance, wear resistance and excellent weather resistance of the UPE resin, and the characteristics of high strength, good toughness, high rigidity, good heat resistance and cold resistance of the LLDPE resin.
Disclosure of Invention
The invention aims to provide a low-cost, high-fluidity and wear-resistant PA6 material and a preparation method thereof, which are used for solving the problems that A6 is easy to absorb water, large in shrinkage rate and low in impact strength in the prior art.
The invention solves the problems through the following technical scheme:
a low cost, high flow and abrasion resistant PA6 material comprising the following components in parts by weight: 50-90 parts of PA6 resin, 2-30 parts of toughening agent, 2-10 parts of LLDPE resin, 0.1-1 part of compatilizer, 0.2-2 parts of lubricant, 0.2-0.4 part of silane coupling agent and 0.2-0.4 part of antioxidant.
Preferably, 70-90 parts of PA6 resin, 4-20 parts of toughening agent, 4-10 parts of LLDPE resin, 0.5-1 part of compatilizer, 0.5-2 parts of lubricant and 0.2-0.4 part of antioxidant.
Preferably, the PA6 resin is a semitransparent or opaque milky white crystalline polymer, the density of the polymer is 1.14-1.16 g/cm3, the melt index is 20-50 g/10min, and the heat distortion temperature is 50-70 ℃.
Preferably, the toughening agent is ultra-high molecular weight polyethylene powder, namely UPE, the density of the toughening agent is 0.93-0.95 g/cm3, and the particle size of the toughening agent is 50-300 nm.
Preferably, the silane coupling agent is vinyl siloxane and allyl siloxane, and common use is vinyl trimethoxy silane and vinyl triethoxy silane; can improve the wettability and the dispersibility of the polymer and the surface organization of the inorganic powder.
preferably, the LLDPE resin is linear low-density polyethylene resin which is non-toxic, tasteless and odorless milky white particles, the density is 0.918-0.935 g/cm3, and the melt index is 1.7-2.3 g/10 min.
preferably, the compatilizer is an endothermic closed-cell chemical nucleation foaming agent, the gas generated by thermal dispersion is carbon dioxide, and the content of the carbon dioxide is 80-85 ml/g.
Preferably, the lubricant is nano-synthesized magnesium-aluminum talc which is in a powder structure, the magnesium-aluminum ratio of the lubricant is 2:1, the average particle size is less than 80 μm, the whiteness is 92, and the specific gravity is 2.1 g/ml.
Also included is a method of making a low cost, high flow and abrasion resistant PA6 material, the method comprising the steps of:
Step 1: weighing UPE resin, a lubricant, an antioxidant, a foaming agent, a lubricant and a coupling agent in proportion, stirring for 3-10 minutes by a mixer, and taking out for later use;
Step 2: the PA6, LLDPE and activated powder resin are weighed according to a proportion, mixed by a high-speed mixer for 3-6 minutes, and uniformly mixed to form a premix.
And step 3: the premix is prepared by a melt blending method through a double-screw extruder, wherein the heating temperature is 190-230 ℃, and the extrusion temperature of a machine head is 180-200 ℃; the rotating speed of the main machine screw is 200-400 r/min, and the feeding rotating speed is 25-35 r/min.
Compared with the prior art, the invention has the following advantages and beneficial effects:
By reasonably selecting the raw material components, the proportion and the special processing method, the problems of large shrinkage, large water absorption, low toughness, poor wear resistance and the like in the traditional PA6 industry are solved, and the wear resistance, weather resistance and chemical resistance of PA6 are further improved by adding UPE; the addition of LLDPE improves the toughness of the material; the application of the foaming agent enhances the interface interaction between the matrix and the substrate and improves the compatibility between the matrix and the substrate; the added lubricant has high thermal stability, high transparency, excellent dispersion performance and good weather resistance, and further solves the problem of uniformity of alloy materials; by adopting the preparation method of melt blending of the double-screw extruder, under the condition of full mixing, the damage of high-speed shearing action on the foaming agent is effectively reduced, and the bamboo PA6 composite material with higher strength and toughness, good processing performance and appearance effect is prepared, and can be widely applied to various fields of electronics, automobiles, household appliances and the like.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
a low cost, high flow and abrasion resistant PA6 material comprising the following components in parts by weight: 50-90 parts of PA6 resin, 2-30 parts of toughening agent, 2-10 parts of LLDPE resin, 0.1-1 part of compatilizer, 0.2-2 parts of lubricant, 0.2-0.4 part of silane coupling agent and 0.2-0.4 part of antioxidant. The PA6 resin is a semitransparent or opaque milky white crystalline polymer, the density of the PA6 resin is 1.14-1.16 g/cm3, the melt index is 20-50 g/10min, and the heat deformation temperature is 50-70 ℃. The toughening agent is ultra-high molecular weight polyethylene powder, namely UPE, the density of the toughening agent is 0.93-0.95 g/cm3, and the particle size of the toughening agent is 50-300 nm. The silane coupling agent is vinyl siloxane and allyl siloxane, and common vinyl trimethoxy silane and vinyl triethoxy silane are used; can improve the wettability and the dispersibility of the polymer and the surface organization of the inorganic powder. The LLDPE resin is linear low-density polyethylene resin, is non-toxic, tasteless and odorless milky white particles, has the density of 0.918-0.935 g/cm3, and has the melt index of 1.7-2.3 g/10 min. The compatilizer is a heat absorption closed-cell type chemical nucleation foaming agent, gas generated by heat dispersion is carbon dioxide, and the content of the carbon dioxide is 80-85 ml/g. The lubricant is nano-synthesized magnesium-aluminum talc with a powder structure, the magnesium-aluminum ratio of the lubricant is 2:1, the average particle size is less than 80 mu m, the whiteness is 92, and the specific gravity is 2.1 g/ml.
The above materials were carried out, and the respective raw materials were weighed in accordance with the raw material formulation of Table 1 to prepare 3 examples and 2 comparative examples, in which the PA6 resin had a density of 1.156g/cm3, a melt flow rate of 55.4g/10min, an impact strength of 10.93KJ/m2, and a Rockwell hardness of 72.2 (R); the LLDPE resin has the melt flow rate of 2g/10min, the density of 0.92g/cm3, the tensile strength of 12MPa and the elongation at break of 500 percent; UPE density of 0.945g/cm3, tensile strength of 27MPa, bending strength of 15MPa, impact strength of 64KJ/m2, Shore hardness of 62(D) and heat distortion temperature of 85 ℃.
3 examples and 2 comparative examples were obtained by the following preparation procedure. The preparation process comprises the following steps:
Step 1, sequentially putting UPE powder, a compatilizer, a lubricant and an antioxidant into a high-speed mixer, then adding a silane coupling agent, stirring at a high speed for 3-5 min to fully stir the powder, and taking out for later use; because the common high-speed mixer is only set with a high-speed and a low-speed, and has no specific speed range, the invention only requires that the high-speed mixing time is 3-6 minutes when the mechanical mixing is carried out in any high-speed mixer;
Step 2, sequentially putting the PA6, LLDPE and activated powder into a high-speed mixer, stirring at a high speed for 3-5 min, and taking out;
Step 3, extruding the premix through a double-screw extruder (the length-diameter ratio of a screw is 40: 1) by adopting a melt blending method, cooling and granulating to obtain a modified reinforced PA6 material, wherein in order to ensure sufficient melt pressure, at least 1 group of kneading blocks with staggered angles of 90 degrees are sheared and combined by the screw kneading blocks to ensure that the UPE is fully melted; at the same time, in order to ensure the effective action of the foaming agent, the sufficient solution pressure (generally 7.0MPa) needs to be maintained, so that the rotation speed of the screw main machine needs to be as large as possible, and the rotation speed of the main feeding needs to be as small as possible. The product property test data are shown in Table 2. The technological parameters of extrusion granulation are as follows: the heating temperature section is as follows: temperature in the first zone: 180 ℃, temperature in zone two: 200 ℃, three-zone temperature: 220 ℃, four zone temperature: 220 ℃, five zone temperature: 230 ℃, six zone temperature: 230 ℃, temperature in seven zones: 230 ℃, eight zone temperature: 230 ℃, nine zone temperature: 230 ℃, head temperature: 200 ℃, melt temperature: at 220 ℃. The rotating speed of the main machine is 250r/min, and the rotating speed of the main feeding is 25 r/min.
in order to clearly show the outstanding performance effect of the composite materials obtained by the preparation method of the modified PA6 material in the above embodiment of the invention, comparative examples 1 and 2 are made as a control group in the embodiment, the preparation method of the composite materials related to comparative examples 1 and 2 is the same as that of examples 1-3, and the specific raw material ratio is shown in Table 1.
the products of examples 1 to 3 and comparative examples 1 to 2 were tested according to the national standard and the performance data are shown in table 2.
table 1 material compounding units of examples 1 to 3 of the present embodiment and comparative examples 1 to 2: kilogram (kilogram)
TABLE 2 Material Performance test data for examples 1-3 of the present example and comparative examples 1-2
Note: (Taber abrasion test conditions): grinding wheel type CS-10, weight mass 1000g, revolution 1000r, speed 72 rpm.
In the data, the tensile strength and the elongation at break are tested according to the national standard GB/T1040.2-2008; the bending strength and the bending modulus are tested according to the national standard GB/T9341-2008; testing the notch impact strength of the cantilever beam according to the national standard GB/T1843-2008; the melt flow rate was tested according to the national standard GB/T3682-2008. Heat aging resistance according to QC/T15-1992, which is stored in an environment of 70 + -2 deg.C for a long time, 200H or more, P represents pass; the xenon lamp ageing test was carried out in accordance with GB/T1865, P indicating pass.
As can be seen from examples 1-3 in Table 2, the PA6 material with low cost, high fluidity and wear resistance prepared by reasonably controlling the proportion and the components in the formula has good mechanical properties (tensile strength of 68.26-80.0MPa, bending strength of 84.35-92.5MPa and notch impact strength of 10.47-14.5KJ/m 2).
By comparing comparative example 1 with other examples, it can be seen that the abrasion, weather and chemical resistance properties of PA6 are further improved by the addition of UPE; comparing comparative example 2 with the other examples, it can be seen that the addition of LLDPE improves the toughness of the material. The application of the foaming agent enhances the interface interaction between the matrix and the substrate and improves the compatibility between the matrix and the substrate; the added lubricant has high thermal stability, high transparency, excellent dispersion performance and good weather resistance, and further solves the problem of uniformity of alloy materials. The defects of PA6 are improved well by combining the characteristics of all materials.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (9)
1. A low cost, high flow and abrasion resistant PA6 material, characterized in that the material comprises the following components in parts by weight: 50-90 parts of PA6 resin, 2-30 parts of toughening agent, 2-10 parts of LLDPE resin, 0.1-1 part of compatilizer, 0.2-2 parts of lubricant, 0.2-0.4 part of silane coupling agent and 0.2-0.4 part of antioxidant.
2. The low cost, high flow, and abrasion resistant PA6 material of claim 1, wherein: 70-90 parts of PA6 resin, 4-20 parts of toughening agent, 4-10 parts of LLDPE resin, 0.5-1 part of compatilizer, 0.5-2 parts of lubricant and 0.2-0.4 part of antioxidant.
3. The low cost, high flow, and abrasion resistant PA6 material of claim 2, wherein: the PA6 resin is a semitransparent or opaque milky white crystalline polymer, the density of the PA6 resin is 1.14-1.16 g/cm3, the melt index is 20-50 g/10min, and the heat deformation temperature is 50-70 ℃.
4. The low cost, high flow, and abrasion resistant PA6 material of claim 1, wherein: the toughening agent is ultra-high molecular weight polyethylene powder, namely UPE, the density of the toughening agent is 0.93-0.95 g/cm3, and the particle size of the toughening agent is 50-300 nm.
5. The low cost, high flow, and abrasion resistant PA6 material of claim 1, wherein: the silane coupling agent is vinyl siloxane and allyl siloxane.
6. The low cost, high flow, and abrasion resistant PA6 material of claim 1, wherein: the LLDPE resin is linear low-density polyethylene resin, is non-toxic, tasteless and odorless milky white particles, has the density of 0.918-0.935 g/cm3, and has the melt index of 1.7-2.3 g/10 min.
7. the low cost, high flow, and abrasion resistant PA6 material of claim 1, wherein: the compatilizer is a heat absorption closed-cell type chemical nucleation foaming agent, gas generated by heat dispersion is carbon dioxide, and the content of the carbon dioxide is 80-85 ml/gram.
8. The low cost, high flow, and abrasion resistant PA6 material of claim 1, wherein: the lubricant is nano-synthesized magnesium-aluminum talc with a powder structure, the magnesium-aluminum ratio of the lubricant is 2:1, the average particle size is less than 80 mu m, the whiteness is 92, and the specific gravity is 2.1 g/ml.
9. A method for preparing a low-cost, high-flow and abrasion-resistant PA6 material, comprising the steps of:
Step 1: weighing UPE resin, a lubricant, an antioxidant, a foaming agent, a lubricant and a coupling agent in proportion, stirring for 3-10 minutes by a mixer, and taking out for later use;
Step 2: the PA6, LLDPE and activated powder resin are weighed according to a proportion, mixed by a high-speed mixer for 3-6 minutes, and uniformly mixed to form a premix.
And step 3: the premix is prepared by a melt blending method through a double-screw extruder, wherein the heating temperature is 190-230 ℃, and the extrusion temperature of a machine head is 180-200 ℃; the rotating speed of the main machine screw is 200-400 r/min, and the feeding rotating speed is 25-35 r/min.
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| CN115260726A (en) * | 2021-04-29 | 2022-11-01 | 广州视源电子科技股份有限公司 | High-gloss low-odor wear-resistant PC/ABS/PMMA alloy material and preparation method thereof |
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Application publication date: 20191210 |