CN111117218A - Polyamide composition with improved color fastness after hot baking and application thereof - Google Patents
Polyamide composition with improved color fastness after hot baking and application thereof Download PDFInfo
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- CN111117218A CN111117218A CN201911415208.9A CN201911415208A CN111117218A CN 111117218 A CN111117218 A CN 111117218A CN 201911415208 A CN201911415208 A CN 201911415208A CN 111117218 A CN111117218 A CN 111117218A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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Abstract
The invention discloses a polyamide composition with improved color fastness after heat baking, which comprises the following raw materials in parts by weight: 19.1-99.3 parts of polyamide 6 resin or/and polyamide 66 resin; 10-50 parts of polyamide 56 resin; 0-35 parts of an additive; wherein the sum of the weight parts of the raw materials is 100 parts. The invention also discloses application of the polyamide composition with improved color fastness after heat baking in extruded products and injection-molded products. The color difference value of the invention after being baked for 48 hours by hot air at 120 ℃ is obviously less than that of polyamide 6 resin, polyamide 66 resin and mixture of polyamide 6 resin and polyamide 66 resin.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyamide composition with improved color fastness after heat baking and application thereof.
Background
Polyamides, commonly referred to as nylons, are polymers having amide linkages in the molecular backbone. It has been widely used in textile, automotive, electronic and electrical, packaging, sports products, etc. Polyamides are generally divided into two groups, one of which is obtained by polycondensation of amino acids or ring-opening polymerization of lactams, also known as AB-type polyamides, the typical representative resin of which is PA 6; one type is polyamides obtained by polycondensation of diacids and diamines, also known as AABB type polyamides, a representative resin of this type of polyamide being PA 66.
The dyed PA6 and PA66 materials are widely used in various industries, and in the field of electronic and electric appliances, PA66 materials used as connection terminals are dyed in different colors so as to be distinguished by engineering installation and maintenance personnel, and PA6 materials used for electric tools and gardening tools are made into various bright color tones according to the design requirements. Unfortunately, bright-colored PA6 or PA66 materials often exhibit severe discoloration when exposed to hot working environments, and researchers have improved this drawback by adding antioxidants and even additives for weathering, but the results have been less than satisfactory.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a polyamide composition with improved color fastness after hot baking and application thereof, and the color difference value of the polyamide composition after hot air baking for 48 hours at 120 ℃ is obviously smaller than that of polyamide 6 resin, polyamide 66 resin and a mixture of polyamide 6 resin and polyamide 66 resin.
The invention provides a polyamide composition with improved color fastness after heat baking, which comprises the following raw materials in parts by weight:
19.1-99.3 parts of polyamide 6 resin or/and polyamide 66 resin;
10-50 parts of polyamide 56 resin;
0-35 parts of an additive;
wherein the sum of the weight parts of the raw materials is 100 parts.
The intrinsic viscosities of the polyamide 6 resin and the polyamide 66 resin are not particularly limited, and the intrinsic viscosities of the two resins are usually 90 to 350ml/g, and preferably 100 to 250 ml/g.
The above intrinsic viscosity is measured at 25 ℃ in concentrated sulfuric acid having a mass fraction of 96% according to ISO 307.
The relative viscosity of the polyamide 6 resin and the polyamide 66 resin is not particularly limited, and the relative viscosity of these two resins is usually 2.0 to 3.2, and preferably 2.4 to 2.8.
The above relative viscosity is measured at 25 ℃ according to ISO 307 in 96% by mass concentrated sulfuric acid.
The terminal amino group content of the polyamide 6 resin and the polyamide 66 resin is not particularly limited, and the terminal amino group content of both resins is usually 40 to 100mmol/kg, preferably 40 to 70 mmol/kg.
Preferably, the relative viscosity of the polyamide 56 resin is 2.4 to 3.2.
Preferably, the relative viscosity of the polyamide 56 resin is 2.4 to 2.7.
The detection method of the relative viscosity comprises the following steps: the polyamide 56 resin is dissolved in a sulfuric acid solution with the mass fraction of 96% for detection, wherein the mass fraction of the polyamide 56 resin is 1%, and the detection method refers to the standard ISO 307.
Preferably, the amino-terminated content of the polyamide 56 resin is 50mmol/kg or more.
Preferably, the amino-terminated group content of the polyamide 56 resin is 60mmol/kg or more.
Preferably, the amino-terminated content of the polyamide 56 resin is 80mmol/kg or more.
The polyamide 56 resin belongs to a semi-bio-based synthetic polymer, and is obtained by performing polycondensation reaction on pentanediamine (obtained by a biological fermentation method) and adipic acid (obtained by conventional chemical synthesis).
The synthesis process of the polyamide 56 resin is similar to that of the polyamide 66, and the specific method comprises the following steps: firstly, mixing 1, 5-pentanediamine and adipic acid according to a molar ratio of 1:1-1.05, adding an antioxidant, carrying out a salt forming reaction at a temperature of 10-130 ℃ and a pressure of 0.1-0.3MPa, pumping the solution into a tubular continuous reactor or a prepolymerization reaction kettle at a temperature of 230-290 ℃ and a pressure of 1-5MPa, and reacting for 30-300min to obtain a prepolymer. Further flash evaporating the obtained prepolymer to remove water, continuously pumping the dehydrated prepolymer into a polycondensation reactor, setting the reaction temperature at 250-300 ℃ under the protection of nitrogen, reacting for 30-200min to obtain polyamide 56, and extruding and granulating the melt thereof to obtain the final product, wherein the detailed synthesis steps can refer to patents CN105885038A, CN103145979A, CN104031263A and the like.
Preferably, the additive comprises at least one of an antioxidant, a lubricant, a reinforcing agent, and a toner.
The reinforcing agent described in the present invention is a fibrous reinforcing filler, which is not particularly limited and functions to improve mechanical strength, such as tensile strength, flexural strength, impact strength, etc., of the polyamide composition.
The fiber-reinforced filler includes glass fiber, carbon fiber, graphite fiber, ceramic fiber, metal fiber, organic fiber (kevlar fiber made of para-aramid), plant fiber, or the like, and one or a combination of more of them may be used. Preferred in the present invention are glass fibers and carbon fibers, and more preferred are glass fibers.
Among the glass fibers, grade E alkali-free glass fibers are preferred.
The diameter of the glass fiber is not particularly limited, and is preferably 7 to 17 micrometers, more preferably 10 to 13 micrometers.
The length of the glass fiber is not particularly limited, and continuous uncut glass fiber filaments may be used, and cut glass chopped fibers may also be used, the chopped glass fibers preferably having a length of 2 to 5 mm.
The cross section of the glass fiber has no special requirement and can be round or rectangular. The rectangular cross section is vertical to the longitudinal direction of the fiber, the longest straight line distance in the rectangular cross section is a long axis, the shortest straight line distance in the rectangular cross section is a short axis, the length of the long axis and the short axis is 1.5-10:1, and the preferable ratio is 3-4: 1.
And the glass fiber is treated by a surface sizing agent.
The surface sizing agent comprises a coupling agent, such as: epoxy group-containing compounds, acrylic acid-containing compounds, polyurethane-containing compounds, and the like, and preferably, the coupling agent is a silane coupling agent-containing compound.
The general formula of the silane coupling agent is as follows:
(X-(CH2)n)k-Si-(O-CmH2m+1)4-k；
wherein, X is amino, ethylene oxide, hydroxyl, etc.;
n is an integer from 2 to 10, preferably from 3 to 4;
m is an integer from 2 to 10, preferably from 3 to 4;
k is an integer from 1 to 3, preferably 1.
The silane coupling agent is used in an amount of 0.025 to 1%, preferably 0.05 to 0.5%, by weight of the glass fiber.
Antioxidants commonly used for polyamide resins include hindered phenol antioxidants, hindered amine antioxidants (radical scavengers), phosphite secondary antioxidants, and the like.
Preferably, the hindered phenol-based antioxidant is at least one of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and bis (2,2,6, 6-tetramethyl-3-piperidinylamino) -isophthalamide, and the hindered amine-based antioxidant is at least one of 4,4 ' -bis (α ' -dimethylbenzyl) diphenylamine, bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate, N ' -bis (2,2,6, 6-tetramethyl-4-piperidinyl) -1, 3-benzenedicarboxamide, poly { [6- [ (1,1,3, 3-tetramethylbutyl) amino ] ] -1,3, 5-triazine-2, 4- [ (2,2,6,6, -tetramethyl-piperidinyl) imino ] -1, 6-hexanediylene [ (2,2,6, 6-tetramethyl-4-piperidinyl) imino ] }.
The phosphite ester auxiliary antioxidant is inorganic phosphorus salt; the inorganic phosphorus salt is preferably disodium phosphite and/or sodium hypophosphite, and the preferred particle size of the inorganic phosphorus salt is 0.1-10 μm, more preferably 0.5-5 μm, and most preferably 1-3 μm.
The sodium hypophosphite can be synthesized by a one-step method: adding yellow phosphorus, lime cream and a sodium carbonate solution into a high-speed emulsification reactor in an inert gas atmosphere, adding a dispersing agent while stirring to greatly increase the specific surface area of phosphorus, so that the reaction speed is increased, heating to 45-90 ℃ for reaction, releasing phosphine and hydrogen, and filtering after the reaction is finished, wherein the filtrate is a sodium hypophosphite solution; introducing carbon dioxide into the sodium hypophosphite solution to remove calcium hydroxide dissolved in the sodium hypophosphite solution, filtering to remove calcium carbonate, adding an arsenic removing agent and a heavy metal removing agent into the filtrate to purify the solution, filtering to remove impurities such as arsenic, heavy metal and the like, carrying out vacuum evaporation concentration on the filtrate, cooling for crystallization, and carrying out centrifugal separation to remove mother liquor, thus obtaining the finished sodium hypophosphite.
The sodium hypophosphite can also be synthesized by a two-step method: adding yellow phosphorus, slaked lime and water into a reactor, and reacting at 98 ℃ to generate calcium hypophosphite, wherein phosphine is generated in the reaction process, and safety protection needs to be paid attention to; filtering to remove unreacted substances, introducing carbon dioxide, further removing a small amount of calcium hydroxide, then adding a sodium carbonate solution and calcium hypophosphite to perform a double decomposition reaction to generate sodium hypophosphite, filtering to remove calcium carbonate after generating the sodium hypophosphite, adding an arsenic removing agent and a heavy metal removing agent into the filtrate to perform solution purification, filtering to remove impurities such as arsenic, heavy metals and the like, performing vacuum evaporation concentration on the filtrate until the mass fraction of the solution is about 20%, filtering to remove calcium carbonate, performing secondary concentration on the filtrate until the liquid surface presents a crystalline membrane, cooling, crystallizing, and performing centrifugal separation to remove a mother solution, thus obtaining a finished product of the sodium hypophosphite.
Disodium phosphite, also known as disodium hydrogen phosphate, generally contains 5 molecules of crystal water, and when heated to 100 ℃ loses all crystal water to form an anhydrate, which decomposes to sodium pyrophosphate at 250 ℃.
The preparation method of the disodium phosphite comprises the following steps: adding disodium hydrogen phosphate dodecahydrate into a dissolving tank, heating for dissolving, adding a small amount of industrial phosphoric acid, adjusting the pH to 8.8-9.0, enabling the temperature of the solution to be 80-85 ℃, pumping the solution into a metering tank, and atomizing by using an atomizer to obtain a finished product of the disodium hydrogen phosphate anhydrous, wherein the atomizer adopts a two-flow pneumatic nozzle, the steam pressure is 0.15-0.3MPa, the steam flow angle of the atomizer forms 30 degrees with the horizontal plane, and the steam-liquid volume ratio is 0.4-5: 1, the temperature of a gas inlet of a hot furnace is 650-750 ℃; during atomization, the drying can be carried out in parallel flow or in countercurrent flow; the inlet temperature of the countercurrent drying is 620-650 ℃, and the outlet temperature of the countercurrent drying is 140-150 ℃. The particle size of 60 percent of the obtained anhydrous disodium hydrogen phosphate is about 90 mu m, and the moisture content of the anhydrous disodium hydrogen phosphate is less than 1 percent.
The weight fraction of the lubricant in the present invention may be 0 to 0.5%, and the lubricant is preferably a carboxylate, a fatty acid ester containing 10 to 44 methylene groups, a fatty acid amide containing 10 to 44 methylene groups, an olefin wax having a molecular weight of 3000g/mol or less, an acidified olefin wax having a molecular weight of 3000g/mol or less, an oxidized olefin wax having a molecular weight of 3000g/mol or less; more preferably a fatty acid ester having 17 to 28 methylene groups, a fatty acid amide having 17 to 28 methylene groups, an olefin wax having a molecular weight of 3000g/mol or less, an acidified olefin wax having a molecular weight of 3000g/mol or less, and an oxidized olefin wax having a molecular weight of 3000g/mol or less.
The carboxylate is preferably at least one of an alkaline earth metal carboxylate, a zinc carboxylate salt and an aluminum carboxylate salt, more preferably at least one of an aluminum carboxylate salt and a magnesium carboxylate salt, and even more preferably at least one of magnesium stearate and aluminum distearate.
The carboxylic acid used in the synthesis of the fatty acid ester is a monocarboxylic acid or a dicarboxylic acid, and examples thereof include stearic acid, palmitic acid, lauric acid, margaric acid, and montanic acid.
The fatty alcohol used in the synthesis of the fatty acid ester is a monohydric or tetrahydric fatty alcohol, such as ethylene glycol, propylene glycol, and glycerol, preferably glycerol and pentaerythritol.
The fatty amine in the synthesis of the fatty acid amide may be a mono-to ternary fatty amine, for example, stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, etc., preferably ethylenediamine or hexamethylenediamine.
The fatty acid ester and the fatty acid amide can be used in combination in any proportion.
The olefin wax, the acidified olefin wax and the oxidized olefin wax are obtained by a series of cracking reactions, the molecular weight of the olefin wax, the acidified olefin wax and the oxidized olefin wax is greater than that of white oil and less than or equal to 3000g/mol, and the olefin wax is solid.
The acidified olefin WAX and the oxidized olefin WAX are obtained by further modifying the olefin WAX, and the common brands are oxidized WAX PED521 of Germany Kelaien and acidified WAX Hi-WAX 4202E of Mitsui chemical.
Nucleating agents useful in the present invention include, but are not limited to: kaolin, talcum powder, mica, wollastonite, solid and/or hollow glass microspheres, boron nitride, nano silicon dioxide, nano carbon black and an organic nucleating agent; organic nucleating agents such as: phenylphosphinate, polyamide oligomer.
The nucleating agent is preferably a polyamide oligomer, carbon black, or a combination of carbon black and other nucleating agents known in the art.
The polyamide oligomer is preferably polyamide 22; the particle diameter of the carbon black is preferably 10 to 100nm as measured in accordance with ASTM D-3849.
The toner of the present invention is not particularly limited, and common toner types include inorganic toner and organic toner, the inorganic toner includes titanium yellow, titanium dioxide, carbon black, etc., and the organic toner includes ultramarine blue, phthalocyanine blue, solvent yellow, solvent red, etc.
The invention also provides the application of the polyamide composition with improved color fastness after heat baking in extruded products and injection-molded products.
The invention can be used for preparing any products formed by extrusion molding and injection molding; such as: binding post, connector, electric tool shell, garden instrument shell etc..
Has the advantages that:
the invention aims to provide a polyamide composition with improved color fastness after hot baking, and surprisingly, the color fastness of the polyamide composition under the hot baking can be obviously improved by adding a certain amount of polyamide 56 resin into polyamide 6 resin or/and polyamide 66 resin. The color difference value of the invention after being baked for 48 hours by hot air at 120 ℃ is obviously less than that of polyamide 6 resin, polyamide 66 resin and mixture of polyamide 6 resin and polyamide 66 resin.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
The examples E1-E12 and comparative examples C1-C12 in the present invention use the following starting materials:
and (2) component A:
a1: PA6, designation YH800, relative viscosity 2.8, terminal amino group content 48meq/kg, available from Yueyang petrochemical Co., Ltd, Hunan;
a2: PA66, brand EPR27, relative viscosity 2.7, amino end group content 46meq/kg, available from Hippocampus engineering plastics, Inc.
B: PA56, designation 1270W, relative viscosity 2.7, terminal amino content 54meq/kg, purchased from Shanghai Kaiser Biotech Co., Ltd;
and (3) component C: alkali-free E-grade glass fiber, grade: ECS 301HP, available from Chongqing International composite materials corporation;
and (3) component D:
d1: antioxidant 1098, CAS accession No.: 23128-74-7, trade name IGNANOX 1098, available from BASF;
d2: inorganic phosphate disodium phosphite, trade mark: h10, available from brungelmann, germany;
d3: radical scavenger 770, designation TINUVIN 770: purchased from basf;
d4: ultraviolet light absorber 234, designation TINUVIN 234: purchased from basf;
and (3) component E:
oxidized high-density polyethylene wax, grade: PED521, acid number 17mgKOH/g, available from Claien specialty Chemicals, Inc., Germany;
a component S:
toner S1: solvent yellow, brand:
YELLOW G, available from Langshan specialty Chemicals, Inc., Germany;
toner S2: solvent green, brand:
GREEN 5B, available from langer specialty chemicals ltd, germany;
toner S3: inorganic iron oxide red, trade mark: BAYERFERRO X130M, available from Langshan specialty Chemicals, Inc., Germany.
The examples E1-E12 and comparative examples C1-C12 in the present invention were prepared by: according to the proportion of each embodiment and comparative example, A, B, D, E, S is premixed, and then added into a first main hopper of a double-screw extruder produced by Nanjing Ruiya equipment Limited company with the screw diameter of 35mm, the length-diameter ratio of the screw is 48:1, the whole extruder is divided into 12 sections of barrels, a component C is fed from a second measuring feeding hopper which is arranged at the 8 th barrel, and the extrusion temperature is set as follows from a first area: 200-280 ℃, the head temperature is set to be 260 ℃, the screw rotating speed is set to be 300rpm, and the composition is obtained through melting plasticization, extrusion and grain cutting.
The resulting composition was dried and subsequently injection molded to give a color block having a thickness of 3mm according to the following process, the injection molding conditions being shown in Table 1:
TABLE 1 injection parameters
Placing the color block in a constant temperature and humidity box (23 ℃, 50% humidity) for storage for 48h, taking out, measuring initial L, a and b values by using a Nippon Konika Meinengda color difference meter CM3600A under a D65 light source, then flatly laying the color block in a hot air drying box, setting the temperature of the drying box at 120 ℃, taking out after 48h, continuously placing the baked color block in the constant temperature and humidity box (23 ℃, 50% humidity) for storage for 48h, taking out, measuring the L, a and b values for the second time, and calculating the color difference value △ E as follows:
the formulations and performance test results for comparative examples C1-C6 are shown in Table 2.
TABLE 2 formulations and performance test results for comparative examples C1-C6
The formulations and performance test results for comparative examples C7-C12 are shown in Table 3.
TABLE 3 formulation and Performance test results for comparative examples C7-C12
The formulations and performance testing results for examples E1-E6 are shown in Table 4.
TABLE 4 formulations and performance test results for examples E1-E6
The formulations and performance testing results for examples E7-E12 are shown in Table 5.
TABLE 5 formulations and performance test results for examples E7-E12
The addition of the PA56 resin to PA6 or PA66 significantly reduces the discoloration after baking, as seen in comparison of comparative examples C1-C6 with examples E1-E6, wherein the color difference after baking is reduced by 55.8% and 73.9% in comparison with C2, C5 and E2, E5, respectively, and comparison of C7-C12 with E7-E12, respectively, which still applies in material systems containing reinforcing fillers. Thus, it can be shown that adding a certain amount of PA56 resin to PA6 or PA66 significantly improves the bake fastness of the polyamide.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The polyamide composition with improved color fastness after hot baking is characterized by comprising the following raw materials in parts by weight:
19.1-99.3 parts of polyamide 6 resin or/and polyamide 66 resin;
10-50 parts of polyamide 56 resin;
0-35 parts of an additive;
wherein the sum of the weight parts of the raw materials is 100 parts.
2. Polyamide composition with improved colorfastness after heat baking according to claim 1, characterized in that the polyamide 56 resin has a relative viscosity comprised between 2.4 and 3.2.
3. Polyamide composition with improved fastness to heat after baking according to claim 1 or 2, characterized in that the polyamide 56 resin has a relative viscosity of from 2.4 to 2.7.
4. Polyamide composition with improved fastness to heat after baking according to any one of claims 1 to 3, characterized in that the polyamide 56 resin has an amino end group content of 50mmol/kg or more.
5. Polyamide composition with improved fastness to heat after baking according to any one of claims 1 to 4, characterized in that the polyamide 56 resin has an amino end group content of 60mmol/kg or more.
6. Polyamide composition with improved fastness to heat after baking according to any one of claims 1 to 5, characterized in that the polyamide 56 resin has an amino end group content of 80mmol/kg or more.
7. Polyamide composition with improved color fastness after heat baking according to any one of claims 1 to 6, characterized in that the additive comprises at least one of an antioxidant, a lubricant, a reinforcing agent, a toner powder.
8. Use of a polyamide composition according to any one of claims 1 to 7 having improved colour fastness after heat baking in extruded and injection moulded articles.
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| CN112795182A (en) * | 2020-12-30 | 2021-05-14 | 国高材高分子材料产业创新中心有限公司 | Plastic-based standard color plate for xenon lamp aging test and preparation method and application thereof |
| CN114507440A (en) * | 2022-03-07 | 2022-05-17 | 金发科技股份有限公司 | Nylon resin composite material and preparation method and application thereof |
| CN115584125A (en) * | 2022-09-19 | 2023-01-10 | 金发科技股份有限公司 | Lubricating ester-resistant PA composition and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112646369A (en) * | 2020-12-18 | 2021-04-13 | 安徽卡洛塑业科技有限公司 | Polyamide composition with reduced yellowness index |
| CN112795182A (en) * | 2020-12-30 | 2021-05-14 | 国高材高分子材料产业创新中心有限公司 | Plastic-based standard color plate for xenon lamp aging test and preparation method and application thereof |
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| CN115584125A (en) * | 2022-09-19 | 2023-01-10 | 金发科技股份有限公司 | Lubricating ester-resistant PA composition and preparation method and application thereof |
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