CN114437460A - High-heat-resistance flame-retardant polypropylene composite material and preparation method thereof - Google Patents
High-heat-resistance flame-retardant polypropylene composite material and preparation method thereof Download PDFInfo
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- CN114437460A CN114437460A CN202210223815.0A CN202210223815A CN114437460A CN 114437460 A CN114437460 A CN 114437460A CN 202210223815 A CN202210223815 A CN 202210223815A CN 114437460 A CN114437460 A CN 114437460A
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- -1 polypropylene Polymers 0.000 title claims abstract description 134
- 239000002131 composite material Substances 0.000 title claims abstract description 132
- 239000003063 flame retardant Substances 0.000 title claims abstract description 129
- 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 128
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 128
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 78
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 73
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 56
- 238000005282 brightening Methods 0.000 claims abstract description 48
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 47
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000000314 lubricant Substances 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 239000003365 glass fiber Substances 0.000 claims abstract description 19
- 239000010445 mica Substances 0.000 claims abstract description 18
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 18
- 239000002667 nucleating agent Substances 0.000 claims abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- 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 abstract description 17
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 16
- 229910021538 borax Inorganic materials 0.000 claims description 30
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 30
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 30
- 239000004328 sodium tetraborate Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 25
- 239000000347 magnesium hydroxide Substances 0.000 claims description 25
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 25
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 23
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 7
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 7
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 7
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 7
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- 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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a high heat-resistant flame-retardant polypropylene composite material and a preparation method thereof, wherein the high heat-resistant flame-retardant polypropylene composite material comprises raw materials of polypropylene resin, heat-resistant brightening functional master batches, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A, and the raw materials comprise the following components in parts by weight: 70-80 parts of polypropylene resin, 20-40 parts of heat-resistant brightening functional master batch, 20-40 parts of composite flame retardant, 10-30 parts of talcum powder, 3-5 parts of polypropylene grafted maleic anhydride compatilizer, 2-3 parts of lubricant, 1-3 parts of silane coupling agent and 1-2 parts of antioxidant A, wherein the heat-resistant brightening functional master batch comprises raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, silane coupling agent, silicone powder, titanium dioxide, phosphoric acid nucleating agent and antioxidant B. The invention aims to solve the technical problems that the heat resistance, the flame retardant property and the glossiness of a polypropylene material in the prior art need to be further improved.
Description
Technical Field
The invention relates to the technical field of polypropylene composite materials, in particular to a high-heat-resistance flame-retardant polypropylene composite material and a preparation method thereof.
Background
Polypropylene (PP) is a polymer obtained by addition polymerization of propylene. As a general plastic, polypropylene has the advantages of low price, good heat resistance and the like, and is widely applied to the fields of automobiles, household appliances, office supplies and various electronic and electrical appliances. At present, polypropylene materials in the market are mostly prepared by blending various auxiliary agents such as glass fibers, inorganic fillers, flame retardants and the like for modification, so that the heat resistance and the flame retardance of the polypropylene materials are improved, but the heat resistance and the flame retardance of the existing polypropylene materials still cannot meet the requirements of higher standards, the polypropylene materials are still easy to soften and burn in the environment of high temperature and open fire, and in the prior art, the glossiness of the polypropylene materials is reduced to a certain extent due to the addition of the flame retardants.
Aiming at the technical problems, the invention discloses a high heat-resistant flame-retardant polypropylene composite material and a preparation method thereof, and the invention can improve the heat-resistant and flame-retardant performances of the polypropylene composite material and simultaneously can well maintain the glossiness of the polypropylene composite material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a high heat-resistant flame-retardant polypropylene composite material and a preparation method thereof, and aims to solve the technical problems that the heat-resistant and flame-retardant properties of a polypropylene material are required to be further improved, the glossiness of the polypropylene material is not high and the like in the prior art.
In order to solve the technical problems, the invention discloses a high heat-resistant flame-retardant polypropylene composite material, which comprises raw materials of polypropylene resin, heat-resistant brightening master batches, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A, wherein the raw materials comprise the following components in parts by weight:
the heat-resistant brightening functional master batch comprises raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, a silane coupling agent, silicone powder, titanium dioxide, a phosphoric acid nucleating agent and an antioxidant B;
the composite flame retardant comprises raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage type polysilsesquioxane, sodium tetraborate solution and a silane coupling agent.
Preferably, the heat-resistant brightening functional master batch comprises the following raw materials in parts by weight:
preferably, the composite flame retardant master batch comprises the following raw materials in parts by weight:
the concentration of the sodium tetraborate solution is 0.1 mol/L.
Preferably, the lubricant is any one or two or more of ethylene bis stearamide, polyethylene wax, zinc stearate, barium stearate, oleamide and erucamide.
Preferably, the antioxidant A and the antioxidant B are both prepared by mixing the antioxidant 1010 and the antioxidant 168 according to the mass ratio of 1: 1.
The invention also discloses a preparation method of the high heat-resistant flame-retardant polypropylene composite material, which comprises the following preparation steps:
the method comprises the following steps: preparing heat-resistant brightening functional master batch
Weighing the raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, a silane coupling agent, silicone powder, titanium dioxide, a phosphoric acid nucleating agent and an antioxidant B according to parts by weight, uniformly mixing by high-temperature melting, and then extruding and granulating by a double-screw extruder to prepare heat-resistant brightening functional master batch;
step two: preparation of composite flame retardant
Weighing raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane, sodium tetraborate solution and a silane coupling agent in parts by weight, sequentially adding the raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane and the silane coupling agent into the sodium tetraborate solution, stirring for 20-40 min, and finally drying and scattering to prepare the composite flame retardant;
step three: preparation of high heat-resistant flame-retardant polypropylene composite master batch
Weighing the raw materials of polypropylene resin, heat-resistant brightening functional master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A according to parts by weight, melting and mixing uniformly at high temperature, and then extruding and granulating by a double-screw extruder to prepare the high heat-resistant flame-retardant polypropylene composite master batch;
step four: preparation of high heat-resistant flame-retardant polypropylene composite material
And directly injection-molding the high-heat-resistant flame-retardant polypropylene composite master batch to prepare the high-heat-resistant flame-retardant polypropylene composite material.
Preferably, in the third step, the rotating speed of the double-screw extruder is 300-500 r/min, and the extrusion temperature of the head is 190-230 ℃.
The invention has the following advantages:
(1) the invention obviously improves the heat resistance of the polypropylene composite material and well keeps the glossiness of the polypropylene composite material by adding the heat-resistant brightening functional master batch, the heat-resistant brightening functional master batch comprises raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, silane coupling agent, silicone powder, titanium dioxide, phosphoric acid series nucleating agent and antioxidant B, firstly, the organic silicon resin is selected as a carrier, the organic silicon resin has excellent heat resistance, the addition of the alkali-free glass fiber, the precipitated barium sulfate and the mica powder can obviously improve the heat resistance of the polypropylene composite material, the silane coupling agent can well modify the organic silicon resin, the interface affinity of the organic silicon resin and the polymer is improved, the dispersion state of the organic silicon resin and the polymer in a polymer base material is improved, and meanwhile, the addition of the precipitated barium sulfate and the mica powder can improve the glossiness of the polypropylene composite material, the silicon powder has good lubricating and dispersing effects, the polypropylene composite material is resistant to sunlight, does not crack or change color under the irradiation of sunlight due to the addition of the titanium dioxide, the glossiness of the polypropylene composite material is ensured, the phosphoric acid nucleating agent has good thermal stability and does not change color under the high-temperature condition, and meanwhile, the addition of the phosphoric acid nucleating agent can improve the crystallinity, so that crystal nuclei are more uniform and fine, and the glossiness of the surface of the polypropylene composite material is improved;
(2) the flame retardant property of the polypropylene composite material is obviously improved by the preparation and addition of the composite flame retardant, the composite flame retardant comprises raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane, sodium tetraborate solution and silane coupling agent, the magnesium hydroxide, the decabromodiphenyl ether and the diatomite all have good flame retardant effect, the three materials form uniformly mixed suspension in the sodium tetraborate solution, the silane coupling agent has good modification effect, the interfacial affinity of the magnesium hydroxide, the diatomite and the like with polymers is improved, the dispersibility of the magnesium hydroxide, the diatomite and the like is improved, meanwhile, the introduction of the cage-type polysilsesquioxane can reduce the viscosity of a polymer system, a heat-resistant Si-0 bond is introduced, the heat resistance is improved, meanwhile, SiO2 is formed after high-temperature calcination and deposited on the surface of the resin as a protective layer, the combustion speed of the resin can be delayed, the combustion heat is reduced, the raw materials in the composite flame retardant play a good synergistic flame-retardant effect, so that the effect of improving the flame-retardant performance of the polypropylene composite material is well achieved.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Embodiment 1 discloses a high heat-resistant flame-retardant polypropylene composite material, which comprises raw materials of polypropylene resin, heat-resistant brightening master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A, wherein the raw materials comprise the following components in parts by weight:
the heat-resistant brightening functional master batch comprises raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, silane coupling agent, silicone powder, titanium dioxide, phosphoric acid nucleating agent and antioxidant B;
the composite flame retardant comprises raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage type polysilsesquioxane, sodium tetraborate solution and a silane coupling agent.
Preferably, the heat-resistant brightening functional master batch comprises the following raw materials in parts by weight:
preferably, the composite flame retardant master batch comprises the following raw materials in parts by weight:
the concentration of the sodium tetraborate solution is 0.1 mol/L.
Preferably, the lubricant is any one or two or more of ethylene bis stearamide, polyethylene wax, zinc stearate, barium stearate, oleamide and erucamide.
Preferably, the antioxidant A and the antioxidant B are both prepared by mixing the antioxidant 1010 and the antioxidant 168 according to the mass ratio of 1: 1.
The embodiment also discloses a preparation method of the high heat-resistant flame-retardant polypropylene composite material, which comprises the following preparation steps:
the method comprises the following steps: preparing heat-resistant brightening functional master batch
Weighing the raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, a silane coupling agent, silicone powder, titanium dioxide, a phosphoric acid nucleating agent and an antioxidant B according to parts by weight, uniformly mixing by high-temperature melting, and then extruding and granulating by a double-screw extruder to prepare heat-resistant brightening functional master batch;
step two: preparation of composite flame retardant
Weighing raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane, sodium tetraborate solution and silane coupling agent in parts by weight, sequentially adding the raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane and silane coupling agent into the sodium tetraborate solution, stirring for 20min, finally drying and scattering to obtain the composite flame retardant;
step three: preparation of high heat-resistant flame-retardant polypropylene composite master batch
Weighing the raw materials of polypropylene resin, heat-resistant brightening functional master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A according to parts by weight, melting and mixing uniformly at high temperature, and then extruding and granulating by a double-screw extruder to prepare the high heat-resistant flame-retardant polypropylene composite master batch;
step four: preparation of high heat-resistant flame-retardant polypropylene composite material
And directly injection-molding the high-heat-resistant flame-retardant polypropylene composite master batch to prepare the high-heat-resistant flame-retardant polypropylene composite material.
Preferably, in the third step, the rotating speed of the double-screw extruder is 300r/min, and the extrusion temperature of the head is 190 ℃.
Example 2
Embodiment 2 discloses a high heat-resistant flame-retardant polypropylene composite material, which comprises raw materials of polypropylene resin, heat-resistant brightening master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A, wherein the raw materials comprise the following components in parts by weight:
the heat-resistant brightening functional master batch comprises raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, silane coupling agent, silicone powder, titanium dioxide, phosphoric acid nucleating agent and antioxidant B;
the composite flame retardant comprises raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage type polysilsesquioxane, sodium tetraborate solution and a silane coupling agent.
Preferably, the heat-resistant brightening functional master batch comprises the following raw materials in parts by weight:
preferably, the composite flame retardant master batch comprises the following raw materials in parts by weight:
the concentration of the sodium tetraborate solution is 0.1 mol/L.
Preferably, the lubricant is any one or two or more of ethylene bis stearamide, polyethylene wax, zinc stearate, barium stearate, oleamide and erucamide.
Preferably, the antioxidant A and the antioxidant B are both prepared by mixing the antioxidant 1010 and the antioxidant 168 according to the mass ratio of 1: 1.
The embodiment also discloses a preparation method of the high heat-resistant flame-retardant polypropylene composite material, which comprises the following preparation steps:
the method comprises the following steps: preparing heat-resistant brightening functional master batch
Weighing the raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, a silane coupling agent, silicone powder, titanium dioxide, a phosphoric acid nucleating agent and an antioxidant B in parts by weight, uniformly mixing by high-temperature melting, and then extruding and granulating by a double-screw extruder to prepare the heat-resistant brightening functional master batch;
step two: preparation of composite flame retardant
Weighing raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane, sodium tetraborate solution and silane coupling agent in parts by weight, sequentially adding the raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane and silane coupling agent into the sodium tetraborate solution, stirring for 20min, finally drying and scattering to obtain the composite flame retardant;
step three: preparation of high heat-resistant flame-retardant polypropylene composite master batch
Weighing the raw materials of polypropylene resin, heat-resistant brightening functional master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A in parts by weight, melting and mixing uniformly at a high temperature, and then extruding and granulating by a double-screw extruder to prepare the high heat-resistant flame-retardant polypropylene composite master batch;
step four: preparation of high heat-resistant flame-retardant polypropylene composite material
And directly injection-molding the high-heat-resistant flame-retardant polypropylene composite master batch to prepare the high-heat-resistant flame-retardant polypropylene composite material.
Preferably, in the third step, the rotating speed of the double-screw extruder is 300r/min, and the extrusion temperature of the head is 190 ℃.
Example 3
Embodiment 3 discloses a high heat-resistant flame-retardant polypropylene composite material, which comprises raw materials of polypropylene resin, heat-resistant brightening master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A, wherein the raw materials comprise the following components in parts by weight:
the heat-resistant brightening functional master batch comprises raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, silane coupling agent, silicone powder, titanium dioxide, phosphoric acid nucleating agent and antioxidant B;
the composite flame retardant comprises raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage type polysilsesquioxane, sodium tetraborate solution and a silane coupling agent.
Preferably, the heat-resistant brightening functional master batch comprises the following raw materials in parts by weight:
preferably, the composite flame retardant master batch comprises the following raw materials in parts by weight:
the concentration of the sodium tetraborate solution is 0.1 mol/L.
Preferably, the lubricant is any one or two or more of ethylene bis stearamide, polyethylene wax, zinc stearate, barium stearate, oleamide and erucamide.
Preferably, the antioxidant A and the antioxidant B are both prepared by mixing the antioxidant 1010 and the antioxidant 168 according to the mass ratio of 1: 1.
The embodiment also discloses a preparation method of the high heat-resistant flame-retardant polypropylene composite material, which comprises the following preparation steps:
the method comprises the following steps: preparing heat-resistant brightening functional master batch
Weighing the raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, a silane coupling agent, silicone powder, titanium dioxide, a phosphoric acid nucleating agent and an antioxidant B according to parts by weight, uniformly mixing by high-temperature melting, and then extruding and granulating by a double-screw extruder to prepare heat-resistant brightening functional master batch;
step two: preparation of composite flame retardant
Weighing raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane, sodium tetraborate solution and silane coupling agent in parts by weight, sequentially adding the raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane and silane coupling agent into the sodium tetraborate solution, stirring for 20min, finally drying and scattering to obtain the composite flame retardant;
step three: preparation of high heat-resistant flame-retardant polypropylene composite master batch
Weighing the raw materials of polypropylene resin, heat-resistant brightening functional master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A according to parts by weight, melting and mixing uniformly at high temperature, and then extruding and granulating by a double-screw extruder to prepare the high heat-resistant flame-retardant polypropylene composite master batch;
step four: preparation of high heat-resistant flame-retardant polypropylene composite material
And directly injection-molding the high-heat-resistant flame-retardant polypropylene composite master batch to prepare the high-heat-resistant flame-retardant polypropylene composite material.
Preferably, in the third step, the rotating speed of the double-screw extruder is 300r/min, and the extrusion temperature of the head is 190 ℃.
Example 4
Embodiment 4 discloses a high heat-resistant flame-retardant polypropylene composite material, which comprises raw materials of polypropylene resin, heat-resistant brightening master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A, wherein the raw materials comprise the following components in parts by weight:
the heat-resistant brightening functional master batch comprises raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, silane coupling agent, silicone powder, titanium dioxide, phosphoric acid nucleating agent and antioxidant B;
the composite flame retardant comprises raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage type polysilsesquioxane, sodium tetraborate solution and a silane coupling agent.
Preferably, the heat-resistant brightening functional master batch comprises the following raw materials in parts by weight:
preferably, the composite flame retardant master batch comprises the following raw materials in parts by weight:
the concentration of the sodium tetraborate solution is 0.1 mol/L.
Preferably, the lubricant is any one or two or more of ethylene bis stearamide, polyethylene wax, zinc stearate, barium stearate, oleamide and erucamide.
Preferably, the antioxidant A and the antioxidant B are both prepared by mixing the antioxidant 1010 and the antioxidant 168 according to the mass ratio of 1: 1.
The embodiment also discloses a preparation method of the high heat-resistant flame-retardant polypropylene composite material, which comprises the following preparation steps:
the method comprises the following steps: preparing heat-resistant brightening functional master batch
Weighing the raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, a silane coupling agent, silicone powder, titanium dioxide, a phosphoric acid nucleating agent and an antioxidant B according to parts by weight, uniformly mixing by high-temperature melting, and then extruding and granulating by a double-screw extruder to prepare heat-resistant brightening functional master batch;
step two: preparation of composite flame retardant
Weighing raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane, sodium tetraborate solution and silane coupling agent in parts by weight, sequentially adding the raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane and silane coupling agent into the sodium tetraborate solution, stirring for 30min, finally drying and scattering to obtain the composite flame retardant;
step three: preparation of high heat-resistant flame-retardant polypropylene composite master batch
Weighing the raw materials of polypropylene resin, heat-resistant brightening functional master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A according to parts by weight, melting and mixing uniformly at high temperature, and then extruding and granulating by a double-screw extruder to prepare the high heat-resistant flame-retardant polypropylene composite master batch;
step four: preparation of high heat-resistant flame-retardant polypropylene composite material
And directly injection-molding the high-heat-resistant flame-retardant polypropylene composite master batch to prepare the high-heat-resistant flame-retardant polypropylene composite material.
Preferably, in the third step, the rotating speed of the double-screw extruder is 400r/min, and the extrusion temperature of the head is 210 ℃.
Example 5
Embodiment 5 discloses a high heat-resistant flame-retardant polypropylene composite material, which comprises raw materials of polypropylene resin, heat-resistant brightening master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A, wherein the raw materials comprise the following components in parts by weight:
the heat-resistant brightening functional master batch comprises raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, silane coupling agent, silicone powder, titanium dioxide, phosphoric acid nucleating agent and antioxidant B;
the composite flame retardant comprises raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage type polysilsesquioxane, sodium tetraborate solution and a silane coupling agent.
Preferably, the heat-resistant brightening functional master batch comprises the following raw materials in parts by weight:
preferably, the composite flame retardant master batch comprises the following raw materials in parts by weight:
the concentration of the sodium tetraborate solution is 0.1 mol/L.
Preferably, the lubricant is any one or two or more of ethylene bis stearamide, polyethylene wax, zinc stearate, barium stearate, oleamide and erucamide.
Preferably, the antioxidant A and the antioxidant B are both prepared by mixing the antioxidant 1010 and the antioxidant 168 according to the mass ratio of 1: 1.
The embodiment also discloses a preparation method of the high heat-resistant flame-retardant polypropylene composite material, which comprises the following preparation steps:
the method comprises the following steps: preparing heat-resistant brightening functional master batch
Weighing the raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, a silane coupling agent, silicone powder, titanium dioxide, a phosphoric acid nucleating agent and an antioxidant B according to parts by weight, uniformly mixing by high-temperature melting, and then extruding and granulating by a double-screw extruder to prepare heat-resistant brightening functional master batch;
step two: preparation of composite flame retardant
Weighing raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane, sodium tetraborate solution and silane coupling agent in parts by weight, sequentially adding the raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane and silane coupling agent into the sodium tetraborate solution, stirring for 40min, finally drying and scattering to obtain the composite flame retardant;
step three: preparation of high heat-resistant flame-retardant polypropylene composite master batch
Weighing the raw materials of polypropylene resin, heat-resistant brightening functional master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A according to parts by weight, melting and mixing uniformly at high temperature, and then extruding and granulating by a double-screw extruder to prepare the high heat-resistant flame-retardant polypropylene composite master batch;
step four: preparation of high heat-resistant flame-retardant polypropylene composite material
And directly injection-molding the high-heat-resistant flame-retardant polypropylene composite master batch to prepare the high-heat-resistant flame-retardant polypropylene composite material.
Preferably, in the third step, the rotating speed of the double-screw extruder is 500r/min, and the extrusion temperature of the head is 230 ℃.
Comparative example
The comparative example is the existing heat-resistant flame-retardant polypropylene material, and the main raw materials comprise polypropylene resin, talcum powder, glass fiber, flame retardant, lubricant and antioxidant.
The heat resistance, flame retardancy and surface gloss of the polypropylene composite materials prepared by examples 1 to 5 of the present application and the existing polypropylene materials in the comparative examples were measured, respectively, and the results are recorded in the following table:
TABLE 1 data table for testing heat-resistant, flame-retardant and surface gloss of polypropylene composite material
| Load deflection temperature (. degree. C.) | Flame retardant Property () | Surface gloss (60 degree) | |
| Example 1 | 126 | V-0 | 91.6 |
| Example 2 | 137 | V-0 | 93.2 |
| Example 3 | 129 | V-0 | 91.1 |
| Example 4 | 142 | V-0 | 93.9 |
| Example 5 | 146 | V-0 | 94.7 |
| Comparative example | 92 | V-1 | 78.5 |
The heat resistance is detected according to the standard GB/T1634.2-2004, the flame retardant property is detected according to the standard UL94, the glossiness is tested according to the standard ASTM D523, the dimension is 8cm multiplied by 3cm, the measurement angle is 60 degrees, the standards are all standards disclosed in the prior art, and the steps for detecting various properties are introduced in detail, so the standards and the specific detection steps of various properties are not described in detail in the application.
From the above table, it can be seen that the heat resistance, the flame retardant property and the surface gloss of the high heat-resistant flame-retardant polypropylene composite material prepared in the embodiments 1 to 5 of the present application are all obviously improved for the comparative example, and from the embodiments 1 and 2, it can be seen that when the addition amount of the heat-resistant brightening master batch is properly increased, the heat resistance and the surface gloss of the polypropylene composite material are both obviously improved, and the polypropylene composite material has a high flame retardant property, and from the embodiments 1 and 3, it can be seen that when the addition amount of the composite flame retardant is properly increased, the polypropylene composite material has a high flame retardant property, but the surface gloss of the polypropylene composite material is slightly reduced, and the addition amount of the composite flame retardant is possibly increased, and the dispersibility of the composite flame retardant in the polymer is affected.
In conclusion, the heat resistance, the flame retardance and the surface gloss of the high heat-resistant flame-retardant polypropylene composite material are remarkably improved by improving the raw materials and the process of the high heat-resistant flame-retardant polypropylene composite material.
Claims (7)
1. The high heat-resistant flame-retardant polypropylene composite material is characterized by comprising raw materials of polypropylene resin, heat-resistant brightening master batches, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A, wherein the raw materials comprise the following components in parts by weight:
the heat-resistant brightening functional master batch comprises raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, a silane coupling agent, silicone powder, titanium dioxide, a phosphoric acid nucleating agent and an antioxidant B;
the composite flame retardant comprises raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane, sodium tetraborate solution and a silane coupling agent.
2. The high heat-resistant flame-retardant polypropylene composite material as claimed in claim 1, wherein the heat-resistant brightening functional master batch comprises the following raw materials in parts by weight:
3. the high heat-resistant flame-retardant polypropylene composite material as claimed in claim 1, wherein the composite flame retardant master batch comprises the following raw materials in parts by weight:
the concentration of the sodium tetraborate solution is 0.1 mol/L.
4. The polypropylene composite material of claim 1, wherein the lubricant is one or a mixture of two or more of ethylene bis stearamide, polyethylene wax, zinc stearate, barium stearate, oleamide and erucamide.
5. The high heat-resistant flame-retardant polypropylene composite material as claimed in claim 2, wherein the antioxidant A and the antioxidant B are both prepared by mixing the antioxidant 1010 and the antioxidant 168 according to a mass ratio of 1: 1.
6. A method for preparing a high heat-resistant flame-retardant polypropylene composite material according to any one of claims 1 to 5, comprising the following steps:
the method comprises the following steps: preparing heat-resistant brightening functional master batch
Weighing the raw materials of organic silicon resin, alkali-free glass fiber, precipitated barium sulfate, mica powder, a silane coupling agent, silicone powder, titanium dioxide, a phosphoric acid nucleating agent and an antioxidant B according to parts by weight, uniformly mixing by high-temperature melting, and then extruding and granulating by a double-screw extruder to prepare heat-resistant brightening functional master batch;
step two: preparation of composite flame retardant
Weighing raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane, sodium tetraborate solution and a silane coupling agent in parts by weight, sequentially adding the raw materials of magnesium hydroxide, decabromodiphenyl ether, diatomite, cage-type polysilsesquioxane and the silane coupling agent into the sodium tetraborate solution, stirring for 20-40 min, and finally drying and scattering to prepare the composite flame retardant;
step three: preparation of high heat-resistant flame-retardant polypropylene composite master batch
Weighing the raw materials of polypropylene resin, heat-resistant brightening functional master batch, a composite flame retardant, talcum powder, a polypropylene grafted maleic anhydride compatilizer, a lubricant, a silane coupling agent and an antioxidant A according to parts by weight, melting and mixing uniformly at high temperature, and then extruding and granulating by a double-screw extruder to prepare the high heat-resistant flame-retardant polypropylene composite master batch;
step four: preparation of high heat-resistant flame-retardant polypropylene composite material
And directly injection-molding the high-heat-resistant flame-retardant polypropylene composite master batch to prepare the high-heat-resistant flame-retardant polypropylene composite material.
7. The method for preparing the high heat-resistant flame-retardant polypropylene composite material as claimed in claim 6, wherein in the third step, the rotation speed of the twin-screw extruder is 300-500 r/min, and the extrusion temperature of the head is 190-230 ℃.
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