CN111849152B - Polyamide composite material and preparation method and application thereof - Google Patents
Polyamide composite material and preparation method and application thereof Download PDFInfo
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- CN111849152B CN111849152B CN202010603901.5A CN202010603901A CN111849152B CN 111849152 B CN111849152 B CN 111849152B CN 202010603901 A CN202010603901 A CN 202010603901A CN 111849152 B CN111849152 B CN 111849152B
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- 229920002647 polyamide Polymers 0.000 title claims abstract description 153
- 239000004952 Polyamide Substances 0.000 title claims abstract description 152
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 45
- 239000011777 magnesium Substances 0.000 claims abstract description 45
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 43
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002699 waste material Substances 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims description 45
- 230000029087 digestion Effects 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 229920006659 PA12 Polymers 0.000 claims description 13
- -1 magnesium fatty acid Chemical class 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000120 microwave digestion Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920006119 nylon 10T Polymers 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011654 magnesium acetate Substances 0.000 claims description 5
- 229940069446 magnesium acetate Drugs 0.000 claims description 5
- 235000011285 magnesium acetate Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 4
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 4
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 4
- VCZQCLHBLSUGML-UHFFFAOYSA-K aluminum octacosanoate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O VCZQCLHBLSUGML-UHFFFAOYSA-K 0.000 claims description 4
- 229940063655 aluminum stearate Drugs 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 3
- 238000009616 inductively coupled plasma Methods 0.000 claims description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 3
- 235000019359 magnesium stearate Nutrition 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229920006152 PA1010 Polymers 0.000 claims description 2
- 229920006153 PA4T Polymers 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- ATYSJAJVVFHRKR-UHFFFAOYSA-L magnesium octacosanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O ATYSJAJVVFHRKR-UHFFFAOYSA-L 0.000 claims description 2
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 claims description 2
- 229920006396 polyamide 1012 Polymers 0.000 claims description 2
- 229920006024 semi-aromatic copolyamide Polymers 0.000 claims description 2
- 238000003466 welding Methods 0.000 abstract description 27
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000049 pigment Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- PVKRXBGSDHHPGS-UHFFFAOYSA-L C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3].C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3] Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3].C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3] PVKRXBGSDHHPGS-UHFFFAOYSA-L 0.000 description 1
- BIVQBWSIGJFXLF-UHFFFAOYSA-N PPM-18 Chemical compound C=1C(=O)C2=CC=CC=C2C(=O)C=1NC(=O)C1=CC=CC=C1 BIVQBWSIGJFXLF-UHFFFAOYSA-N 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- VZMQWZVOXMCQKY-UHFFFAOYSA-L dimagnesium;octadecanoate Chemical compound [Mg+2].[Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VZMQWZVOXMCQKY-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention provides a polyamide composite material, which is characterized in that a polyamide resin matrix contains a certain amount of magnesium element and aluminum element by adding a magnesium-containing organic salt and an aluminum-containing organic salt, so that the laser welding performance of a workpiece can be improved. The invention provides two preparation methods simultaneously, and discloses a method which can be used for recycling polyamide waste materials simultaneously and improves the utilization value of the recycled polyamide obtained by extracting the polyamide waste materials.
Description
Technical Field
The invention relates to the technical field of green high polymer materials, in particular to a polyamide composite material and a preparation method and application thereof.
Background
In the field of automobile industry, polyamide materials are also widely used for interior and exterior trim parts, functional parts and structural parts. The trend of light weight as automobile materials is that more and more plastic parts are also appeared on parts under automobile engine hoods. In order to obtain automobile parts with high structural strength, the conventional polyamide composite material for the automobile mostly adopts a laser welding mode, and the obtained parts have small seams, high strength and long service life. Meanwhile, due to the continuous development of economy, the used polyamide waste is generally directly discarded as garbage, and the waste is huge in quantity, so that energy waste and environmental pollution are caused. Therefore, a problem of recycling of the recovered polyamide has been proposed worldwide.
Nowadays, in order to obtain a part with high structural strength, a polyamide composite material is mostly welded by laser, and the obtained part has fine joint, high strength and long service life. Laser welded parts typically include upper and lower body portions, the upper body being required to transmit laser light to the interface of the upper and lower bodies, and the lower body being required to absorb laser light to convert the light source into heat energy, typically by selecting a pigment that is capable of transmitting or absorbing laser light to achieve the function of laser welding the upper and lower bodies. However, it has been found that the polyamide resin obtained by recycling is subjected to laser welding with a primary-color sample after adding a special pigment for laser welding, and the weld strength and the weld appearance are not satisfactory.
According to the welding effect, the laser welding has the defects that: 1) weak welding strength; 2) an undesirable appearance. The reasons for weakening the weld strength are: the thickness of the laser transmission part is too high or the laser transmittance is not good, so that the laser energy cannot fully reach a welding interface; the resin interface which is not sufficiently melted and joined is present at the joint, and heat and mass conduction occurs, or a gas-forming cavity which is decomposed by laser ablation is present at the joint. Moreover, by laser welding, flash can also occur: the reason for flash is several: 1, the material has too high fluidity and low melting point or plasticizing temperature, namely the material is easy to overflow; 2. the material is decomposed to generate gas to push the molten part to overflow; 3. the generation of the 1 st and 2 nd spots is promoted because of high transmittance or high capability of inputting laser by equipment.
At the present stage, researchers mainly focus on the aspects of high temperature resistance, fluidity improvement and flame retardance improvement on the influence of trace elements in the polyamide composite material on the material performance, and do not examine the influence of the content of the trace elements on the laser welding performance of the polyamide. For example, European patent EP0862595B1 discloses a polyamide composition in which the melt viscosity can be reduced by adding 0.05 to 5% by weight of a magnesium salt (example magnesium acetate) and the resin is selected from the group consisting of PA 66: the impact strength is improved when PA6 is 1 to 40. Japanese patent JP0853618A discloses a flame-retardant polyamide, which is capable of suppressing the problems of gas, foaming and coloring caused by the decomposition of a flame retardant by adding a certain amount of magnesium aluminum salt into a bromine-antimony flame-retardant system, and improving the heat resistance to the flame retardancy.
Disclosure of Invention
The invention aims to provide a polyamide composite material, which contains 20-150ppm of magnesium element and 60-300ppm of aluminum element. The existence of the magnesium element and the aluminum element can improve the laser welding performance of the polyamide composite material.
Another object of the present invention is to provide a method for producing the above polyamide composite material and use thereof.
The invention is realized by the following technical scheme:
a polyamide composite material comprises polyamide resin, and based on the total weight of the polyamide composite material, the polyamide composite material contains 20-150ppm of magnesium element and 60-300ppm of aluminum element, wherein the magnesium element is derived from magnesium-containing organic salt, and the aluminum element is derived from aluminum-containing organic salt.
Preferably, the content of the magnesium element is 60-120ppm, and the content of the aluminum element is 80-190 ppm.
More preferably, the content of the magnesium element is 70-100ppm, and the content of the aluminum element is 100-160 ppm.
The method for testing the content of the magnesium element and the aluminum element comprises the following steps: ICP-OES, specifically, after completely dissolving a polyamide composite material by using a solvent, filtering by using a filter screen with the aperture less than or equal to 50 microns, and adding the filtered polyamide solution into deionized water to precipitate a solid sample; processing the sample into a fine strip shape or a powder shape with the diameter not more than 2mm and the length not more than 5mm by using crushing equipment, and uniformly mixing; taking a sample of 0.1 +/-0.005 g (accurate to 0.001 g), putting the sample into a microwave digestion tank, adding 8 mL of digestion acid (concentrated nitric acid) into the digestion tank in a chemical fume hood to enable the digestion tank to be completely immersed in the sample, slowly adding 2 mL of hydrogen peroxide, reacting the sample for 1-2 min, covering a cover, sealing the digestion tank, and putting the digestion tank into a microwave digestion furnace for digestion; after digestion is completed, taking out the digestion tank, cooling to room temperature, transferring the solution in the microwave digestion tank into a volumetric flask by using a 0.45 um filter membrane, washing the microwave digestion tank for multiple times by using a proper amount of distilled water, transferring the washing liquid into the volumetric flask, diluting the solution to a scale mark (50 mL) by using the distilled water, shaking up and waiting for measurement; and transferring the digestion solution to a pipe to be tested after the digestion solution is subjected to constant volume, and measuring by using an inductively coupled plasma atomic emission spectrometer.
The magnesium-containing organic salt is selected from at least one of magnesium acetate and magnesium fatty acid, and the magnesium fatty acid is selected from at least one of magnesium stearate and magnesium montanate; the aluminum-containing organic salt is selected from at least one of aluminum acetate and fatty acid aluminum, and the fatty acid aluminum is selected from at least one of aluminum stearate and aluminum montanate.
The polyamide is selected from one or more of aliphatic polyamide, semi-aromatic polyamide and copolyamide; the aliphatic polyamide is selected from at least one of PA6, PA66, PA46, PA56, PA12, PA1010, PA1012 and PA1212, the semi-aromatic polyamide is selected from at least one of PA4T, PA6T, PA9T and PA10T, and the copolyamide is selected from at least one of PA10T1010, PA6T610 and PA10T 1012.
The preparation method of the polyamide composite material comprises the following two steps:
the first method comprises the following steps: adding a polyamide-containing raw material (at least one of polyamide waste, polyamide reclaimed materials and polyamide new materials) into a compound solvent, heating to 50 ℃ to the reflux temperature of the solution, stirring until the solution is dissolved, adding a magnesium-containing organic salt and an aluminum-containing organic salt according to the designed content of magnesium/aluminum elements, stirring for dissolving, and filtering to obtain a polyamide solution; adding the polyamide solution into deionized water, and separating liquid to obtain a polyamide composite material; the compound solvent comprises, by weight, 10-30 parts of phenol and 15-40 parts of toluene; the weight ratio of the polyamide-containing raw material to the compound solvent is 1:10-1: 2.
When polyamide-containing raw materials are polyamide waste materials and polyamide reclaimed materials, the method further comprises a decoloring step, wherein before the polyamide solution is added into deionized water, a decoloring agent is added, the solution is heated to 50 ℃ until the reflux temperature of the solution is kept for 0.5-2 hours, and then the solution is cooled to be lower than 50 ℃ and then filtered (the decoloring agent comprises at least one of activated clay and activated carbon, and the weight ratio of the decoloring agent to the polyamide waste materials is (1: 8) - (1: 12)).
The polyamide is at least one of polyamide waste material, polyamide reclaimed material and polyamide new material. The novel polyamide material is newly synthesized, and contains more than or equal to 99wt% of polyamide resin; the polyamide reclaimed material is polyamide obtained by treating polyamide waste through a recovery process, and contains more than or equal to 99wt% of polyamide resin; the polyamide waste is discarded polyamide articles, wherein the polyamide resin content is in the range of 25-90 wt%.
And the second method comprises the following steps: the method comprises the following steps: according to the designed content of magnesium/aluminum elements, a polyamide-containing raw material (at least one of polyamide waste, polyamide reclaimed materials and polyamide new materials), a magnesium-containing organic salt and an aluminum-containing organic salt are uniformly mixed, and then are extruded and granulated through a double-screw extruder to obtain the polyamide composite material, wherein the temperature range of a screw is 20-30 ℃ higher than the melting point of polyamide resin, and the length-diameter ratio of the screw is 40: 1-52: 1. The polyamide is at least one of polyamide waste material, polyamide reclaimed material and polyamide new material. The novel polyamide material is newly synthesized, and contains more than or equal to 99wt% of polyamide resin; the polyamide reclaimed material is polyamide obtained by treating polyamide waste through a recovery process, and contains more than or equal to 99wt% of polyamide resin; the polyamide waste is discarded polyamide articles, wherein the polyamide resin content is in the range of 25-90 wt%.
The polyamide composite material prepared by the invention is applied to preparing laser welding parts. The laser part comprises an upper body part which can allow laser to penetrate and reach the lower body interface, and the lower body part is required to absorb the laser and convert a light source into heat energy.
The lower part of the workpiece contains laser absorption pigment, and the laser absorption pigment can convert light energy into heat energy to achieve the effect of welding the upper part and the lower part.
The invention has the following beneficial effects
According to the invention, a certain amount of aluminum-containing organic salt and magnesium-containing organic salt are added into the polyamide composite material, so that the content of aluminum element and magnesium element is controlled, and the laser welding performance of the polyamide composite material can be improved. The invention provides two preparation methods simultaneously, wherein the method can recover and obtain the polyamide reclaimed material from the polyamide waste and control the content of magnesium/aluminum elements in the resin matrix of the polyamide reclaimed material, and improves the utilization value of the polyamide waste.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the invention are as follows:
PA12 waste: recycled materials from water heating pipelines, automobile engine peripheral parts and the like contain a small amount of toner, and the content of PA12 is about 95-97% theoretically.
PA66 waste: recycled materials from parts such as gears and bearings in mechanical equipment contain glass fiber reinforcement, and theoretically, the content of PA66 is about 65% -70%.
PA10T waste: recycled material from engine peripheral components, containing glass fiber reinforcement, theoretically having a PA10T content of 60-70%.
PA12 New Material: arkema, P201 TL;
PA12 reclaimed material: self-making, namely crushing the polyamide waste PA12, adding a compound solvent (the weight ratio of phenol to toluene =1: 1) which is 3 times of the weight of the polyamide waste, heating to 80 ℃, stirring for dissolving, cooling to 30 ℃, and filtering to obtain a polyamide solution; and adding the polyamide solution into deionized water, and separating liquid to obtain a PA12 reclaimed material.
Phenol: commercially pure, commercially available;
toluene: commercially pure, commercially available;
magnesium chloride: 40-50 micron particle size, and sieving.
Magnesium stearate: it is commercially available.
Aluminum stearate: it is commercially available.
Aluminum hypophosphite: 40-50 micron particle size, and sieving.
Magnesium acetate: it is commercially available.
Aluminum montanate: it is commercially available.
Black pigment: carbon black, Raven M, available from BIRLA;
method for testing various performances
(1) And (3) testing the laser welding performance: molding the material into a sample bar having dimensions of 2X 13X 120mm, superposing a natural-color upper body and a black lower body in the thickness direction of 2mm on a laser welding sample stage to ensure that the overall length of the sample bar superposed in the longitudinal direction is about 160mm, and welding the superposed portions in the width direction using a laser having a power of 20W to form 5 parallel weld lines. And calculating the welding combination area according to the theoretical radius of the laser. The welded sample strips were stored at 25 ℃ and 50% relative humidity for 24 hours and then subjected to tensile test using a universal tester at a beam speed of 5 mm/min. The measured strength is the weld strength in units: MPa.
(2) Evaluation of welding appearance: due to the adoption of the air pump clamp, the sample expanded after laser melting is easily extruded out of the gap between the upper body and the lower body of the welded sample strip, and flash is formed. And (3) evaluating the flash condition, judging the grade according to the diameter of any dimension of the flash by grade judgment, wherein the grade of no flash is 1, the grade of d which is more than 0mm and less than or equal to 0.5mm is 2, the grade of d which is more than 0.5mm and less than or equal to 1mm is 3, the grade of d which is more than 1mm and less than or equal to 1.5mm is 4, and the grade of d which is more than 1.5mm and less than or equal to 5.
(3) And (3) testing the content of magnesium aluminum element: ICP-OES, specifically, after completely dissolving a polyamide composite material by using a solvent, filtering by using a filter screen with the aperture of 50 microns, and adding the filtered polyamide solution into deionized water to precipitate a solid sample; processing the sample into a fine strip shape or a powder shape with the diameter not more than 2mm and the length not more than 5mm by using crushing equipment, and uniformly mixing; taking a sample of 0.1 +/-0.005 g (accurate to 0.001 g), putting the sample into a microwave digestion tank, adding 8 mL of digestion acid (concentrated nitric acid) into the digestion tank in a chemical fume hood to enable the digestion tank to be completely immersed in the sample, slowly adding 2 mL of hydrogen peroxide, reacting the sample for 1-2 min, covering a cover, sealing the digestion tank, and putting the digestion tank into a microwave digestion furnace for digestion; after digestion is completed, taking out the digestion tank, cooling to room temperature, transferring the solution in the microwave digestion tank into a volumetric flask by using a 0.45 um filter membrane, washing the microwave digestion tank for multiple times by using a proper amount of distilled water, transferring the washing liquid into the volumetric flask, diluting the solution to a scale mark (50 mL) by using the distilled water, shaking up and waiting for measurement; and transferring the digestion solution to a pipe to be tested after the digestion solution is subjected to constant volume, and measuring by using an inductively coupled plasma atomic emission spectrometer.
According to the laser welding comparison, after the black sample strip and the original color sample strip are subjected to laser welding, corresponding evaluation tests are carried out. In the following examples and comparative examples, the formulation of the laser-welded bars, the black bars, differed from the primary color bars only in whether or not black pigment was added. The formulations of the black bars are given in the following table.
Preparation of polyamide composite material:
preparation of polyamide composites for examples 1-7 and comparative examples 1-5: adding 100g of polyamide raw material (PA 12 waste in examples 1-4, PA12 reclaimed material in example 5, PA66 waste in example 6, PA10T waste in example 7 and PA12 waste in comparative examples 1-5) into 100g of phenol/200 g of toluene compound solvent, heating to 100 ℃, stirring until the mixture is dissolved, adding aluminum-containing organic salt and magnesium-containing organic salt according to the set amount of magnesium-aluminum element, adding 10g of activated carbon, keeping the temperature, stirring for 1 hour, cooling to below 50 ℃, and filtering to obtain a polyamide solution; and adding the polyamide solution into 5000g of deionized water, precipitating the polyamide in the deionized water to obtain a solid, and separating to obtain the polyamide composite material.
Example 8: adding 100g of PA12 new material into 100g of phenol/200 g of toluene compound solvent, heating to 100 ℃, stirring until the mixture is dissolved, adding aluminum-containing organic salt and magnesium-containing organic salt according to the set amount of magnesium-aluminum element, cooling to below 50 ℃, and filtering to obtain polyamide solution; and adding the polyamide solution into 5000g of deionized water, precipitating the polyamide in the deionized water to obtain a solid, and separating to obtain the polyamide composite material.
Examples 9-11 and comparative example 6: according to the set content of magnesium and aluminum elements, polyamide-containing raw materials (PA 12 waste materials in example 9 and comparative example 6, PA12 reclaimed materials in example 10 and PA12 fresh materials in example 11), magnesium-containing organic salt and aluminum-containing organic salt (magnesium chloride and aluminum hypophosphite in comparative example 6) are uniformly mixed and extruded and granulated through a double-screw extruder to obtain the polyamide composite material, wherein the temperature range of a screw is 240-260 ℃, and the length-diameter ratio of the screw is 44: 1.
Preparation of laser-welded black bars: and (3) uniformly mixing 99.7 parts of the polyamide composite material and 0.3 part of black pigment through a double-screw extruder, extruding and granulating, and then testing the content of magnesium and aluminum elements and the laser welding performance according to the testing method.
Table 1: examples and comparative examples polyamide composite materials magnesium aluminum content and results of laser welding performance test after preparation of laser welded sample strips
| Example 12 | Example 13 | Example 14 | Example 15 | Example 16 | Example 17 | |
| Polyamide composite material source | Example 1 | Practice ofExample 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Magnesium element, ppm | 35 | 121 | 80 | 65 | 102 | 85 |
| Source of magnesium element | Magnesium acetate | Magnesium acetate | Magnesium acetate | Magnesium acetate | Magnesium stearate | Magnesium acetate |
| Aluminum element, ppm | 70 | 230 | 150 | 106 | 145 | 113 |
| Source of aluminum element | Aluminum stearate | Aluminum stearate | Aluminum stearate | Aluminum stearate | Aluminum stearate/brown colorAluminum coalite | Aluminum montanate |
| Welding strength (MPa) | 66.3 | 66.9 | 74.1 | 71.6 | 71.3 | 76.4 |
| Degree of weld appearance flash | 3 | 3 | 1 | 2 | 2 | 1 |
TABLE 1
| Example 18 | Example 19 | Example 20 | Example 21 | Example 22 | |
| Polyamide composite material source | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 |
| Magnesium element, ppm | 97 | 40 | 65 | 110 | 68 |
| Source of magnesium element | Magnesium stearate | Magnesium acetate | Magnesium acetate | Magnesium acetate | Magnesium acetate |
| Aluminum element, ppm | 150 | 83 | 170 | 93 | 87 |
| Source of aluminum element | Aluminum stearate | Aluminum stearate | Aluminum stearate | Aluminum stearate | Aluminum stearate |
| Welding strength (MPa) | 75.2 | 67.9 | 70.9 | 71.2 | 71.5 |
| Degree of weld appearance flash | 1 | 3 | 2 | 2 | 2 |
As can be seen from examples 12 to 18 and comparative examples 7 to 11, the laser weldability of the polyamide composite material can be improved by adding a certain amount of the organic salt containing magnesium and the organic salt containing aluminum. The content of the magnesium-aluminum element falls in a further preferable range, so that the improvement effect is better.
From example 15/20/21/22, it can be seen that the laser weldability was improved by using the polyamide composite material obtained by the two production methods.
TABLE 1
| Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 | Comparative example 12 | |
| Polyamide composite material source | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Magnesium element, ppm | 18 | 74 | 5 | 5 | 420 | 45 |
| Source of magnesium element | Magnesium stearate | Magnesium stearate | N/A | N/A | Magnesium stearate | Magnesium chloride |
| Aluminum element, ppm | 53 | 6 | 68 | 482 | 6 | 78 |
| Source of aluminum element | Aluminum stearate | N/A | Aluminum stearate | Aluminum stearate | N/A | Aluminum hypophosphite |
| Welding strength (MPa) | 59.1 | 58.7 | 58.3 | 56.7 | 57.1 | 59.7 |
| Degree of weld appearance flash | 4 | 5 | 5 | 5 | 5 | 5 |
Claims (12)
1. A polyamide composite material, characterized by comprising a polyamide resin and containing 20-150ppm of magnesium element and 60-300ppm of aluminum element based on the total weight of the polyamide composite material, wherein the magnesium element is derived from a magnesium-containing organic salt, and the aluminum element is derived from an aluminum-containing organic salt.
2. The polyamide composite material according to claim 1, wherein the magnesium element is contained in an amount of 60 to 120ppm and the aluminum element is contained in an amount of 80 to 190ppm, based on the total weight of the polyamide composite material.
3. The polyamide composite material as claimed in claim 2, wherein the magnesium element is in a range of 70 to 100ppm and the aluminum element is in a range of 100 to 160ppm, based on the total weight of the polyamide composite material.
4. The polyamide composite material as claimed in any one of claims 1 to 3, wherein the contents of the magnesium element and the aluminum element in a certain weight are measured by the following method: ICP-OES, specifically, after completely dissolving a polyamide composite material by using a solvent, filtering by using a filter screen with the aperture less than or equal to 50 microns, and adding the filtered polyamide solution into deionized water to precipitate a solid sample; processing the sample into a fine strip shape or a powder shape with the diameter not more than 2mm and the length not more than 5mm by using crushing equipment, and uniformly mixing; taking a 0.1 +/-0.005 g sample, putting the sample into a microwave digestion tank, adding 8 mL of concentrated nitric acid into the digestion tank in a chemical fume hood to enable the digestion tank to be completely immersed in the sample, slowly adding 2 mL of hydrogen peroxide to enable the sample to react for 1-2 min, covering a cover, sealing the digestion tank, and putting the digestion tank into a microwave digestion furnace for digestion; after digestion is completed, taking out the digestion tank, cooling to room temperature, transferring the solution in the microwave digestion tank into a 50mL volumetric flask by using a 0.45-micrometer filter membrane, washing the microwave digestion tank for multiple times by using a proper amount of distilled water, transferring the washing liquid into the volumetric flask, diluting the solution to a scale mark by using the distilled water, shaking up and measuring; and transferring the digestion solution to a pipe to be tested after the digestion solution is subjected to constant volume, and measuring by using an inductively coupled plasma atomic emission spectrometer.
5. The polyamide composite material according to any one of claims 1 to 3, wherein the magnesium-containing organic salt is at least one selected from magnesium acetate and magnesium fatty acid, and the magnesium fatty acid is at least one selected from magnesium stearate and magnesium montanate; the aluminum-containing organic salt is selected from at least one of aluminum acetate and fatty acid aluminum, and the fatty acid aluminum is selected from at least one of aluminum stearate and aluminum montanate.
6. The polyamide composite material as claimed in any one of claims 1 to 3, wherein the polyamide resin is one or more selected from aliphatic polyamide, semi-aromatic polyamide and copolyamide; the aliphatic polyamide is selected from at least one of PA6, PA66, PA46, PA56, PA12, PA1010, PA1012 and PA1212, the semi-aromatic polyamide is selected from at least one of PA4T, PA6T, PA9T and PA10T, and the copolyamide is selected from at least one of PA10T1010, PA6T610 and PA10T 1012.
7. Process for the preparation of a polyamide composite material according to any one of claims 1 to 6, characterized in that it comprises the following steps: adding a polyamide-containing raw material into a compound solvent, heating to 50 ℃ to the reflux temperature of the solution, stirring until the solution is dissolved, adding a magnesium-containing organic salt and an aluminum-containing organic salt according to the designed content of magnesium/aluminum elements, stirring for dissolving, and filtering to obtain a polyamide solution; adding the polyamide solution into deionized water, and separating liquid to obtain a polyamide composite material; the compound solvent comprises, by weight, 10-30 parts of phenol and 15-40 parts of toluene; the weight ratio of the polyamide-containing raw material to the compound solvent is 1:10-1: 2;
the polyamide-containing raw material is selected from at least one of polyamide waste material, polyamide reclaimed material and polyamide new material.
8. The preparation method of the polyamide composite material as claimed in claim 7, wherein when the polyamide-containing raw material is polyamide waste and polyamide reclaimed material, the preparation method further comprises a decoloring step, wherein before the polyamide solution is added into deionized water, a decoloring agent is added, the solution is heated to 50 ℃ until the reflux temperature of the solution is kept for 0.5-2 hours, and then the solution is cooled to below 50 ℃ and then filtered, wherein the decoloring agent comprises at least one of activated clay and activated carbon, and the weight ratio of the decoloring agent to the polyamide waste is (1: 8) - (1: 12).
9. The method for preparing a polyamide composite material according to claim 7 or 8, wherein the polyamide resin is derived from at least one of a polyamide waste material, a polyamide reclaimed material, and a polyamide virgin material; the novel polyamide material is newly synthesized, and contains more than or equal to 99wt% of polyamide resin; the polyamide reclaimed material is polyamide obtained by treating polyamide waste through a recovery process, and contains more than or equal to 99wt% of polyamide resin; the polyamide waste is discarded polyamide articles, wherein the polyamide resin content is in the range of 25-90 wt%.
10. Process for the preparation of a polyamide composite material according to any one of claims 1 to 6, characterized in that it comprises the following steps: uniformly mixing a polyamide-containing raw material, a magnesium-containing organic salt and an aluminum-containing organic salt according to the designed content of magnesium/aluminum elements, and then extruding and granulating through a double-screw extruder to obtain a polyamide composite material, wherein the temperature range of a screw is 20-30 ℃ higher than the melting point of polyamide resin, and the length-diameter ratio of the screw is 40: 1-52: 1;
the polyamide-containing raw material is selected from at least one of polyamide waste material, polyamide reclaimed material and polyamide new material.
11. The method for preparing a polyamide composite material according to claim 10, wherein the polyamide resin is derived from at least one of a polyamide waste material, a polyamide reclaimed material, and a polyamide virgin material; the novel polyamide material is newly synthesized, and contains more than or equal to 99wt% of polyamide resin; the polyamide reclaimed material is polyamide obtained by treating polyamide waste through a recovery process, and contains more than or equal to 99wt% of polyamide resin; the polyamide waste is discarded polyamide articles, wherein the polyamide resin content is in the range of 25-90 wt%.
12. Use of the polyamide composite material according to any one of claims 1 to 6 for the preparation of laser welded articles.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0853618A (en) * | 1995-03-31 | 1996-02-27 | Toray Ind Inc | Flame-retardant polyamide resin composition |
| CN101175821A (en) * | 2005-05-16 | 2008-05-07 | 三井化学株式会社 | Flame retardant polyamide composition |
| CN103665844A (en) * | 2013-11-29 | 2014-03-26 | 天津金发新材料有限公司 | High-welding-performance glass fiber reinforced polyamide composite material as well as preparation method and application thereof |
| CN107057349A (en) * | 2017-05-17 | 2017-08-18 | 江苏金发科技新材料有限公司 | Can laser welding polyamide compoiste material |
| CN109401315A (en) * | 2018-05-22 | 2019-03-01 | 宁波聚特普新材料有限公司 | A kind of lithium ion battery is with can laser welding poly arylidene thio-ester material and preparation method |
| CN109401219A (en) * | 2018-05-22 | 2019-03-01 | 宁波聚特普新材料有限公司 | A kind of polyester composite and preparation method thereof for laser welding |
| CN109679339A (en) * | 2018-12-27 | 2019-04-26 | 会通新材料(上海)有限公司 | A kind of improvement release property and 56 composition of polyamide flexible and its application |
| CN109735099A (en) * | 2018-12-27 | 2019-05-10 | 会通新材料(上海)有限公司 | It is a kind of improve light aging resisting characteristic 56 composition of polyamide and its application |
| CN110951250A (en) * | 2014-05-30 | 2020-04-03 | 奥升德高性能材料公司 | Low-phosphorus low-color polyamide |
| CN111040443A (en) * | 2019-12-27 | 2020-04-21 | 湖南华曙高科技有限责任公司 | Polyamide powder material for selective laser sintering and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5272337B2 (en) * | 2006-06-22 | 2013-08-28 | 東レ株式会社 | Thermoplastic resin composition for long object fixing jig and method for producing the same |
| WO2009151145A1 (en) * | 2008-06-10 | 2009-12-17 | 宇部興産株式会社 | Novel polyamide resin composition and polyamide resin-containing product |
| CN107163571B (en) * | 2017-05-17 | 2019-11-22 | 江苏金发科技新材料有限公司 | Laser welding long-life flat fiber modified polyamide composite material |
| CN111117235A (en) * | 2019-12-31 | 2020-05-08 | 会通新材料(上海)有限公司 | Polyamide 56 composition for increasing laser transmissivity and application thereof |
| CN111849152B (en) * | 2020-06-29 | 2022-02-18 | 金发科技股份有限公司 | Polyamide composite material and preparation method and application thereof |
-
2020
- 2020-06-29 CN CN202010603901.5A patent/CN111849152B/en active Active
- 2020-12-29 WO PCT/CN2020/140813 patent/WO2022001055A1/en active Application Filing
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0853618A (en) * | 1995-03-31 | 1996-02-27 | Toray Ind Inc | Flame-retardant polyamide resin composition |
| CN101175821A (en) * | 2005-05-16 | 2008-05-07 | 三井化学株式会社 | Flame retardant polyamide composition |
| CN103665844A (en) * | 2013-11-29 | 2014-03-26 | 天津金发新材料有限公司 | High-welding-performance glass fiber reinforced polyamide composite material as well as preparation method and application thereof |
| CN110951250A (en) * | 2014-05-30 | 2020-04-03 | 奥升德高性能材料公司 | Low-phosphorus low-color polyamide |
| CN107057349A (en) * | 2017-05-17 | 2017-08-18 | 江苏金发科技新材料有限公司 | Can laser welding polyamide compoiste material |
| CN109401315A (en) * | 2018-05-22 | 2019-03-01 | 宁波聚特普新材料有限公司 | A kind of lithium ion battery is with can laser welding poly arylidene thio-ester material and preparation method |
| CN109401219A (en) * | 2018-05-22 | 2019-03-01 | 宁波聚特普新材料有限公司 | A kind of polyester composite and preparation method thereof for laser welding |
| CN109679339A (en) * | 2018-12-27 | 2019-04-26 | 会通新材料(上海)有限公司 | A kind of improvement release property and 56 composition of polyamide flexible and its application |
| CN109735099A (en) * | 2018-12-27 | 2019-05-10 | 会通新材料(上海)有限公司 | It is a kind of improve light aging resisting characteristic 56 composition of polyamide and its application |
| CN111040443A (en) * | 2019-12-27 | 2020-04-21 | 湖南华曙高科技有限责任公司 | Polyamide powder material for selective laser sintering and preparation method thereof |
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