CN116178939A - Halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material and preparation method thereof - Google Patents
Halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 239000003063 flame retardant Substances 0.000 title claims abstract description 57
- 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 55
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 25
- 229920005610 lignin Polymers 0.000 claims abstract description 23
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 229920000856 Amylose Polymers 0.000 claims abstract description 18
- 239000000314 lubricant Substances 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 150000001721 carbon Chemical class 0.000 claims abstract description 13
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000013329 compounding Methods 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 229920001610 polycaprolactone Polymers 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 229920002261 Corn starch Polymers 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 3
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008120 corn starch Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical group NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 125000005498 phthalate group Chemical group 0.000 claims description 3
- -1 polysiloxane Polymers 0.000 claims description 3
- 229920001592 potato starch Polymers 0.000 claims description 3
- 150000004756 silanes Chemical class 0.000 claims description 3
- 229940037312 stearamide Drugs 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
-
- 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
Abstract
A halogen-free flame-retardant high GWIT high heat conduction polyamide 6 material relates to the technical field of high polymer materials, and comprises the following materials in parts by mass: polyamide 6:26-43 parts; and (3) heat conducting powder: 45-55 parts; modifying into a carbon agent: 5-8 parts of a lubricant; compounding an antioxidant: 0.3-0.8 part; and (3) a lubricant: 0.5-1.5 parts; MCA flame retardant: 5-8 parts of a lubricant; coupling agent: 0.5-1 part; the modified carbon agent is one or a mixture of lignin and amylose, and the heat conductivity of the material is improved by adding the heat conducting powder, namely, the heat conductivity coefficient is more than or equal to 0.8W/(m.k); the modified carbon forming agent is added, so that the rapid carbon forming property of the material under the conditions of combustion and high temperature is improved, the effect of isolating oxygen is achieved, and the addition of MCA has the effect of flame retardance. The combination of the heat conducting powder, the carbon forming agent and the MCA not only improves the flame retardance of the material, namely the UL94/1mmV0 flame retardant grade, but also improves the high GWIT performance of the material, namely the GWIT/1mm can meet the requirements of no ignition and no spark in the whole process at the temperature of more than or equal to 775 ℃, and finally can simultaneously meet the requirements of high flame retardant grade, high heat conduction and high GWIT.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material and a preparation method thereof.
Background
Polyamide 6 (PA 6 for short) belongs to crystalline thermoplastic engineering plastics, has the advantages of better toughness, chemical resistance, self-lubricating property and the like, and the modified material is widely applied to the fields of electronics, electrics, machinery, automobiles, electric tools and the like. Along with the continuous development of technology and the continuous improvement of human demands, the requirements on materials are also higher and higher, and polyamide 6 is needed for LED lamp cap materials, coil skeleton materials and the like in the field of electronics and electrics. With the improvement of safety consciousness, higher requirements are put on the thermal conductivity, the high Glow Wire Ignition Temperature (GWIT), the flame retardant grade and the like of materials.
The existing halogen-free flame-retardant high GWIT high heat conduction polyamide 6 material can refer to Chinese patent with publication number CN112724699A, which discloses a high GWIT high heat conduction nylon composite material, wherein heat conduction powder and inorganic hydroxide are added, so that the GWIT/1mm of the material can reach more than 750 ℃, the heat conduction coefficient can reach more than 1.0W/(m.k), but the UL94 flame retardant rating is more than 3.0mm thickness V1 rating; chinese patent CN108892947B discloses a halogen-free flame-retardant heat-conducting nylon material, and the heat conductivity coefficient of the material is more than or equal to 0.75W/(m.k), the UL94 flame-retardant grade is more than or equal to V2, and the performance of high GWIT is not reflected by adding heat-conducting powder and modified crosslinked starch; chinese patent CN108192340a discloses a MCA flame retardant PA6 material with high glow wire ignition temperature, by adding MCA and glow wire synergist, GWIT of the material can reach 750 ℃, UL94 flame retardant rating of 0.8mm can meet UL94-V0 rating, but no thermal conductivity is reflected.
At present, the traditional heat-conducting polyamide 6 generally has only heat-conducting performance, does not have the characteristics of high flame retardant level (such as 1.0mm/UL 94-V0) and high GWIT (such as the thickness of 1.0mm is more than or equal to 775 ℃), the coil skeleton MCA flame-retardant polyamide 6 material generally only meets the requirement of Glow Wire Flammability Index (GWFI) 960 ℃, cannot meet the requirement of GWIT is more than or equal to 775 ℃ or is very unstable, flame retardance is generally of UL94-V2, and does not have the characteristic of high heat conduction. There is therefore a need to develop polyamide 6 materials which simultaneously meet high flame retardant ratings, high thermal conductivity and high GWIT.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material which can simultaneously meet the requirements of high flame retardant grade, high heat conductivity and high GWIT.
The aim of the invention can be achieved by the following technical scheme: the halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material consists of the following materials in parts by weight:
polyamide 6:26-43 parts;
and (3) heat conducting powder: 45-55 parts;
modifying into a carbon agent: 5-8 parts of a lubricant;
compounding an antioxidant: 0.3-0.8 part;
and (3) a lubricant: 0.5-1.5 parts;
MCA flame retardant: 5-8 parts of a lubricant;
coupling agent: 0.5-1 part;
wherein the modified carbon-forming agent is one or a mixture of lignin and amylose, and the mesh number of the modified carbon-forming agent is 80-120.
Preferably, the modified carbon-forming agent comprises the following materials in parts by mass:
one of the lignin or the amylose or a mixture thereof: 60 parts;
polycaprolactone: 30 parts;
glycerol: 10 parts;
and (3) a main antioxidant: 0.2 parts;
auxiliary antioxidant: 0.4 parts;
wherein the average molecular weight of the polycaprolactone is 50000.
Preferably, the lignin is one or a mixture of lignosulfonate and alkaline lignin, and the amylose is one or a mixture of corn starch, bean starch and potato starch.
Preferably, the heat conducting powder is a mixture of magnesium oxide, aluminum oxide and zinc oxide.
Preferably, the MCA flame retardant is melamine cyanurate with the particle size of 1.4-1.8 mu m.
Preferably, the compound antioxidant is one or more of hindered phenol antioxidants and phosphite antioxidants; the lubricant is one or more of vinyl bis-stearamide, polysiloxane, calcium stearate, silicone powder and ethylene bis-stearamide; the coupling agent is phthalate esters or silanes.
The invention provides a preparation method of a halogen-free flame-retardant high GWIT high heat conduction polyamide 6 material, which comprises the following steps:
s1, uniformly mixing the dried polyamide 6 and a coupling agent by using a high-speed mixer at normal temperature to form a first mixture;
s2, sequentially adding the modified carbon forming agent, the compound antioxidant, the lubricant and the MCA flame retardant into the first mixture, uniformly mixing to form a second mixture, and adding the second mixture into a main feeding port of an extruder;
s3, adding the heat conducting powder into a side feeding port of the extruder after weighing by a weightlessness scale, and uniformly mixing the heat conducting powder with the mixture II to form a mixture III;
and S4, carrying out melt extrusion granulation and drying on the mixture III to obtain the halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material.
Preferably, the extruder is a twin-screw extruder, the rotating speed of the twin-screw extruder is set to be 200-350 rpm, the temperature of one to two areas is 190-210 ℃, the temperature of three to five areas is 220-240 ℃, and the temperature of five to ten areas is 220-240 ℃.
The beneficial effects of the invention are as follows:
the heat conduction coefficient of the material is more than or equal to 0.8W/(m.k) through adding the heat conduction powder; the modified carbon forming agent is added, so that the rapid carbon forming property of the material under the conditions of combustion and high temperature is improved, the effect of isolating oxygen is achieved, and the addition of MCA has the effect of flame retardance. The combination of the heat conducting powder, the carbon forming agent and the MCA not only improves the flame retardance of the material, namely the UL94/1mm V0 flame retardant grade, but also improves the high GWIT performance of the material, namely GWIT/1mm can meet the requirements of no ignition and no spark in the whole process at the temperature of more than or equal to 775 ℃, and finally can simultaneously meet the requirements of high flame retardant grade, high heat conduction and high GWIT.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material consists of the following materials in parts by weight:
polyamide 6:26-43 parts;
and (3) heat conducting powder: 45-55 parts;
modifying into a carbon agent: 5-8 parts of a lubricant;
compounding an antioxidant: 0.3-0.8 part;
and (3) a lubricant: 0.5-1.5 parts;
MCA flame retardant: 5-8 parts of a lubricant;
coupling agent: 0.5-1 part;
wherein the modified carbon-forming agent is one or a mixture of lignin and amylose, and the mesh number of the modified carbon-forming agent is 80-120; the relative viscosity of the polyamide 6 is 2.0-2.2.
The modified carbon agent consists of the following materials in parts by weight:
one of the lignin or the amylose or a mixture thereof: 60 parts;
polycaprolactone: 30 parts;
glycerol: 10 parts;
primary antioxidant (1076): 0.2 parts;
auxiliary antioxidant (168): 0.4 parts;
the manufacturers of the main antioxidant and the auxiliary antioxidant are Tianjin An Long new material Co.Ltd.
Wherein the average molecular weight of the polycaprolactone is 50000.
Polycaprolactone (PCL for short) belongs to a biodegradable material, and has a melting point (Tm) of about 60 ℃ and a decomposition temperature (Td) of about 250 ℃, so that the processing temperature range is wider, lignin and amylose are easy to change color or carbonize when being subjected to high temperature, PCL with low melting point is adopted as a coating carrier, and in addition, the PCL has a glass transition temperature (Tg) of about-60 ℃, so that the PCL has good flexibility, the flexibility of a modified carbon agent and polyamide mixed material can be improved, and meanwhile, the PCL is also used as a hot melt adhesive component, so that the binding force among different components of the mixture can be improved. The glycerol is added for plasticizing lignin or amylose, so that the lignin or amylose has certain thermoplastic characteristics, and can be coated at the same time, thereby playing a role in protection.
The lignin is one or a mixture of lignosulfonate and alkaline lignin, and the amylose is one or a mixture of corn starch, bean starch and potato starch.
Lignin is a macromolecule formed by connecting phenylpropane structural units through carbon-carbon bonds and ether bonds, and has high pyrolytic carbon yield, carbonization yield is about 70% at 300 ℃, and carbonization yield is 40% even at 800 ℃. Amylose is a linear macromolecule with multiple glucosyl groups connected by glycosidic bonds, and has high carbon content, low decomposition temperature and easy carbonization. In addition, the sources of lignin and starch are mainly crop straws and the like, and belong to degradable biomass materials, and the lignin and starch have large yield and wide sources.
The preparation method of the modified carbon agent comprises the following steps:
s1, placing lignin or amylose or a mixture of lignin and amylose into a charging basket of a low-speed mixer, and adding glycerol while stirring to ensure that powder is completely wetted to form a mixture I;
s2, adding an antioxidant and polycaprolactone into the mixture I for mixing for 3-5min to form a mixture II;
s3, adding the mixture II into a main feeding barrel of an extruder, and performing melt extrusion granulation and drying to obtain the modified carbon forming agent, wherein the extruder is a double-screw extruder, the rotating speed of the double-screw extruder is 200-300 rpm, the temperature of one to two areas is 50-60 ℃, the temperature of three to five areas is 60-80 ℃, and the temperature of five to ten areas is 70-80 ℃.
The heat conducting powder is a mixture of magnesium oxide, aluminum oxide and zinc oxide.
The MCA flame retardant is melamine cyanurate with the grain diameter of 1.4-1.8 mu m.
The compound antioxidant is one or more of hindered phenol antioxidants and phosphite antioxidants; the lubricant is one or more of vinyl bis-stearamide, polysiloxane, calcium stearate, silicone powder and ethylene bis-stearamide; the coupling agent is phthalate esters or silanes.
The invention provides a preparation method of a halogen-free flame-retardant high GWIT high heat conduction polyamide 6 material, which comprises the following steps:
s1, uniformly mixing the dried polyamide 6 and a coupling agent by using a high-speed mixer at normal temperature to form a first mixture;
s2, sequentially adding the modified carbon forming agent, the compound antioxidant, the lubricant and the MCA flame retardant into the first mixture, uniformly mixing to form a second mixture, and adding the second mixture into a main feeding port of an extruder;
s3, adding the heat conducting powder into a side feeding port of the extruder after weighing by a weightlessness scale, and uniformly mixing the heat conducting powder with the mixture II to form a mixture III;
and S4, carrying out melt extrusion granulation and drying on the mixture III to obtain the halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material.
The extruder is a double-screw extruder, the rotating speed of the double-screw extruder is set to be 200-350 rpm, the temperature of one to two areas is 190-210 ℃, the temperature of three to five areas is 220-240 ℃, and the temperature of five to ten areas is 220-240 ℃.
Table I Material manufacturer and brand
Table 2 examples and comparative examples composition ratios table
Wherein the carbon forming agent modified by amylose is named A, the carbon forming agent modified by lignin is named B, and the carbon forming agent modified by the mixture of the two is named C.
Table 3 test data
Thermal conductivity: the vertical thermal conductivity is tested according to an ASTME1461 laser method, and the test thickness is 1.0mm;
glow Wire Ignition Temperature (GWIT): testing according to IEC60695-2-12 standard, wherein the test thickness is 1.0mm;
flame retardant properties: the thickness was 1.0mm as measured in accordance with UL 94-2016;
extrusion processability was as follows: easy to process, normal to process, and impossible to process are respectively expressed as++, +, -and the like.
As can be seen from tables 2 and 3, in examples 1 to 3, with the other variables being the same, the thermal conductivity was gradually increased with the increase of the heat conductive powder, and the GWIT of 775 ℃ or more and the UL94/1mmV0 flame retardant rating were satisfied.
As can be seen from comparison of examples 3 and 4, with the same amount of the heat conductive powder, as the modified carbon and flame retardant are increased, the heat conductivity and GWIT values are also gradually increased, the heat conductivity value can reach 1.12W/(m·k) at maximum, the GWIT value can reach 800 ℃ at maximum, and the UL94/1mmV0 flame retardant rating is satisfied at the same time, so example 4 is a stoichiometric optimum.
As is clear from the comparison of examples 1, 5 and 6, the lignin, amylose and the mixture thereof have similar effects when the other variables are the same, the thermal conductivity of example 1 and example 6 are both 0.83W/(m.k), the thermal conductivity of example 5 is 0.02W/(m.k) more than that of example 1 and example 6, and the GWIT and flame retardancy of examples 1, 5 and 6 are the same.
Comparison of comparative example 1 and example 4 shows that the performance of GWIT775 and V0 cannot be satisfied simultaneously in the absence of the modified carbon-forming agent when the other variables are the same.
As is clear from the comparison between comparative example 2 and example 4, the compounding effect of the MCA flame retardant was lacking in the case where other variables were the same, and thus the performance of GWIT775 and V0 could not be satisfied at the same time.
As is clear from comparison of comparative example 3 and example 4, the content of the heat conductive powder was reduced, so that the heat conductivity of the material was lowered, and the heat conductivity value was lowered to 0.72W/(m.k).
Comparison of comparative example 4 and example 4 shows that the reduction in GWIT and flame retardant rating is due to the reduction in modified to carbon and MCA flame retardant.
As is clear from the comparison between comparative example 5 and example 4, polyamide 6 was reduced and the heat conductive powder was increased, and the properties of heat conductivity, GWIT775 and V0 were simultaneously satisfied, but the extrusion process was severe in drawing and breakage, resulting in mass production failure.
Comparison of comparative example 6 and example 4 shows that in the case where polyamide 6, modified carbon former and MCA flame retardant are reduced and heat conductive powder is increased, while the heat conductivity is high, GWIT value is only 750 ℃, the requirement that GWIT is not satisfied at 775 ℃ or more, while flame retardancy UL94 is V1, the UL94/1mmV0 flame retardant rating is not satisfied, so that flame retardant effect and GWIT are reduced.
The heat conduction coefficient of the material is more than or equal to 0.8W/(m.k) through adding the heat conduction powder; the modified carbon forming agent is added, so that the rapid carbon forming property of the material under the conditions of combustion and high temperature is improved, the effect of isolating oxygen is achieved, and the addition of MCA has the effect of flame retardance. The combination of the heat conducting powder, the carbon forming agent and the MCA not only improves the flame retardance of the material, namely the UL94/1mmV0 flame retardant grade, but also improves the high GWIT performance of the material, namely the GWIT/1mm can meet the requirements of no ignition and no spark in the whole process at the temperature of more than or equal to 775 ℃, and finally can simultaneously meet the requirements of high flame retardant grade, high heat conduction and high GWIT.
The invention has been described above with reference to preferred embodiments, but the scope of the invention is not limited thereto, and any and all technical solutions falling within the scope of the claims are within the scope of the invention. Various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict.
Claims (8)
1. The halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material is characterized by comprising the following materials in parts by weight:
polyamide 6:26-43 parts;
and (3) heat conducting powder: 45-55 parts;
modifying into a carbon agent: 5-8 parts of a lubricant;
compounding an antioxidant: 0.3-0.8 part;
and (3) a lubricant: 0.5-1.5 parts;
MCA flame retardant: 5-8 parts of a lubricant;
coupling agent: 0.5-1 part;
wherein the modified carbon-forming agent is one or a mixture of lignin and amylose, and the mesh number of the modified carbon-forming agent is 80-120.
2. The halogen-free flame-retardant high-GWIT high-heat-conductivity polyamide 6 material of claim 1, wherein the modified carbon-forming agent comprises the following materials in parts by mass:
one of the lignin or the amylose or a mixture thereof: 60 parts;
polycaprolactone: 30 parts;
glycerol: 10 parts;
and (3) a main antioxidant: 0.2 parts;
auxiliary antioxidant: 0.4 parts;
wherein the average molecular weight of the polycaprolactone is 50000.
3. The halogen-free flame retardant high GWIT high thermal conductivity polyamide 6 material of claim 1, wherein the lignin is one or a mixture of lignosulfonate and alkaline lignin, and the amylose is one or a mixture of corn starch, bean starch and potato starch.
4. The halogen-free flame retardant high GWIT high thermal conductivity polyamide 6 material of claim 1, wherein the thermal conductive powder is a mixture of magnesium oxide, aluminum oxide, zinc oxide.
5. The halogen-free flame-retardant high-GWIT high-heat-conductivity polyamide 6 material of claim 1, wherein the MCA flame retardant is melamine cyanurate with a particle size of 1.4-1.8 μm.
6. The halogen-free flame-retardant high-GWIT high-heat-conductivity polyamide 6 material of claim 1, wherein the compound antioxidant is one or more of hindered phenol antioxidants and phosphite antioxidants; the lubricant is one or more of vinyl bis-stearamide, polysiloxane, calcium stearate, silicone powder and ethylene bis-stearamide; the coupling agent is phthalate esters or silanes.
7. The preparation method of the halogen-free flame-retardant high GWIT high heat conduction polyamide 6 material is characterized by comprising the following steps:
s1, uniformly mixing the dried polyamide 6 and a coupling agent by using a high-speed mixer at normal temperature to form a first mixture;
s2, sequentially adding the modified carbon forming agent, the compound antioxidant, the lubricant and the MCA flame retardant into the first mixture, uniformly mixing to form a second mixture, and adding the second mixture into a main feeding port of an extruder;
s3, adding the heat conducting powder into a side feeding port of the extruder after weighing by a weightlessness scale, and uniformly mixing the heat conducting powder with the mixture II to form a mixture III;
and S4, carrying out melt extrusion granulation and drying on the mixture III to obtain the halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material.
8. The method for preparing a halogen-free flame-retardant high-GWIT high-heat-conductivity polyamide 6 material according to claim 7, wherein the extruder is a twin-screw extruder, the rotation speed of the twin-screw extruder is set to be 200-350 rpm, the temperature of one or two zones is 190-210 ℃, the temperature of three or five zones is 220-240 ℃, and the temperature of five or ten zones is 220-240 ℃.
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