CN115746547A - Irradiation crosslinking long glass fiber reinforced high-temperature-resistant nylon composite material and preparation method thereof - Google Patents
Irradiation crosslinking long glass fiber reinforced high-temperature-resistant nylon composite material and preparation method thereof Download PDFInfo
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- 238000004132 cross linking Methods 0.000 title claims abstract description 45
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 5
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 claims description 5
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- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 claims description 4
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- GUTLYIVDDKVIGB-OUBTZVSYSA-N Cobalt-60 Chemical compound [60Co] GUTLYIVDDKVIGB-OUBTZVSYSA-N 0.000 claims description 3
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- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
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- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 4
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- 239000010941 cobalt Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
An irradiation cross-linked long glass fiber reinforced high temperature resistant nylon composite material comprises: 45-90 parts of polyamide resin, 10-60 parts of long glass fiber, 0.1-3 parts of stabilizer, 0.1-5 parts of crosslinking sensitizer, 0.1-1 part of lubricant and 0.1-5 parts of functional filler. The preparation method comprises the following steps: 1. premixing a stabilizer, a crosslinking sensitizer, a lubricant and a functional filler in a high-speed mixer to prepare a powder mixture; 2. and adding the polyamide resin and powder mixture according to the proportion through a weight loss scale from a main feed inlet of a double-screw extruder, melting and plasticizing in the double-screw extruder, and then granulating and drying through a long glass fiber mould head to obtain the irradiation crosslinking long glass fiber reinforced high temperature resistant nylon composite material. The irradiation crosslinking long glass fiber reinforced polyamide composite material can not generate melting collapse at the local temperature of 400 ℃ and under a certain load, so that a workpiece keeps high dimensional stability under the extreme temperature condition.
Description
Technical Field
The invention relates to the field of modification processing of polymer composite materials, in particular to an irradiation crosslinking long glass fiber reinforced high-temperature-resistant nylon composite material and a preparation method thereof.
Background
The irradiation crosslinking is a technical means for initiating crosslinking reaction between polymer long chains by using various radiations, and the irradiation source can be selected from electron beams, gamma rays, neutron beams, particle beams and the like according to the category and performance requirements of the polymer.
The thermoplastic engineering plastic can be rapidly melted and plasticized at a certain temperature, and can be conveniently and rapidly manufactured into products with various shapes by injection molding, mould pressing and other forming modes, which is a remarkable advantage of thermoplastic materials compared with thermosetting plastics. But the thermoplastic material can not compete with the thermosetting plastic in terms of dimensional stability and instantaneous high temperature resistance, so that the application scenes are limited. Particularly in electric appliances and automobile parts, the local temperature is far higher than the melting point of the plastic in an instant high-temperature environment, which can cause instant melting of materials, failure of parts and accidents.
The Polyamide (PA) is the variety with the largest yield, the largest variety and the widest application among five general engineering plastics. The method has wide application in the fields of electric appliances, automobiles, machinery, construction, textile, medical treatment and the like. The irradiation crosslinking long glass fiber reinforced high temperature resistant nylon composite material is prepared by using an irradiation crosslinking technology, and the easy processing and forming performance of a thermoplastic material and the excellent size stability and instantaneous high temperature resistance of a thermosetting material are combined, so that the irradiation crosslinking long glass fiber reinforced polyamide composite material can not be subjected to melting collapse at the local temperature of 400 ℃ under a certain load, a workpiece can keep good high size stability under the extreme temperature condition, and the safety and reliability of the product can be improved.
The development and application of radiation cross-linked polyamide materials are still in the primary stage, and the types of materials are few. Existing radiation-crosslinked polyamide materials still have certain disadvantages and present certain risks at the end of use.
Chinese patent No. CN112079967A discloses a radiation cross-linked nylon material and a preparation method thereof, wherein a polyfunctional monomer cross-linking agent, a heat stabilizer and an ethylene-vinyl acetate copolymer are added into nylon 6 or nylon 66 resin for blending and extrusion, and then a cobalt source and an electron accelerator are used for irradiation, and the irradiation dose is 10-200 kGy. Compared with the traditional nylon 6/nylon 66, the heat resistance and the mechanical property are improved, and the water absorption of the material is reduced to a certain extent, so that the material can be a substitute product of a high-price and high-heat-resistance thermoplastic material. However, the material of the invention can still flow under the conditions of 300 ℃ and 1.2kg, and only the material is described to be subjected to micro-crosslinking, a stable non-melting and non-melting net structure is not formed, and the material cannot be applied to a high-temperature environment with short time at higher temperature.
Therefore, it is an object of the present invention to overcome the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide an irradiation crosslinking long glass fiber reinforced high-temperature resistant nylon composite material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention on the material level is as follows:
an irradiation crosslinking long glass fiber reinforced high temperature resistant nylon composite material comprises the following raw materials in parts by mass:
45-90 parts of polyamide resin;
10-60 parts of long glass fiber;
0.1-3 parts of a stabilizer;
0.1 to 5 portions of crosslinking sensitizer;
0.1-1 part of a lubricant;
0.1-5 parts of functional filler.
1. According to a further technical scheme, the following components in parts by mass are preferably selected as raw materials:
55-80 parts of polyamide resin;
20-50 parts of long glass fiber;
0.1-1 part of stabilizer;
2-5 parts of a crosslinking sensitizer;
0.2-1 part of a lubricant;
0.1-3 parts of functional filler.
2. In a further technical scheme, the polyamide resin is one or more of aliphatic polyamide resins PA6, PA46, PA56, PA66, PA11, PA12, PA610, PA1010, PA1012, PA612 and PA 1212.
3. In a further technical scheme, the long glass fiber is E glass fiber with the length of 5-30 mm and the diameter of 9-14 mu m.
4. In a further technical scheme, the stabilizer is one or more of an inorganic copper compound and an organic copper salt complex, or a mixture of the inorganic copper compound and a bromine-containing compound. The preferable stabilizer is one or more of cuprous iodide, potassium bromide, cuprous bromide, copper stearate and a tri (tribromoneopentyl) phosphate mixture.
5. In a further technical scheme, the crosslinking sensitizer is one or more of high-boiling point and low-volatility trimethyl allyl isocyanate (TMAIC), triallyl isocyanurate (TAIC) and tris (2-hydroxyethyl) isocyanurate Triacrylate (THEICA).
6. In a further technical scheme, the crosslinking sensitizer is preferably one or a mixture of trimethyl allyl isocyanate (TMAIC) and tris (2-hydroxyethyl) isocyanurate triacrylate (THEIPTA).
7. According to a further technical scheme, the lubricant is one or more of silicone, OP wax, polyester wax and ethylene-acrylic acid copolymer.
8. According to a further technical scheme, the functional filler is one or more of glass beads, hollow glass beads, spherical silicon oxide, calcium carbonate, talcum powder, mica and whiskers.
In order to achieve the purpose, the technical scheme adopted by the invention in the aspect of the method is as follows:
a preparation method of an irradiation cross-linked long glass fiber reinforced high-temperature-resistant nylon composite material comprises the following steps:
premixing a stabilizer, a crosslinking sensitizer, a lubricant and a functional filler in a high-speed mixer to prepare a powder mixture;
and step two, adding the dried polyamide resin and the powder mixture according to the proportion through a weightlessness scale from a double-screw extruder to a main feed inlet, melting and plasticizing in the double-screw extruder, and then granulating and drying through a long glass fiber die head to obtain the irradiation crosslinking long glass fiber reinforced high temperature resistant nylon composite material.
1. The further technical scheme is that the irradiation crosslinking long glass fiber reinforced high temperature resistant nylon product is obtained by injection molding and irradiation processing by an electron accelerator or cobalt-60 with the irradiation dose of 8-20 megarads (megarads).
The working principle and the advantages of the invention are as follows:
according to the irradiation crosslinking long glass fiber reinforced high-temperature-resistant nylon composite material, a crosslinking sensitizer with high boiling point, low volatility and low self-polymerization tendency is adopted, so that the crosslinking result is stable; compared with short glass fiber or non-reinforced material, the long glass fiber and functional filler reinforced nylon composite material has excellent mechanical properties, high dimensional stability and low warping property, and the long glass fiber can better form the functions of supporting and bridging in the state that the temperature is higher than the melting point, so that the shape of the product is stabilized, the deformation of the product at a short-term high temperature is avoided, the product bears higher temperature and higher pressure, and the application applicability of nylon is widened.
According to the invention, the irradiation crosslinking long glass fiber reinforced nylon composite material is adopted, so that the mechanical properties such as tensile strength, flexural modulus, flexural strength and the like of the nylon material are greatly improved, meanwhile, the short-time high temperature pressure resistance of the irradiation crosslinking reinforced nylon material is greatly improved, the material can bear higher temperature and higher pressure, and the safety and reliability of the material are greatly improved.
The nylon composite material is prepared by a double-screw extruder, the product is subjected to injection molding or compression molding, and the product is irradiated by an electron beam irradiation accelerator or cobalt 60, so that the final product has good mechanical properties and dimensional stability, and can meet the requirements that the material has good heat deformation resistance under an extremely short-time high-temperature environment, and the safety, reliability and application range are greatly improved.
Detailed Description
The invention is further described below with reference to the following examples:
the embodiment is as follows: the present disclosure will be described in detail, and it is understood that variations and modifications can be made by the techniques taught in the present disclosure without departing from the spirit and scope of the present disclosure by those skilled in the art after understanding the embodiments of the present disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The singular forms "a", "an", "the" and "the", as used herein, also include the plural forms. As used herein, the terms "comprising," "including," "having," and the like are open-ended terms that mean including but not limited to.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
The raw materials and auxiliary information used in the examples and comparative examples are as follows:
polyamide 66 resin (PA 66), nerma ERP24;
polyamide 12 resin (PA 12), japanese yu 3014U;
polyamide 6 resin (PA 6), barlingite BL3240;
short glass fibers: mount Taishan T435N;
long glass fiber: the giant rock EDR14-2000-988A;
a stabilizer: bruggculen, H3336;
functional filler: hollow glass microspheres, saint lyte HM30;
crosslinking and crosslinking agent: fangruida, high purity TAIC;
anbang chemical, TMAIC (bp 402.7 ℃);
high crystallinity chemical, thecta (boiling point 360 ℃);
lubricant: STRUKTOL, V-WAX OP.
The embodiment is as follows: 0.1-1 part of stabilizer, 0.1-1 part of lubricant, 0.1-5 parts of functional filler and other powdery additives are premixed in a high-speed mixer to prepare a powder mixture, dried 45-90 parts of polyamide resin, 0.1-5 parts of crosslinking sensitizer and 0.1-7 parts of powder mixture are added from the main feed inlet of a double-screw extruder according to the proportion by a weightless scale, the mixture is melted and plasticized in the double-screw extruder at 200-280 ℃, and the mixture is granulated through a long glass fiber die head to obtain the irradiation crosslinking long glass fiber reinforced high temperature resistant nylon composite material. And (3) drying the irradiation crosslinked long glass fiber reinforced high-temperature-resistant nylon composite material, then performing injection molding processing, and performing irradiation treatment and testing.
Irradiation processing conditions: the electron beam irradiation dose was 150kGy and 200kGy.
The method for testing the content of the cross-linking agent in the injection molding sample comprises the following steps: using ethanol as a solvent, cutting an injection molding sample by 5g, and performing Soxhlet extraction at 100 ℃ for 24h, wherein the mass loss percentage before and after extraction is the content of the cross-linking agent.
The gel content test method of the irradiation cross-linked polyamide part comprises the following steps: using formic acid as a solvent, weighing 0.5g of chopped parts before and after irradiation, and ultrasonically dissolving for 6 hours at 60 ℃, wherein the difference value between formic acid insoluble substances after irradiation and formic acid insoluble substances before irradiation accounts for the mass percent of the dissolved substances before irradiation, namely the gel content.
Vicat softening evaluation: the test was carried out according to GB/T1633-2000, with the selection of 10N,120 ℃/min. The upper limit of the apparatus test is 300 ℃.
Hot-pressing resistance: evaluation was performed using an internal test method. A circular sample plate with a thickness of 1mm is pressed by using a press head of a soldering iron weighing 1.5 kg and at 400 ℃, and the hot pressing time is 10s. The heat and pressure resistance of the material was evaluated by the melting marks after hot pressing. O is indentation, + + + is almost no indentation, + + is slight indentation, + is not indentation but deeper.
Table 1: examples A1 to A8 and comparative examples A9 and A10, the respective component ratios and the respective performance tests of the products
As can be seen from the above table, comparative examples 1 and 2 are similar to the base resin formulations of examples 1, 2 and 3, respectively, but the crosslinking sensitizers TAC and TMPTMA with low boiling point are used, so that the gel content is low, the hot-pressing resistance is poor, and the Vicat softening temperature is low. The reason is that the temperature is high in the production process of the short glass fiber reinforced nylon 66, and high-speed friction is generated between the glass fibers and the screw meshing thread block rotating at high speed to cause local overheating, low-boiling-point crosslinking sensitizers such as TAC and TMPTMA are seriously volatilized, and the high temperature is easy to self-polymerize to fail. And the short glass fiber is used for reinforcement, so that the glass fiber has shorter retention length, and the framework effect is weaker than that of the long glass fiber.
In the embodiment 1-8, the long glass fiber reinforced nylon is produced through a die head of the die, the glass fiber is not rubbed and sheared with a thread block, and the plastic in a double-screw extruder is easy to plasticize and has stable temperature. And the boiling points of TMAIC and THEIPTA are far higher than the processing temperature, the volatilization is neglected, the self-polymerization tendency is far lower than that of TAC and TMPTMA, therefore, the crosslinking result is stable, and the heat resistance is excellent.
According to the embodiments and the respective proportions, the irradiation crosslinking long glass fiber reinforced high temperature resistant nylon composite material has stable and excellent performance, and the irradiation crosslinking long glass fiber reinforced polyamide composite material can not generate melting collapse at the local temperature of 400 ℃ and under a certain load by combining the easy processing and forming performance of a thermoplastic material and the excellent size stability and instantaneous high temperature resistance of a thermosetting material, so that a product keeps high size stability under the extreme temperature condition, the safety and reliability of the product can be improved, and the application range can be greatly improved.
The invention adopts trimethyl allyl isocyanate (TMAIC) and tris (2-hydroxyethyl) isocyanurate triacrylate (THEIPCTA) with higher boiling point, low volatility, low self-polymerization tendency and high reaction activity as crosslinking sensitizers, thereby avoiding a great deal of volatilization and self-polymerization of sensitizers such as TAIC, TAC, TMPTMA and the like in the production process and having stable crosslinking result; compared with short glass fiber or non-reinforced material, the long glass fiber and functional filler reinforced nylon composite material has excellent mechanical properties, high dimensional stability and low warping property, and the long glass fiber can better form the functions of supporting and bridging in the state that the temperature is higher than the melting point, so that the shape of the product is stabilized, the deformation at high temperature in a short period is avoided, and the product can bear higher temperature and higher pressure.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (10)
1. The irradiation crosslinking long glass fiber reinforced high temperature resistant nylon composite material is characterized in that:
the raw materials comprise the following components in parts by mass:
45-90 parts of polyamide resin;
10 to 60 parts of long glass fiber;
0.1 to 3 parts of a stabilizer;
0.1 to 5 portions of crosslinking sensitizer;
0.1 to 1 part of lubricant;
0.1 to 5 portions of functional filler.
2. The nylon composite of claim 1, wherein:
the raw materials comprise the following components in parts by mass:
55-80 parts of polyamide resin;
20 to 50 parts of long glass fiber;
0.1 to 1 part of stabilizer;
2 to 5 parts of crosslinking sensitizer;
0.2 to 1 part of a lubricant;
0.1 to 3 parts of functional filler.
3. The nylon composite of claim 1, wherein: the polyamide resin is one or more of aliphatic polyamide resins PA6, PA46, PA56, PA66, PA11, PA12, PA610, PA1010, PA1012, PA612 and PA 1212.
4. The nylon composite of claim 1, wherein: the long glass fiber is an E glass fiber with the length of 5-30mm and the diameter of 9-14 mu m.
5. The nylon composite of claim 1, wherein: the stabilizer is one or more of inorganic copper compound and organic copper salt complex.
6. The nylon composite of claim 1, wherein: the crosslinking sensitizer is one or more of high-boiling point and low-volatility trimethallyl allyl isocyanate, triallyl isocyanurate and tris (2-hydroxyethyl) isocyanurate triacrylate.
7. The nylon composite of claim 1, wherein: the lubricant is one or more of silicone, OP wax, polyester wax and ethylene-acrylic acid copolymer.
8. The nylon composite of claim 1, wherein: the functional filler is one or more of glass beads, hollow glass beads, spherical silicon oxide, calcium carbonate, talcum powder, mica and whiskers.
9. A preparation method of an irradiation crosslinking long glass fiber reinforced high-temperature-resistant nylon composite material, which is used for preparing the nylon composite material of any one of claims 1 to 8, and is characterized in that:
the preparation method comprises the following steps:
premixing a stabilizer, a crosslinking sensitizer, a lubricant and a functional filler in a high-speed mixer to prepare a powder mixture;
and step two, adding the dried polyamide resin and the powder mixture according to the proportion through a weight loss scale from a main feeding port of a double-screw extruder, melting and plasticizing in the double-screw extruder, adding long glass fibers through long glass fiber special equipment, and granulating and drying to obtain the irradiation crosslinking long glass fiber reinforced high-temperature resistant nylon composite material.
10. The method for preparing a nylon composite material according to claim 9, wherein:
and (3) performing injection molding, and performing irradiation processing by using an electron accelerator or cobalt-60 with the irradiation dose of 8-20 megarads to obtain the irradiation crosslinking long glass fiber reinforced high-temperature-resistant nylon product.
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