CN115612261A - Hydrolysis-resistant flame-retardant polyester composite material capable of being subjected to laser welding and preparation method thereof - Google Patents
Hydrolysis-resistant flame-retardant polyester composite material capable of being subjected to laser welding and preparation method thereof Download PDFInfo
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- CN115612261A CN115612261A CN202211311735.7A CN202211311735A CN115612261A CN 115612261 A CN115612261 A CN 115612261A CN 202211311735 A CN202211311735 A CN 202211311735A CN 115612261 A CN115612261 A CN 115612261A
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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Abstract
The invention relates to a hydrolysis-resistant flame-retardant polyester composite material capable of being subjected to laser welding, which comprises the following components in percentage by weight: polyester resin, polysulfone resin, a high-light-transmission synergist, a light-transmission reinforced filler, a light-transmission hydrolysis-resistant agent, an anti-reflection agent, a compatilizer, a halogen-free flame retardant, a lubricant and an antioxidant. The invention also provides a preparation method of the polyester composite material for laser welding, which comprises the following steps: polyester resin, polysulfone resin, high-light-transmission synergist, light-transmission reinforced filler, light-transmission hydrolysis resistant agent, anti-reflection agent, compatilizer, halogen-free flame retardant, lubricant and antioxidant are mixed, and are granulated by an extruder at the granulation temperature of 250-310 ℃. The product of the invention has excellent hydrolysis resistance, higher laser transmittance, environmental protection and flame retardance, and is particularly suitable for the field of laser welding and the field with high requirements on material transmittance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a hydrolysis-resistant flame-retardant polyester composite material capable of being subjected to laser welding and a preparation method thereof.
Background
Plastic laser welding is a technique whereby the heat generated by a laser beam melts the plastic contact surface, thereby bonding thermoplastic sheets, films, or molded parts together. The laser welding is applied to the advantages of plastic part welding: the welding is precise and firm, the sealing is airtight and water-tight, and no plastic residue is generated in the welding process. The laser welding technology is fast, and is particularly suitable for the flow line processing of automobile plastic parts. In addition, laser welding techniques are contemplated for complex geometries that are difficult to bond using other welding methods.
The polybutylene terephthalate is a semi-crystalline thermoplastic polyester and has excellent performances of high heat resistance, fatigue resistance, self-lubrication and the like. Thermoplastic Polyester (PBT) materials are widely used in electronic and electric appliances, automobile parts, machinery, household electrical appliances and the like because of their heat resistance, weather resistance, chemical resistance, good electrical characteristics, low water absorption and good gloss. However, compared to other crystalline materials such as polyamides, the polyester material PBT has a lower laser transparency, which is the main reason that although PBT material exhibits otherwise excellent properties (low water absorption, economy), it is still less adopted as a material for laser welding component at present. In addition, the PBT has the defects of low notch impact strength, large molding shrinkage, easy hydrolysis, low flame retardance and the like, and further limits the application range of the product.
A common method for providing flame retardancy to thermoplastic polyesters involves the addition of halogenated organic compounds as flame retardants and antimony compounds as flame retardant synergists. However, the use of halogenated flame retardants tends to corrode compounding extruder barrels, molding machine surfaces, and other equipment with which they come into contact at elevated temperatures, and certain halogenated flame retardants also have a detrimental effect on the electrical properties of the compounded polyester composite. In addition, such a flame retardant is added in a large amount, and causes inhibition and absorption of laser light transmittance, thereby making it difficult to achieve laser welding. Therefore, the method has great practical significance and technical difficulty in improving the laser welding performance of the flame-retardant reinforced polyester material. The invention combines the matrix resin materials, and researches the high performance characteristics of the materials through mixing in a certain proportion, reinforcement, flame retardance, hydrolysis resistance and anti-reflection modification.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a hydrolysis-resistant flame-retardant polyester composite material capable of being welded by laser and a preparation method thereof.
In order to solve the technical problems, the invention aims to realize that: the invention relates to a hydrolysis-resistant flame-retardant polyester composite material capable of being subjected to laser welding, which comprises the following components in parts by weight:
10-40 parts of polyester resin;
10-40 parts of polysulfone resin;
5-20 parts of high-light-transmission synergist;
10-50 parts of light-transmitting reinforced filler;
0.3-1.0 part of light-transmitting hydrolysis-resistant agent;
3-10 parts of a compatilizer;
5-20 parts of halogen-free flame retardant;
0.2-1.0 part of lubricant;
0.2-1.0 part of antioxidant;
0.3-0.5 part of anti-reflection agent.
The invention is further configured to: the polyester resin is one or a mixture of more than two of polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate; at least some of the end groups of the polyester have been neutralized with a sodium or potassium salt.
The invention is further configured to: the polysulfone resin is one or a mixture of more than two of polysulfone, polysulfone containing methylene, polyethersulfone and polyphenylsulfone.
The invention is further configured to: the high-light-transmission synergist is non-crystalline copolyester, and specifically is one or a mixture of more than two of polyethylene glycol terephthalate-1, 4-cyclohexanedimethanol ester, poly (1, 4-cyclohexanedimethanol terephthalate) and terephthalic acid-isophthalic acid-1, 4-cyclohexanediaddition ester.
The invention is further configured to: the light-transmitting reinforced filler is one or a mixture of more than two of flat glass fibers, calcium sulfate flat whiskers, calcium carbonate flat whiskers, magnesium carbonate flat whiskers, basic magnesium sulfate whiskers and aluminum oxide magnesium whiskers.
The invention is further configured to: the length of the cross section of the flat glass fiber is 20-35 μm, the width is 4-10 μm, and the length of the glass fiber is 2500-3000 μm;
the magnesium carbonate flat whisker has the flatness of 3-6, the length of the cross section of 0.3-1.2 mu m, the width of 0.1-0.2 mu m and the length of 15-30 mu m;
the calcium carbonate flat whisker has the flatness of 5-20, the length of the cross section of 0.5-5 mu m, the width of 0.1-0.2 mu m and the length of 10-50 mu m;
the flatness of the calcium sulfate flat whisker is 5-50, the length of the cross section is 0.5-10 mu m, the width is 0.1-0.2 mu m, and the length of the whisker is 15-100 mu m;
the maximum length of the aluminum oxide magnesium whisker is 20-30mm, the diameter is 50-100 mu m, and the length-diameter ratio is 20-400;
the basic magnesium sulfate whisker has the average length of 15 microns, the diameter of 0.5 micron and the length-diameter ratio of 20-40.
The invention is further configured to: the anti-reflection agent is one or a mixture of more than two of sodium cobaltate, potassium cobaltate, sodium borate, potassium borate, sodium citrate, potassium citrate, sodium oxalate and potassium oxalate.
The invention is further configured to: the light-transmitting hydrolysis-resistant agent is at least one of monomer type carbodiimide and polymerization type carbodiimide.
The invention is further configured to: the compatilizer is hydrogenated styrene-butadiene block copolymer.
The invention is further configured to: the antioxidant is at least one of phenols, phosphites, amines and hindered phenol antioxidants.
The invention is further configured to: the lubricant is at least one of sodium stearate, calcium stearate, aluminum stearate and magnesium stearate.
The invention is further configured to: the halogen-free flame retardant is at least one of phenoxy polyphosphazene and resorcinol bis (di-2, 6-xylyl) phosphate.
A preparation method of a hydrolysis-resistant flame-retardant polyester composite material capable of being subjected to laser welding comprises the following steps: the hydrolysis-resistant reinforced flame-retardant polyester composite material is prepared by uniformly mixing polyester resin, glass fiber, halogen-free flame retardant, hydrolysis resistance agent, antioxidant and lubricant according to a ratio, adding the mixture into a feeder of an extruder, and granulating by a double-screw extruder at a granulation temperature range of 250-310 ℃ and a rotation speed range of 250-600 rpm.
In conclusion, the invention has the following beneficial effects:
1. the laser transmittance of the flame-retardant polyester composition can be greatly improved by adding a small amount of the anti-reflection agent, and particularly, the uniformity of the laser transmittance of a sample or a component at different positions from an injection gate is obviously improved, so that the laser weldability is improved.
2. The introduction of the novel hydrolysis resistant agent can react with carboxylic acid generated by the decomposition of the polymer to generate a stable ureido compound without side effect. Thereby slowing down the hydrolysis of the polymer, prolonging the service life of the polymer and simultaneously solving the problem of the reduction of the comprehensive performance of the polyester material caused by hydrolysis. And the hydrolysis resistance is improved, and the laser welding performance is not influenced, so that the material has excellent electrical performance hardly influenced by temperature and humidity. And the synergistic effect of the antioxidant and the hydrolysis-resistant auxiliary agent can effectively inhibit the foaming phenomenon caused by the decomposition of the flame retardant and the decomposition of the polyester resin in the laser welding process.
3. The polysulfone has high hardness, high impact strength, good heat, cold and aging resistance, good hydrolysis resistance, good dimensional stability and self-extinguishing property, and can be used at 160-170 ℃ for a long time. Therefore, the introduction of the polysulfone material is beneficial to improving the laser transmittance and hydrolysis resistance of the polyester resin, and the dosage of the flame retardant can be greatly reduced while the excellent flame retardance is maintained.
4. The resorcinol bis (di-2, 6-xylyl) phosphate and the phenoxy polyphosphazene are used as flame retardants, have good compatibility with PBT resin, high flame retardant efficiency, and do not influence light transmission and laser transmission like halogen antimony and phosphorus nitrogen flame retardants.
Drawings
FIG. 1 is a graph of laser transmission and weld strength data for an example of the present invention versus a prior art comparative example;
FIG. 2 shows hydrolysis resistance data of examples of the present invention and a conventional comparative example;
FIG. 3 is an SEM scanning electron micrograph of flat fiberglass in an embodiment of the invention;
FIG. 4 is an SEM scanning electron micrograph of magnesium carbonate whiskers in an embodiment of the invention;
FIG. 5 is an SEM scanning electron micrograph of calcium carbonate whiskers in an embodiment of the invention;
FIG. 6 is an SEM scanning electron micrograph of calcium sulfate flat whiskers in an embodiment of the invention;
FIG. 7 is an SEM scanning electron micrograph of magnesia alumina whiskers of an embodiment of the present invention;
FIG. 8 is an SEM scanning electron micrograph of basic magnesium sulfate whiskers in an embodiment of the invention.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in conjunction with specific examples, but it should be understood that these descriptions are only for the purpose of further illustrating the features and advantages of the present invention, and are not intended to limit the patent claims of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention will be further described with reference to the accompanying drawings and preferred embodiments.
The invention relates to a laser-weldable hydrolysis-resistant reinforced flame-retardant polyester composite material, which comprises the following components: polyester resin, polysulfone resin, a high-light-transmission composite synergist, a light-transmission reinforced filler, a light hydrolysis resistant agent, an anti-reflection agent, a compatilizer, a halogen-free flame retardant, a lubricant and an antioxidant.
Preferred polyester resins include one or a mixture of two or more of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PPT). More preferred polyesters are those in which at least some of the end groups have been neutralized with a sodium or potassium salt. It is particularly preferred to use polybutylene terephthalate having an intrinsic viscosity of at least about 0.7 dL/g. PBT having a higher intrinsic viscosity in the range of 0.9 to 1.3dL/g can be used in applications where improved mechanical properties are required, such as improved tensile strength and elongation at break.
The preferred polysulfone resin comprises one or more of polysulfone PSF, methylene polysulfone PSU-2, polyether sulfone PES and polyphenylene sulfone PPSU. More preferably, PSF having a weight average molecular weight of 4 to 10 ten thousand is used. It is particularly preferred to use a PSF having a weight average molecular weight of 5 to 6 ten thousand.
The preferred high light-transmission composite synergist comprises one or more than two of polyethylene terephthalate-1, 4-cyclohexane dimethanol ester (PETG), poly (1, 4-cyclohexane dimethanol terephthalate) (PCTG) and 1, 4-cyclohexane di-adduct terephthalate-isophthalate (PCTA). More preferably, PETG with 1-4-cyclohexanedimethanol in an amount of 30-40% by mass, and particularly preferably PETG with 1-4-cyclohexanedimethanol in an amount of 34-36% by mass is used.
Preferred light-transmitting reinforcing fillers include one or a mixture of two or more of flat glass fibers, calcium sulfate flat whiskers, calcium carbonate flat whiskers, magnesium carbonate flat whiskers, basic magnesium sulfate whiskers and aluminum oxide magnesium whiskers. More preferably, flat glass fibers having a cross-sectional length of 20 to 35 μm, a width of 4 to 10 μm, and a glass fiber length of 2500 to 3000 μm are used. FIG. 3 is an SEM scanning electron micrograph of a preferred flat glass fiber in an embodiment of the present invention. Preferred magnesium carbonate whiskers have a flatness of 3 to 6, a cross-section of 0.3 to 1.2 μm in length, a width of 0.1 to 0.2 μm, and a whisker length of 15 to 30 μm, see FIG. 4. Preferred calcium carbonate whiskers have a flatness of 5 to 20, a cross-section of 0.5 to 5 μm in length, a width of 0.1 to 0.2 μm, and a whisker length of 10 to 50 μm, see FIG. 5. Preferred calcium sulfate whiskers have a flatness of 5-50, a cross-section of 0.5-10 μm in length, 0.1-0.2 μm in width, and a whisker length of 15-100 μm, see figure 6. The preferred aluminum oxide magnesium whiskers have a maximum length of 20 to 30mm, a diameter of 50 to 100 μm and an aspect ratio of 20 to 400, see FIG. 7. The preferred basic magnesium sulfate whisker has the average length of 15 microns, the diameter of 0.5 micron and the length-diameter ratio of 20-40, as shown in figure 8.
The preferable permeability-increasing agent is one or a mixture of more than two of sodium cobaltate, potassium cobaltate, sodium borate, potassium borate, sodium citrate, potassium citrate, sodium oxalate and potassium oxalate. More preferably, sodium cobaltate or potassium cobaltate is used. It is particularly preferred to use sodium cobaltate.
The preferred light-transmitting hydrolysis resistant agent is at least one of a monomeric carbodiimide, a polymeric carbodiimide, and a polymeric chain extender containing an epoxy functional group. More preferably, liquid type and solid type polymeric carbodiimides are used. It is particularly preferable to use a solid type polymeric carbodiimide.
Preferred flame retardants are at least one of phenoxypolyphosphazenes and resorcinol bis (di-2, 6-xylyl) phosphate. More preferably, resorcinol bis (di-2, 6-xylyl) phosphate is used.
The preferred lubricant is at least one of sodium stearate, calcium stearate, aluminum stearate, zinc stearate, and magnesium stearate. More preferably, sodium stearate is used.
As the antioxidant used in the present invention, there is no particular limitation, and any commercially available product can be used. The antioxidant may include at least one of phenols, phosphites, amines, hindered phenols.
The polyester composite of the present invention may contain other additives such as dyes, pigments, mold release agents, copper salt heat stabilizers, ultraviolet stabilizers, and the like, in addition to the above components, provided that they do not affect the physical properties, hydrolysis resistance, or flame retardancy of the composition.
The polyester composite of the present invention is in the form of a blend of molten mixtures in which all the polymeric components are well dispersed in each other and all the non-polymeric ingredients are uniformly dispersed in and bound by the polymer matrix, such that the blend forms a unified whole. The blend can be prepared by mixing the component materials using a single screw extruder or a twin screw extruder, with a twin screw extruder being particularly preferred to obtain a polyester composite material having excellent properties. Alternatively, some of the materials may be mixed in an extruder while other materials may then be added and further melt mixed until homogeneous. In the preparation of the hydrolysis-resistant reinforced flame-retardant polyester composite material, the mixing sequence can be as follows: the individual components may be melted in one process, or the filler and/or other components may be fed from a side feeder, and so forth, as will be appreciated by those skilled in the art.
Example 1
Adding polyester resin, polysulfone resin, high-light-transmittance filler, halogen-free flame retardant, hydrolysis resistance agent, antioxidant and lubricant into a high-speed mixer according to the proportion, uniformly mixing, adding into a feeder of an extruder, and granulating by a double-screw extruder at the granulation temperature range of 250-310 ℃ and the rotation speed range of 250-600 rpm to obtain the hydrolysis-resistant reinforced flame-retardant polyester composite particles. The resulting pellets were injection molded into standard bars and tested as follows:
tensile strength: ISO 527
Impact strength of the simply supported beam notch: ISO 179
Flame retardant performance (1.6 mm): UL94
Laser transmittance: the size of the sample strip is 125mm 1 mm 6mm, and the laser transmission rate is measured by a laser transmission rate measuring instrument, and the laser wavelength is 960nm.
Laser welding strength: the size of the sample strip is 125mm < 13mm < 1.6mm, the light absorption and transmission sample strips are welded by a laser welding instrument, the width of a welding wire is 2mm, each group of welding tests is 5 sample strips, the sample strips are kept stand for 24 hours at normal temperature after welding, and a universal testing machine is adopted to perform tensile test to obtain the welding strength.
Hydrolysis resistance: and (4) after being boiled in water at 70 ℃ for 168 hours, testing the tensile strength and the notch impact strength, and calculating the performance retention rate.
Comparative example
The differences between comparative examples 1-4 and examples 1-6 are in the components and the mixture ratio of the formulation system, and the specific mixture ratio is shown in Table 1.
TABLE 1 formulation
As can be seen from fig. 1, the polyester composite manufactured using the examples had excellent laser transmittance and welding strength during laser welding in each case.
As can be seen from FIG. 2, the polyester composite produced using the examples has excellent hydrolysis resistance in each case against the boiling process.
Unless otherwise specified, in the present invention, if the terms "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate the orientation or positional relationship indicated based on the actual shown orientation or positional relationship, it is only for convenience of describing the present invention and simplifying the description, but it does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, therefore, the terms describing the orientation or positional relationship in the present invention are only used for exemplary illustration and are not to be construed as limiting the patent, and it is possible for a person having ordinary skill in the art to combine the embodiments and understand the specific meaning of the above terms according to the specific situation.
Unless expressly stated or limited otherwise, the terms "disposed," "connected," and "connected" are to be construed broadly and encompass, for example, being fixedly connected, detachably connected, or integrally connected; the connection may be direct or indirect through an intermediate medium, and the connection may be internal to the two elements. The specific meanings of the above terms in the present invention can be understood in a specific case to those of ordinary skill in the art.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A hydrolysis-resistant flame-retardant polyester composite material capable of being welded by laser is characterized by comprising the following components in parts by weight:
10-40 parts of polyester resin;
10-40 parts of polysulfone resin;
5-20 parts of a high-light-transmission synergist;
10-50 parts of light-transmitting reinforced filler;
0.3-1.0 part of light-transmitting hydrolysis-resistant agent;
3-10 parts of a compatilizer;
5-20 parts of a halogen-free flame retardant;
0.2-1.0 part of lubricant;
0.2-1.0 part of antioxidant;
0.3-0.5 part of anti-reflection agent.
2. The laser-weldable hydrolysis-resistant flame-retardant polyester composite material as claimed in claim 1, wherein the polyester resin is one or a mixture of two or more of polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate; at least some of the end groups of said polyester have been neutralized with a sodium or potassium salt; the polysulfone resin is one or a mixture of more than two of polysulfone, polysulfone containing methylene, polyethersulfone and polyphenylsulfone.
3. The laser-weldable hydrolysis-resistant flame-retardant polyester composite material as claimed in claim 1, wherein the high-transparency synergist is a non-crystalline copolyester, specifically one or a mixture of more than two of polyethylene terephthalate-1, 4-cyclohexanedimethanol ester, and terephthalic acid-isophthalic acid-1, 4-cyclohexanediaddition ester.
4. The laser-weldable polyester composite material resistant to hydrolysis and flame retardance as claimed in claim 1, wherein said light-transmitting reinforcing filler is one or a mixture of two or more of flat glass fibers, calcium sulfate flat whiskers, calcium carbonate flat whiskers, magnesium carbonate flat whiskers, basic magnesium sulfate whiskers and aluminum magnesium oxide whiskers.
5. The laser-weldable hydrolysis-resistant flame-retardant polyester composite material as claimed in claim 1, wherein the anti-reflection agent is one or a mixture of more than two of sodium cobaltate, potassium cobaltate, sodium borate, potassium borate, sodium citrate, potassium citrate, sodium oxalate and potassium oxalate.
6. The laser-weldable hydrolysis-resistant flame-retardant polyester composite material as claimed in claim 1, wherein the light-transmissive hydrolysis-resistant agent is at least one of monomeric carbodiimide and polymeric carbodiimide.
7. The laser weldable hydrolysis resistant flame retardant polyester composite of claim 1, wherein the compatibilizer is a hydrogenated styrene-butadiene block copolymer; the antioxidant is at least one of phenols, phosphites, amines and hindered phenol antioxidants.
8. The laser-weldable hydrolysis-resistant flame-retardant polyester composite material as claimed in claim 1, wherein the lubricant is at least one of sodium stearate, calcium stearate, aluminum stearate, and magnesium stearate.
9. The laser weldable hydrolysis resistant flame retardant polyester composite of claim 1, wherein the halogen free flame retardant is at least one of phenoxypolyphosphazene and resorcinol bis (di-2, 6-xylyl) phosphate.
10. The method for preparing the laser-weldable hydrolysis-resistant flame-retardant polyester composite material according to any one of claims 1 to 9, comprising the following steps: the hydrolysis-resistant reinforced flame-retardant polyester composite material is prepared by uniformly mixing polyester resin, glass fiber, halogen-free flame retardant, hydrolysis resistance agent, antioxidant and lubricant according to a ratio, adding the mixture into a feeder of an extruder, and granulating by a double-screw extruder at a granulation temperature range of 250-310 ℃ and a rotation speed range of 250-600 rpm.
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| CN116515258A (en) * | 2023-04-25 | 2023-08-01 | 金发科技股份有限公司 | PBT composite material and preparation method and application thereof |
| CN118772637A (en) * | 2024-06-28 | 2024-10-15 | 浙江兄弟新材料有限公司 | Laser-weldable polyphenylene sulfide composite material and preparation method thereof |
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