CN114410059A - High-strength polyformaldehyde and preparation method thereof - Google Patents
High-strength polyformaldehyde and preparation method thereof Download PDFInfo
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- CN114410059A CN114410059A CN202210103647.1A CN202210103647A CN114410059A CN 114410059 A CN114410059 A CN 114410059A CN 202210103647 A CN202210103647 A CN 202210103647A CN 114410059 A CN114410059 A CN 114410059A
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The invention belongs to the field of high polymer material processing, and discloses a highly reinforced polyformaldehyde and a preparation method thereof.
Description
Technical Field
The invention belongs to the field of processing of high molecular materials, relates to a high molecular polymer, and particularly relates to a high-strength polyformaldehyde and a preparation method thereof.
Background
Polyformaldehyde (POM) is thermoplastic engineering plastic which takes [ -CH2-O- ] as a main chain, has no branching, high melting point, high density and high crystallization, has excellent mechanical property, creep resistance, fatigue resistance, wear-resisting self-lubricating property, chemical resistance and the like, is the closest metal variety in the engineering plastic, can replace nonferrous metals such as copper, aluminum, zinc and the like and alloy products, and is widely applied to the fields of electronics, electricity, automobiles, light industry, machinery, chemical industry, building materials and the like.
However, the application field of polyformaldehyde is limited due to high crystallinity, large notch sensitivity, easy residual internal stress of products and insufficient strength and toughness, and the strength, rigidity, dimensional stability and creep resistance of polyformaldehyde are further improved after the polyformaldehyde is modified by glass fibers.
Leaf shujin, application of engineering plastics, 2011, 39 (8): 52-55, researching the influence of the viscosity of polyformaldehyde and the type and content of the glass fiber exposure preventing agent, and the injection molding process on the surface gloss and the mechanical property of the polyformaldehyde composite material, and showing that the surface gloss of a polyformaldehyde composite material product is gradually increased along with the reduction of the viscosity of polyformaldehyde, the increase of the content of the glass fiber exposure preventing agent, the increase of the injection speed, the pressure and the mold temperature; with the increase of the content of the glass fiber exposure preventing agent, the mechanical property of the polyformaldehyde composite material gradually rises.
Liuyu, plastics industry, 2019, 47 (9): 56-59, optimally designing the processing process conditions of the glass fiber reinforced polyformaldehyde through an orthogonal experiment, and determining four processing process parameters of optimal screw combination, extrusion temperature, screw rotating speed and feeding speed so as to obtain the high-performance glass fiber reinforced polyformaldehyde composite material.
Crisis, school, etc. [ plastics ], 2014, 43 (2): 23-25, preparing the long glass fiber reinforced polyformaldehyde composite material by adopting a melt impregnation process, and researching the influence of different glass fiber contents on the mechanical properties and the forms of the polyformaldehyde composite material, wherein the results show that the mechanical properties of the long glass fiber reinforced polyformaldehyde composite material are increased along with the increase of the glass fiber content, and the glass fibers have good dispersibility in matrix resin. As an inorganic fiber material, glass fibers have smooth surfaces, few active functional groups and low reaction activity, are difficult to form strong interface interaction with a polyformaldehyde resin matrix, and are easy to generate interface debonding, and most researches do not perform effective surface functionalization treatment on the glass fibers according to the molecular characteristics of matrix resin, so that the interface interaction of a composite system is weak, the dispersibility is poor, and the mechanical property is not improved remarkably.
Disclosure of Invention
In order to improve the mechanical property of polyformaldehyde, the invention provides a highly-enhanced polyformaldehyde and a preparation method thereof, which are urgently required for the practical application of the enhanced polyformaldehyde, and are characterized in that: the method is characterized in that the strong adhesion property of polydopamine is utilized, the polydopamine is used as a bridging molecule to bond low-dimensional carbon nanoparticles such as graphene and carbon nanotubes on the surface of glass fiber, so that the carbon nanoparticles @ PDA @ glass fiber hybrid filler is obtained, the roughness of the surface of the glass fiber is increased, a strong mechanical/chemical meshing effect is formed between the glass fiber and a polyformaldehyde matrix, a multistage reinforcing structure of the polyformaldehyde matrix-fiber interface is constructed, the interface strength and the interface stress transfer capacity of the material are remarkably improved, the efficient reinforcing effect of the hybrid filler on polyformaldehyde is exerted, and the mechanical strength and the modulus of the hybrid filler are greatly improved.
The aim of the invention is achieved by the following technical measures, wherein the raw material fractions are parts by weight except for special specifications.
The high-reinforcement polyformaldehyde is formed by compounding polyformaldehyde and carbon nano particles @ PDA @ glass fiber hybrid filler. The preparation method comprises the following two steps:
step 1: preparation of carbon nanoparticle @ PDA @ glass fiber hybrid filler:
respectively putting 1-20 parts of carbon nanoparticles and 5-30 parts of chopped glass fibers into a beaker, respectively adding a water-ethanol mixed solvent with the volume ratio of 1:9 to prepare a carbon nanoparticle dispersion liquid and a glass fiber dispersion liquid with the concentration of 5-30%, wherein the carbon nanoparticle dispersion liquid is ultrasonically dispersed for 10-120min, the glass fiber dispersion liquid is uniformly stirred, respectively adding 0.01-10 parts of aminosilane coupling agent, stirring in a water bath at 30-80 ℃ for 0.5-3h, carrying out suction filtration and cleaning, and drying at 120 ℃ for 3h to obtain the aminated carbon nanoparticles and the aminated glass fibers.
Dispersing 1-20 parts of aminated carbon nanoparticles into 100-1000mL deionized water, performing ultrasonic treatment at 20-80 ℃ for 10min-2h, then adding 0.1-5 parts of dopamine hydrochloride into the carbon nanoparticle dispersion liquid, adding tris (hydroxymethyl) aminomethane after full dissolution, adjusting the pH value to 8.5, and stirring at room temperature for reaction for 5-20 h; and then adding 5-30 parts of aminated glass fiber, stirring at room temperature for 5-20h, washing with deionized water and absolute ethyl alcohol, and drying to obtain the carbon nanoparticle @ PDA @ glass fiber hybrid filler.
Preferably, the carbon nanoparticles are any one or more of carbon nanotubes and graphene;
preferably, the aminosilane coupling agent is any one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane and N-beta- (aminoethyl) -gamma-aminopropyltriethoxysilane.
Step 2: preparing a polyformaldehyde/carbon nanoparticle @ PDA @ glass fiber hybrid filler composite material:
adding 100 parts of polyformaldehyde, 0.05-5 parts of antioxidant and 5-30 parts of carbon nano particle @ PDA @ glass fiber hybrid filler into a high-speed mixer, uniformly mixing, melting and mixing by using a double-screw extruder, and extruding and granulating at the screw rotating speed of 50-200 rpm and the charging barrel temperature of 150 ℃ and 190 ℃ to obtain the high-strength polyformaldehyde.
Preferably, the antioxidant is any one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (i.e., Irganox1010), N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexamethylenediamine (i.e., Irganox 1098), octadecyl beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate (i.e., Irganox 1076), triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylbenzyl) propionate (i.e., Irganox 245), and 2, 6-di-tert-butyl-4-methylphenol (i.e., BHT (264)).
The tensile strength, the bending strength and the modulus of the high-reinforced polyformaldehyde prepared by the method are improved by 10-20% compared with those of glass fiber reinforced polyformaldehyde with the same dosage.
The invention has the following advantages:
carbon nanoparticles such as Graphene (GE) are carbon materials formed by closely stacking sp2 hybridized carbon atoms into a single-layer two-dimensional honeycomb lattice structure, the strength of the carbon nanoparticles reaches 130GPa, is 100 times higher than that of steel, and is the highest material at present; carbon Nanotubes (CNTs) can be regarded as hollow tubes with extremely small radial dimension, which are formed by the graphene sheets curling around a central axis, and have a tube diameter of 1-30nm, an axial length of up to micron level, a large length-diameter ratio, and excellent mechanical properties. Poly Dopamine (PDA) is a mussel bionic material, is obtained by self-polymerization of dopamine in a weakly alkaline environment, contains a large amount of catechol, primary amine and secondary amine in a molecular structure, can be adhered to various substrates through hydrogen bond action, chelation, pi-pi interaction and covalent bond action, and has excellent interface adhesion performance.
According to the invention, firstly, amino silane coupling agent is adopted to treat carbon nano particles and glass fibers, amino groups are introduced to the surfaces of the carbon nano particles and the glass fibers, and aminated carbon nano particles and aminated glass fibers are obtained; then, by utilizing the strong adhesion property of polydopamine, taking the polydopamine as a bridging molecule, bonding low-dimensional and high-strength carbon nano particles such as graphene and carbon nano tubes on the surface of glass fiber through Schiff base reaction of active groups such as phenolic hydroxyl groups and amino groups of the molecules with carbon nano particles and amino groups on the surface of the glass fiber and hydrogen bonding action of the active groups with oxygen-containing groups of the carbon nano particles, increasing the roughness of the surface of the glass fiber, and simultaneously enhancing the hydrogen bonding action with C-O groups of polyformaldehyde molecules, so that a strong mechanical/chemical meshing action is formed between the polyformaldehyde molecules and a polyformaldehyde matrix, a polyformaldehyde matrix-fiber interface multistage reinforcing structure is constructed, the interface strength and the interface stress transfer capacity of the material are remarkably improved, the high-efficiency reinforcing action of the glass fiber/carbon nano particle hybrid filler on polyformaldehyde is exerted, and the mechanical strength and the modulus of the polyformaldehyde are greatly improved; on the other hand, the introduction of a large amount of amino groups is beneficial to improving the absorption of the composite system to formaldehyde and formic acid generated by the degradation of polyformaldehyde, thereby effectively improving the thermal stability of the composite material.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for illustrative purposes and should not be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations of the present invention based on the above disclosure. The starting materials used in the examples are, unless otherwise specified, commercially available from conventional sources.
Example 1
Putting 5 parts of carbon nanotubes and 10 parts of chopped glass fibers into two beakers respectively, adding a water-ethanol mixed solvent with the volume ratio of 1:9 respectively to prepare a carbon nanotube dispersion liquid and a glass fiber dispersion liquid with the concentration of 5%, wherein the carbon nanotube dispersion liquid is subjected to ultrasonic dispersion for 30min, the glass fiber dispersion liquid is uniformly stirred, adding 0.5 part of gamma-aminopropyltrimethoxysilane respectively, stirring for 1h in a water bath at 50 ℃, performing suction filtration and cleaning, and drying for 3h at 120 ℃ to obtain the aminated carbon nanotubes and the aminated glass fibers.
Dispersing 5 parts of aminated carbon nanotube in 200mL of deionized water, performing ultrasonic treatment at 50 ℃ for 30min, then adding 1 part of dopamine hydrochloride into the dispersion liquid, fully dissolving, adding tris (hydroxymethyl) aminomethane to adjust the pH value to 8.5, and stirring and reacting at room temperature for 5 h; and then adding 10 parts of aminated glass fiber, stirring at room temperature for 5 hours, washing with deionized water and absolute ethyl alcohol, and drying to obtain the carbon nanotube @ PDA @ glass fiber hybrid filler.
Adding 100 parts of polyformaldehyde and 0.5 part of Irganox1010 and 10 parts of carbon nano tube @ PDA @ glass fiber hybrid filler into a high-speed mixer for uniform mixing, then carrying out melt mixing by using a double-screw extruder, and carrying out extrusion granulation, wherein the rotating speed of a screw is 100 revolutions per minute, and the temperature of a charging barrel is 150-.
Example 2
Respectively putting 8 parts of graphene and 20 parts of chopped glass fibers into two beakers, respectively adding water-ethanol solutions with the volume ratio of 1:9 to prepare a 10% carbon nanotube dispersion liquid and a glass fiber dispersion liquid, wherein the graphene dispersion liquid is subjected to ultrasonic dispersion for 90min, the glass fiber dispersion liquid is uniformly stirred, respectively adding 1 part of gamma-aminopropyltriethoxysilane, stirring for 2h in a water bath at 60 ℃, performing suction filtration and cleaning, and drying for 3h at 120 ℃ to obtain aminated graphene and aminated glass fibers;
dispersing 8 parts of aminated graphene in 500mL of deionized water, performing ultrasonic treatment at 60 ℃ for 1h, then adding 3 parts of dopamine hydrochloride into the graphene dispersion liquid, fully dissolving, adding tris (hydroxymethyl) aminomethane to adjust the pH value to 8.5, and stirring and reacting at room temperature for 12 h; then adding 20 parts of aminated glass fiber, stirring at room temperature for 12 hours, washing with deionized water and absolute ethyl alcohol, and drying to obtain the graphene @ PDA @ glass fiber hybrid filler;
100 parts of polyformaldehyde and 1 part of Irganox 245 and 20 parts of graphene @ PDA @ glass fiber hybrid filler are added into a high-speed mixer to be uniformly mixed, and then a double-screw extruder is used for melting and mixing, extrusion granulation is carried out, the rotating speed of a screw is 150 revolutions per minute, the temperature of a charging barrel is 150 ℃ plus 190 ℃, and the high-reinforcement polyformaldehyde is obtained.
Example 3
Respectively putting 10 parts of carbon nanotubes and 30 parts of chopped glass fibers into two beakers, respectively adding water-ethanol solutions with the volume ratio of 1:9 to prepare a carbon nanotube dispersion liquid and a glass fiber dispersion liquid with the concentration of 30%, wherein the carbon nanotube dispersion liquid is ultrasonically dispersed for 120min, the glass fiber dispersion liquid is uniformly stirred, respectively adding 2 parts of N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, stirring for 3 hours in a water bath at the temperature of 80 ℃, performing suction filtration and cleaning, and drying for 3 hours at the temperature of 120 ℃ to obtain an aminated carbon nanotube and an aminated glass fiber;
dispersing 10 parts of aminated carbon nanotube in 1000mL of deionized water, performing ultrasonic treatment at 80 ℃ for 2h, then adding 5 parts of dopamine hydrochloride into the carbon nanotube dispersion liquid, fully dissolving, adding tris (hydroxymethyl) aminomethane to adjust the pH value to 8.5, and stirring and reacting at room temperature for 20 h; then adding 30 parts of aminated glass fiber, stirring at room temperature for 20 hours, washing with deionized water and absolute ethyl alcohol, and drying to obtain the carbon nanotube @ PDA @ glass fiber hybrid filler;
100 parts of polyformaldehyde and 2 parts of Irganox 1098 and 30 parts of carbon nano tube @ PDA @ glass fiber hybrid filler are added into a high-speed mixer to be uniformly mixed, and then a double-screw extruder is used for melting and mixing, extrusion granulation is carried out, the rotating speed of a screw is 200 revolutions per minute, the temperature of a charging barrel is 150-.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the embodiments and descriptions given above are only illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The high-strength polyformaldehyde is characterized in that the high-strength polyformaldehyde is formed by compounding polyformaldehyde and carbon nano particles @ PDA @ glass fiber hybrid filler.
2. A preparation method of high-strength polyformaldehyde is characterized by at least comprising the following steps:
step 1: preparing a carbon nano particle @ PDA @ glass fiber hybrid filler;
step 2: preparing a polyformaldehyde/carbon nano particle @ PDA @ glass fiber hybrid filler composite material.
3. The process for producing highly reinforced paraformaldehyde according to claim 2, wherein the step 1 comprises:
respectively putting 1-20 parts of carbon nanoparticles and 5-30 parts of chopped glass fibers into a beaker, respectively adding a water-ethanol mixed solvent with a volume ratio of 1:9 to prepare a solution with a concentration of 5-30%, wherein the carbon nanoparticle dispersion liquid is ultrasonically dispersed for 10-120min, the glass fiber dispersion liquid is uniformly stirred, respectively adding 0.01-10 parts of aminosilane coupling agent, then stirring in a water bath at 30-80 ℃ for 0.5-3h, carrying out suction filtration and cleaning, and drying at 120 ℃ for 3h to obtain aminated carbon nanoparticles and aminated glass fibers;
dispersing 1-20 parts of aminated carbon nanoparticles into 100-1000mL deionized water, performing ultrasonic treatment at 20-80 ℃ for 10min-2h, then adding 0.1-5 parts of dopamine hydrochloride into the carbon nanoparticle dispersion liquid, adding tris (hydroxymethyl) aminomethane after full dissolution to adjust the pH value to 8.5, and stirring at room temperature for reaction for 5-20 h; and then adding 5-30 parts of aminated glass fiber, stirring at room temperature for 5-20h, washing with deionized water and absolute ethyl alcohol, and drying to obtain the carbon nanoparticle @ PDA @ glass fiber hybrid filler.
4. The method for preparing the high-strength polyformaldehyde according to claim 3, wherein the carbon nanoparticles are any one or more of carbon nanotubes and graphene.
5. The method for preparing the highly reinforced polyformaldehyde according to claim 3, wherein the aminosilane coupling agent is one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, and N-beta- (aminoethyl) -gamma-aminopropyltriethoxysilane.
6. The process for producing highly reinforced paraformaldehyde according to claim 2, wherein the step 2 comprises:
adding 100 parts of polyformaldehyde, 0.05-5 parts of antioxidant and 5-30 parts of carbon nano particle @ PDA @ glass fiber hybrid filler into a high-speed mixer, uniformly mixing, melting and mixing by using a double-screw extruder, and extruding and granulating at the screw rotating speed of 50-200 rpm and the charging barrel temperature of 150 ℃ and 190 ℃ to obtain the high-strength polyformaldehyde.
7. The process according to claim 6, wherein the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (i.e., Irganox1010), N, any one or more of N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexamethylenediamine (i.e., Irganox 1098), octadecyl beta- (4-hydroxy-3, 5-di-tert-butylphenyl) propionate (i.e., Irganox 1076), triethylene glycol bis-3- (3-tert-butyl-4-hydroxy-5-methylbenzyl) propionate (i.e., Irganox 245), and 2, 6-di-tert-butyl-4-methylphenol (i.e., BHT (264)).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115449098A (en) * | 2022-09-28 | 2022-12-09 | 重庆云天化天聚新材料有限公司 | Preparation method of low-cost conductive glass fiber reinforced polyformaldehyde |
| CN116023694A (en) * | 2022-12-14 | 2023-04-28 | 华东理工大学 | Post-treatment enhancement method for TPU (thermoplastic polyurethane) product |
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| CN104672776A (en) * | 2015-02-06 | 2015-06-03 | 合肥康龄养生科技有限公司 | Carbon fibre reinforced polyformaldehyde composite material with high mechanical strength and preparation method thereof |
| KR20190037556A (en) * | 2017-09-29 | 2019-04-08 | 코오롱플라스틱 주식회사 | Long Fiber Reinforced Polyoxymethylene Resin Composition And Article Produced from The Same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449098A (en) * | 2022-09-28 | 2022-12-09 | 重庆云天化天聚新材料有限公司 | Preparation method of low-cost conductive glass fiber reinforced polyformaldehyde |
| CN116023694A (en) * | 2022-12-14 | 2023-04-28 | 华东理工大学 | Post-treatment enhancement method for TPU (thermoplastic polyurethane) product |
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