CN112646363A - Halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material, preparation method thereof, product thereof and preparation method of product - Google Patents
Halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material, preparation method thereof, product thereof and preparation method of product Download PDFInfo
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- CN112646363A CN112646363A CN202011503689.1A CN202011503689A CN112646363A CN 112646363 A CN112646363 A CN 112646363A CN 202011503689 A CN202011503689 A CN 202011503689A CN 112646363 A CN112646363 A CN 112646363A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 101
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000003365 glass fiber Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000002245 particle Substances 0.000 claims abstract description 66
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000000314 lubricant Substances 0.000 claims abstract description 15
- 239000012745 toughening agent Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 238000001746 injection moulding Methods 0.000 claims abstract description 13
- 239000002216 antistatic agent Substances 0.000 claims abstract description 12
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 26
- 238000012545 processing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 2
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract description 2
- 229920002292 Nylon 6 Polymers 0.000 description 88
- 230000000052 comparative effect Effects 0.000 description 17
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 poly (aluminium dihydrogen dicyanamide phosphate Chemical compound 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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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
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- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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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
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Abstract
The invention provides a halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material, which comprises halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles; the halogen-free flame-retardant glass fiber reinforced PA6 particle comprises the following raw material components in parts by weight: medium viscosity PA 620-55 parts, glass fiber 20-50 parts, halogen-free flame retardant 10-25 parts, toughening agent 2-8 parts, antioxidant 0.1-1 part and lubricant 0.1-1 part; the permanent antistatic PA6 particle comprises the following raw material components in parts by weight: 620-70 parts of low-viscosity PA, 30-80 parts of permanent antistatic agent and 0.1-1 part of antioxidant. According to the invention, by utilizing the characteristic that the melt index of the permanent antistatic PA6 particles is far greater than that of the halogen-free flame-retardant glass fiber reinforced PA6 particles, when the product is formed by injection molding, the high-melt-index permanent antistatic PA6 is in a coating state on the halogen-free flame-retardant glass fiber reinforced PA6, and the product which is excellent in mechanical property, good in flame-retardant effect, continuous and stable in antistatic effect, good in surface gloss, free of glass fiber exposure and flame retardant precipitation phenomenon can be prepared.
Description
Technical Field
The invention relates to the technical field of organic polymer materials, in particular to a halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material, a preparation method thereof, a product thereof and a preparation method of the product.
Background
The glass fiber reinforced nylon 6(GFPA6) has the advantages of excellent mechanical property, good heat resistance, good dimensional stability, light weight, corrosion resistance, high efficiency in forming and processing and the like, so that the defects of large and heavy steel density, high possibility of corrosion, easy generation of electric sparks, difficulty in carrying and mounting, high processing and manufacturing cost, high maintenance cost and the like of the steel can be overcome by replacing the traditional steel parts with the GFPA6 under a coal mine. In recent years, with the advance of "replacing steel with plastic", GFPA6 has been widely used in the fields of coal mine mechanical parts, coal mine electronic appliance housings, and the like. However, the PA6 material has high surface resistivity which reaches 1014～1015Omega, surface static electricity is easy to accumulate, and fire or explosion is easy to be caused by surface discharge. GFPA6 belongs to flammable materials, the combustion speed is high, the heat release is large, and the flame retardant property of the material can be further reduced due to the 'wick' effect caused by the addition of glass fibers, so when GFPA6 is used as a mining material, flame retardant antistatic treatment must be carried out. The GFPA6 traditional flame-retardant antistatic method adopts a halogen-containing flame retardant and a surfactant type antistatic agent, but a halogen-containing flame-retardant system can generate toxic smoke during combustion, seriously harms human health and causes environmental pollution, and the surfactant type antistatic agent can be gradually separated out along with the lapse of time, so that the antistatic effect is attenuated, and finally, the halogen-containing flame-retardant system can completely lose efficacy. When the flame-retardant antistatic GFPA6 material is applied to a closed environment of a coal mine, the interior of the closed environment is complex in topography and severe in environment and is rich in corrosive gas and explosive gas, and the traditional flame-retardant antistatic GFPA6 material is easy to cause secondary disasters. Meanwhile, when the traditional flame-retardant antistatic GFPA6 material is prepared into a product by injection molding, glass fibers are easy to separate out of the surface of the product, and the appearance of the product is seriously influenced.
Therefore, there is a need to develop a new halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material, and to prepare a product with high surface quality and excellent flame-retardant antistatic performance by using the composite material.
Disclosure of Invention
In view of the above, the invention provides a halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material, and a halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with excellent flame-retardant antistatic performance and high surface quality is prepared by using the composite material, and also provides a preparation method of the composite material and a preparation method of the composite material product.
The halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material comprises halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles;
the halogen-free flame-retardant glass fiber reinforced PA6 particle comprises the following raw material components in parts by weight: medium viscosity PA 620-55 parts, glass fiber 20-50 parts, halogen-free flame retardant 10-25 parts, toughening agent 2-8 parts, antioxidant 0.1-1 part and lubricant 0.1-1 part;
the permanent antistatic PA6 particle comprises the following raw material components in parts by weight: 620-70 parts of low-viscosity PA, 30-80 parts of permanent antistatic agent and 0.1-1 part of antioxidant.
Further, the viscosity of the medium viscosity PA6 is 2.4-2.9, and the viscosity of the low viscosity PA6 is less than or equal to 2.1. The selected PA6 can be one or more, and the viscosity can meet the requirement.
Further, the halogen-free flame retardant is a mixture of aluminum diethylphosphinate and aluminum polydicyanamide dihydrogen phosphate; the mass ratio of the aluminum diethylphosphinate to the poly (aluminium dihydrogen melamine phosphate) is (8-24): (1-8). The structural schematic diagram of the poly (aluminium dihydrogen dicyanamide phosphate) (MPAP) is as follows:
further, the permanent antistatic agent is a polyether ester amide permanent antistatic agent; the glass fiber is alkali-free glass fiber; the antioxidant is a phenol high-performance antioxidant 1098; the toughening agent is at least one of maleic anhydride grafted POE and acrylate grafted POE; the lubricant is at least one of silicone and grafted silicone.
The preparation method of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material comprises the following steps:
taking the medium viscosity PA6, the glass fiber, the halogen-free flame retardant, the toughening agent, the antioxidant and the lubricant according to the proportion, uniformly mixing to obtain a mixed material A, taking the low viscosity PA6, the permanent antistatic agent and the antioxidant according to the proportion, uniformly mixing to obtain a mixed material B, respectively carrying out melt extrusion and cooling granulation on the mixed material A and the mixed material B by adopting a double-screw extruder under the condition that the processing temperature is 220-250 ℃, then placing the obtained particles in an oven with the working temperature of 110-130 ℃, and drying for 4-6h to obtain the halogen-free flame-retardant glass fiber reinforced PA6 particles and the permanent antistatic PA6 particles.
The invention also provides a high-surface-quality halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product, and the raw materials of the product comprise halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles.
Further, the mass ratio of the halogen-free flame-retardant glass fiber reinforced PA6 particles to the permanent antistatic PA6 particles is (6-9): (1-4), preferably (7-8): (2-3).
The preparation method of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with high surface quality, provided by the invention, comprises the following steps:
uniformly mixing the halogen-free flame-retardant glass fiber reinforced PA6 particles and the permanent antistatic PA6 particles according to the proportion, and then placing the mixed materials in an injection molding machine with the processing temperature of 240-270 ℃ and the injection pressure of 90-120MPa for injection molding to obtain the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with high surface quality. The preparation method has simple and easily-controlled process and is easy to realize industrialization.
The invention has the beneficial effects that:
the composite material provided by the invention comprises halogen-free flame-retardant glass fiber reinforced PA6 particles prepared from a medium-viscosity PA6 base material and permanent antistatic PA6 particles prepared from a low-viscosity PA6 base material, and utilizes the characteristic that the melt index of the permanent antistatic PA6 particles is far greater than that of the halogen-free flame-retardant glass fiber reinforced PA6 particles, when the product is formed by injection molding, the high-melt-index permanent antistatic PA6 has high flow speed, and is in a coating state on the halogen-free flame-retardant glass fiber reinforced PA6, most of the permanent antistatic PA6 is distributed on the surface of the injection molded product, while most of glass fibers and flame retardants which influence the surface quality of the product are easy to separate out are distributed in the product, the problem that when the product is formed by injection molding the PA6 composite material directly prepared by mixing and extruding various raw material components in the traditional process, the glass fibers and the flame retardants are easy to separate out is solved, the effect, meanwhile, the permanent antistatic PA6 is distributed on the surface of the product in most parts, so that the surface resistance of the product can be greatly reduced.
The initial decomposition temperature of the poly-di-melamine aluminum dihydrogen phosphate (MPAP) adopted by the invention is up to 349 ℃, the poly-di-melamine aluminum dihydrogen phosphate (MPAP) and diethyl aluminum phosphinate are compounded to form the halogen-free flame retardant, the phosphorus, nitrogen and aluminum ternary synergistic effect is adopted, the flame retardant effect is excellent, the thermal stability is good, and the migration is not easy. Solves the problems of poor heat resistance, low flame retardant efficiency, easy precipitation and the like of the traditional triazine derivatives such as Melamine Cyanurate (MCA), melamine polyphosphate (MPP) and aluminum diethylphosphinate in composite use.
The halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with high surface quality prepared by the invention has the advantages of excellent mechanical property, good flame-retardant effect, continuous and stable antistatic effect, good surface gloss, no glass fiber exposure and no flame retardant precipitation phenomenon, and can be used in the flame-retardant antistatic field with high requirements on various colors and surface appearances.
Drawings
The invention is further described below with reference to the following figures and examples:
FIG. 1 is a photograph of the appearance of articles made in examples 1-3 and comparative examples 1-3, wherein: (1) the photograph of the appearance of the article prepared in example 1, (2) the photograph of the appearance of the article prepared in example 2, (3) the photograph of the appearance of the article prepared in example 3, (4) the photograph of the appearance of the article prepared in comparative example 1, (5) the photograph of the appearance of the article prepared in comparative example 1, and (6) the photograph of the appearance of the article prepared in comparative example 1.
Detailed Description
The following are specific examples:
example 1
The halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material provided by the embodiment comprises halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles; the raw material component proportion of the halogen-free flame-retardant glass fiber reinforced PA6 particle and the raw material component proportion of the permanent antistatic PA6 particle are shown in the following table:
wherein the toughening agent is maleic anhydride grafted POE, and the lubricant is silicone. The toughening agent can be replaced by acrylate grafted POE or a mixture of maleic anhydride grafted POE and acrylate grafted POE, and the lubricant can be replaced by grafted silicone or a mixture of silicone and grafted silicone.
The preparation method of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material provided by the embodiment comprises the following steps: taking the medium viscosity PA6, the glass fiber, the halogen-free flame retardant, the toughening agent, the antioxidant and the lubricant according to the proportion, uniformly mixing to obtain a mixed material A, taking the low viscosity PA6, the permanent antistatic agent and the antioxidant according to the proportion, uniformly mixing to obtain a mixed material B, respectively carrying out melt extrusion and cooling granulation on the mixed material A and the mixed material B by adopting a double-screw extruder under the condition that the processing temperature is 220-250 ℃, then placing the obtained particles in an oven with the working temperature of 120 ℃, and drying for 4h to obtain the halogen-free flame-retardant glass fiber reinforced PA6 particles and the permanent antistatic PA6 particles. The twin-screw extruder has a plurality of working zones, and the temperature of each working zone is set according to the range of the processing temperature when the twin-screw extruder is set.
The embodiment also provides a halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with high surface quality, and the raw materials of the product comprise halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles in a mass ratio of 8: 2. The preparation method of the product comprises the following steps: uniformly mixing the halogen-free flame-retardant glass fiber reinforced PA6 particles and the permanent antistatic PA6 particles according to the proportion, and then placing the mixed materials in an injection molding machine with the processing temperature of 240-270 ℃ and the injection pressure of 100MPa for injection molding to obtain the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with high surface quality. The injection molding machine has a plurality of working sections, and the temperature of each working section is set in accordance with the range of the processing temperature when setting.
Example 2
The halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material provided by the embodiment comprises halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles; the raw material component proportion of the halogen-free flame-retardant glass fiber reinforced PA6 particle and the raw material component proportion of the permanent antistatic PA6 particle are shown in the following table:
in this example, the toughening agent and the lubricant were the same as in example 1.
The preparation method of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material provided by the embodiment is the same as that of embodiment 1.
The embodiment also provides a halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with high surface quality, and the raw materials of the product comprise halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles in a mass ratio of 7: 3. The preparation of the article was the same as in example 1.
Example 3
The halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material provided by the embodiment comprises halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles; the raw material component proportion of the halogen-free flame-retardant glass fiber reinforced PA6 particle and the raw material component proportion of the permanent antistatic PA6 particle are shown in the following table:
in this example, the toughening agent and the lubricant were the same as in example 1.
The preparation method of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material provided by the embodiment is the same as that of embodiment 1.
The embodiment also provides a halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with high surface quality, and the raw materials of the product comprise halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles in a mass ratio of 8: 2. The preparation of the article was the same as in example 1.
Comparative example 1
The raw material components of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material provided by the comparative example are as follows:
wherein, the toughening agent and the lubricant are the same as those in the embodiment 1.
The preparation method of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material comprises the following steps: the preparation method comprises the steps of uniformly mixing the raw material components according to the proportion to obtain a mixed material, carrying out melt extrusion and cooling granulation on the mixed material by adopting a double-screw extruder at the processing temperature of 220-250 ℃, then placing the obtained particles in an oven at the working temperature of 120 ℃, and drying for 4 hours to obtain the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 particles.
In the comparative example, the obtained halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 particles were injection-molded in an injection molding machine with a processing temperature of 240 ℃ and an injection pressure of 100MPa to obtain a comparative product.
Comparative example 2
The raw material components of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material provided by the comparative example are as follows:
wherein, the toughening agent and the lubricant are the same as those in the example 2.
The preparation method of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material and the method for preparing a comparative product by using the composite material are the same as the comparative example 1.
Comparative example 3
The raw material components of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material provided by the comparative example are as follows:
wherein, the toughening agent and the lubricant are the same as those in the embodiment 3.
The preparation method of the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material and the method for preparing a comparative product by using the composite material are the same as the comparative example 1.
The PA6 composite articles provided in examples 1-3 and comparative examples 1-3 were subjected to performance testing, the results of which are shown in the following table:
as can be seen from the above table, the halogen-free flame-retardant glass fiber reinforced PA6 particles and the permanent antistatic PA6 particles are prepared according to respective formulations, and then the halogen-free flame-retardant glass fiber reinforced PA6 particles and the permanent antistatic PA6 particles are adopted according to a specific proportion to prepare the product by injection molding, so that the surface quality of the product can be improved, the product with high surface quality can be prepared, meanwhile, the surface resistance of the product can be greatly reduced, and the antistatic effect is continuous and stable.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (8)
1. A halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material is characterized in that: comprises halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles;
the halogen-free flame-retardant glass fiber reinforced PA6 particle comprises the following raw material components in parts by weight: medium viscosity PA 620-55 parts, glass fiber 20-50 parts, halogen-free flame retardant 10-25 parts, toughening agent 2-8 parts, antioxidant 0.1-1 part and lubricant 0.1-1 part;
the permanent antistatic PA6 particle comprises the following raw material components in parts by weight: 620-70 parts of low-viscosity PA, 30-80 parts of permanent antistatic agent and 0.1-1 part of antioxidant.
2. The halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material as claimed in claim 1, characterized in that: the viscosity of the medium viscosity PA6 is 2.4-2.9, and the viscosity of the low viscosity PA6 is less than or equal to 2.1.
3. The halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material as claimed in claim 1, characterized in that: the halogen-free flame retardant is a mixture of aluminum diethylphosphinate and aluminum polydicyanamide dihydrogen phosphate salt; the mass ratio of the aluminum diethylphosphinate to the poly (aluminium dihydrogen melamine phosphate) is (8-24): (1-8).
4. The halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material as claimed in claim 1, characterized in that: the permanent antistatic agent is polyether ester amide permanent antistatic agent; the glass fiber is alkali-free glass fiber; the antioxidant is a phenol high-performance antioxidant 1098; the toughening agent is at least one of maleic anhydride grafted POE and acrylate grafted POE; the lubricant is at least one of silicone and grafted silicone.
5. A preparation method of a halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material is characterized by comprising the following steps: the method comprises the following steps:
taking the medium viscosity PA6, the glass fiber, the halogen-free flame retardant, the toughening agent, the antioxidant and the lubricant according to the proportion, uniformly mixing to obtain a mixed material A, taking the low viscosity PA6, the permanent antistatic agent and the antioxidant according to the proportion, uniformly mixing to obtain a mixed material B, respectively carrying out melt extrusion and cooling granulation on the mixed material A and the mixed material B by adopting a double-screw extruder under the condition that the processing temperature is 220-250 ℃, then placing the obtained particles in an oven with the working temperature of 110-130 ℃, and drying for 4-6h to obtain the halogen-free flame-retardant glass fiber reinforced PA6 particles and the permanent antistatic PA6 particles.
6. A halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with high surface quality is characterized in that: the raw materials of the product comprise halogen-free flame-retardant glass fiber reinforced PA6 particles and permanent antistatic PA6 particles.
7. The high surface quality halogen-free flame retardant permanent antistatic glass fiber reinforced PA6 composite product according to claim 6, characterized in that: the mass ratio of the halogen-free flame-retardant glass fiber reinforced PA6 particles to the permanent antistatic PA6 particles is (6-9): (1-4).
8. A preparation method of a halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with high surface quality is characterized by comprising the following steps: the method comprises the following steps:
uniformly mixing the halogen-free flame-retardant glass fiber reinforced PA6 particles and the permanent antistatic PA6 particles according to the proportion, and then placing the mixed materials in an injection molding machine with the processing temperature of 240-270 ℃ and the injection pressure of 90-120MPa for injection molding to obtain the halogen-free flame-retardant permanent antistatic glass fiber reinforced PA6 composite material product with high surface quality.
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| CN115637044A (en) * | 2022-11-18 | 2023-01-24 | 聚力防静电科技(广东)有限公司 | Halogen-free flame-retardant permanent antistatic polyamide composition and preparation method thereof |
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Application publication date: 20210413 |