CN115490954A - Polypropylene composite material and preparation method and application thereof - Google Patents
Polypropylene composite material and preparation method and application thereof Download PDFInfo
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- CN115490954A CN115490954A CN202211039583.XA CN202211039583A CN115490954A CN 115490954 A CN115490954 A CN 115490954A CN 202211039583 A CN202211039583 A CN 202211039583A CN 115490954 A CN115490954 A CN 115490954A
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- polypropylene
- polypropylene composite
- flame retardant
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 109
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 109
- -1 Polypropylene Polymers 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 62
- 239000003063 flame retardant Substances 0.000 claims abstract description 61
- 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 claims abstract description 56
- 239000004677 Nylon Substances 0.000 claims abstract description 33
- 229920001778 nylon Polymers 0.000 claims abstract description 33
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 33
- 230000003078 antioxidant effect Effects 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000002781 deodorant agent Substances 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000314 lubricant Substances 0.000 claims description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 8
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 8
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229920002943 EPDM rubber Polymers 0.000 claims description 5
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920000388 Polyphosphate Polymers 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001205 polyphosphate Substances 0.000 claims description 3
- 235000011176 polyphosphates Nutrition 0.000 claims description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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 18
- 229920001410 Microfiber Polymers 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 8
- 239000003658 microfiber Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group 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 description 3
- 230000009471 action Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
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- 239000007924 injection Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920006152 PA1010 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to a polypropylene composite material and a preparation method and application thereof, belonging to the technical field of high polymer materials, wherein the polypropylene composite material comprises the following components: polypropylene resin, nylon resin, a flame-retardant system, montmorillonite and an auxiliary agent; wherein the nylon resin is distributed in the polypropylene resin in a fibrous shape; by blending nylon resin into polypropylene resin, the carbon forming effect of the nylon resin is better than that of the polypropylene resin, the carbon forming effect is improved, and the flame retardance is improved; compared with spherical nylon resin, the fibrous nylon resin has larger specific surface area and higher strength, and additionally, the oxygen passage is increased, and the flame retardant property is improved.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a polypropylene composite material and a preparation method and application thereof.
Background
The polypropylene (PP) has the advantages of small density, low hygroscopicity, easy molding and processing, excellent impact strength, chemical corrosion resistance, good electrical insulation and the like, and can be widely applied to the fields of electronic appliances, automobiles, textiles, building materials and the like. However, PP is extremely easy to burn, and a large amount of molten drops are generated during burning, so that the spread of fire is accelerated, secondary disasters such as scald of personnel in a fire scene are caused, and the application of PP is limited.
The halogen flame retardant has great harm to the ecological environment and human health, so the green and environment-friendly halogen-free flame retardant is developed rapidly. The halogen-free flame retardant mainly comprises an inorganic flame retardant, an organic silicon flame retardant, a halogen-free intumescent flame retardant and the like. The halogen-free flame retardant for polypropylene mainly comprises inorganic metal compounds such as aluminum, magnesium and the like, and a halogen-free intumescent flame retardant which is compounded by taking ammonium polyphosphate as a main body. The halogen flame retardant has the defects of low flame retardant effect, large addition amount and the like, and seriously damages the mechanical property of a matrix, and the flame retardant effect of the halogen flame retardant can be improved to a certain extent by adding certain inorganic nano particles.
Disclosure of Invention
The application provides a polypropylene composite material and a preparation method and application thereof, and aims to solve the problem that the flame retardant property of the existing polypropylene material is poor.
In a first aspect, the present application provides a polypropylene composite.
Specifically, the polypropylene composite material comprises the following components: polypropylene resin, nylon resin, a flame-retardant system, montmorillonite and an auxiliary agent;
wherein the nylon resin is distributed in the polypropylene resin in a fibrous shape.
As an alternative embodiment, the montmorillonite is modified montmorillonite containing ester quaternary ammonium salt.
As an alternative embodiment, the adjuvant comprises: a compatibilizer, an antioxidant, and a lubricant.
As an alternative embodiment, the antioxidant comprises a primary antioxidant and a secondary antioxidant; and/or
The primary antioxidant comprises at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine;
the secondary antioxidant comprises a phosphite antioxidant.
As an alternative embodiment, the polypropylene composite further comprises an odor scavenger.
As an alternative embodiment, the flame retardant system is a intumescent flame retardant system comprising a primary flame retardant, a secondary flame retardant, and a char-forming agent.
As an alternative embodiment, the polypropylene composite material comprises the following components in parts by mass: 40-70 parts of polypropylene resin, 1-5 parts of low-odor compatilizer, 0.5-2.0 parts of deodorant, 5-20 parts of nylon resin, 10-15 parts of main flame retardant, 5-10 parts of auxiliary flame retardant, 2-6 parts of char forming agent, 1-6 parts of montmorillonite, 0.2-0.4 part of main antioxidant, 0.2-0.4 part of auxiliary antioxidant and 0.3-0.6 part of lubricant.
As an alternative embodiment, the polypropylene comprises at least one of homo-polypropylene, random co-polypropylene or block co-polypropylene; and/or
The melt index of the polypropylene is 5-30g/10min; and/or
The compatibilizer comprises at least one of maleic anhydride grafted polypropylene, maleic anhydride grafted EPDM, and maleic anhydride grafted ethylene-octene copolymer; and/or
The deodorant is a reactive deodorant, and the reactive deodorant comprises epoxy resin; and/or
The main flame retardant comprises ammonium polyphosphate; and/or
The auxiliary flame retardant comprises at least one of melamine polyphosphate, melamine cyanurate and triphenyl phosphate; and/or
The char-forming agent comprises pentaerythritol; and/or
The lubricant comprises at least one of EBS and PETS.
In a second aspect, the present application provides a method for preparing a polypropylene composite material, so as to achieve the preparation of the polypropylene composite material according to any one of the embodiments of the first aspect.
Specifically, the method comprises the following steps:
premixing the components of the polypropylene composite material to obtain a premix;
performing first extrusion granulation on the premix to obtain master batches;
and carrying out second extrusion granulation on the master batch by using a micro-nano laminated co-extrusion device to obtain the polypropylene composite material.
In a third aspect, the present application provides a component for use as a polypropylene composite as described in any one of the embodiments of the first aspect.
In particular, at least part of the material of the member comprises a polypropylene composite as described above.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the method provided by the embodiment of the application, the nylon resin is blended into the polypropylene resin, so that the carbon forming effect of the nylon resin is better than that of the polypropylene resin, the carbon forming effect is improved, and the flame retardance is improved; compared with spherical nylon resin, the fibrous nylon resin has larger specific surface area and higher strength, and additionally, the oxygen passage is increased, and the flame retardant property is improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a schematic structural diagram of a micro-nano laminated co-extrusion device provided in an embodiment of the present application;
FIG. 2 is a flow chart of a method provided by an embodiment of the present application;
reference numerals: 1-left single-screw extruder, 2-right single-screw extruder, 3-melt pump, 4-four-layer distributor, 5-four-layer multiplier, 6-three-layer distributor, 7-neck mold and 8-traction roller.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making creative efforts shall fall within the protection scope of the present application.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or can be prepared by an existing method.
The embodiment of the application provides a polypropylene composite material, which comprises the following components: polypropylene resin (PP resin), nylon resin, a flame-retardant system, montmorillonite and an auxiliary agent;
wherein the nylon resin is distributed in the polypropylene resin in a fibrous manner.
Specifically, the nylon resin can be realized by one or a combination of more of common nylon resins, such as nylon resins PA6, PA66, PA1010 or PA610, and the like, and by adopting the design, the nylon resin has better carbon forming effect than the polypropylene resin by blending the nylon resin into the polypropylene resin, so that the carbon forming effect is improved, and the flame retardance is improved; compared with spherical nylon resin, the fibrous nylon resin has larger specific surface area and higher strength, and additionally, the oxygen passage is increased, and the flame retardant property is improved.
Meanwhile, the mechanical property of the nylon resin is higher than that of the polypropylene resin, and the mechanical property of the polypropylene resin can be improved to a certain extent after the nylon resin and the polypropylene resin are melt blended.
In some embodiments, the montmorillonite is an esterquat-containing modified montmorillonite.
In this example, the ester group-containing quaternary ammonium salt modified montmorillonite is prepared by: firstly, adding montmorillonite powder into deionized water, fully stirring to obtain a dispersion liquid with the concentration of 30-60g/L, adding ester-group-containing quaternary ammonium salt surfactant, heating to 70-85 ℃, fully stirring, and carrying out condensation reflux reaction for 2-4 hours to obtain a uniform suspension; and ultrasonically dispersing the suspension uniformly, then centrifugally separating to remove supernatant to obtain a precipitate, washing, drying and grinding the obtained precipitate to obtain the quaternary ammonium salt modified montmorillonite.
In some embodiments, the adjuvant comprises: a compatibilizer, an antioxidant, and a lubricant. Further, the antioxidant includes a primary antioxidant and a secondary antioxidant, and specifically, the primary antioxidant may be at least one selected from the group consisting of pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], octadecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, and N, N' -bis- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexanediamine; the secondary antioxidant may be selected from phosphite antioxidants; the compatilizer is a low-odor compatilizer, and can be selected from any one or more of maleic anhydride grafted polypropylene, maleic anhydride grafted EPDM (ethylene-propylene-diene monomer) or maleic anhydride grafted ethylene-octene copolymer; the lubricant may be selected from a mixture of one or more of EBS and PETS.
To meet the higher demand for low odor, in some embodiments, the polypropylene composite further comprises an odor eliminating agent. The deodorant is a reactive deodorant, and the reactive deodorant comprises epoxy resin, specifically, one or more combinations of epoxy resin E44, E51 and SM601, which can react with residual maleic anhydride in the compatilizer to reduce odor and VOC.
In some embodiments, the flame retardant system is a intumescent flame retardant system that includes a primary flame retardant, a secondary flame retardant, and a char-forming agent.
In the embodiment, the main flame retardant is ammonium polyphosphate (APP); the auxiliary flame retardant is one or a mixture of more of melamine polyphosphate, melamine cyanurate or triphenyl phosphate; the char-forming agent is pentaerythritol PER; the main flame retardant, the auxiliary flame retardant and the char-forming agent jointly form an intumescent flame retardant system, the polypropylene material is flame-retardant in a synergistic manner, and meanwhile, the nylon resin can also be used as a good char-forming agent of the polypropylene resin, so that the char-forming effect is further improved, and the flame retardance is improved.
In this embodiment, the polypropylene composite material includes, in parts by mass: 40-70 parts of polypropylene resin, 1-5 parts of low-odor compatilizer, 0.5-2.0 parts of deodorant, 5-20 parts of nylon resin, 10-15 parts of main flame retardant, 5-10 parts of auxiliary flame retardant, 2-6 parts of char forming agent, 1-6 parts of montmorillonite, 0.2-0.4 part of main antioxidant, 0.2-0.4 part of auxiliary antioxidant and 0.3-0.6 part of lubricant.
The polypropylene resin is used as matrix resin, the mass part of the polypropylene resin is controlled to be 40-70 parts, under the composition, the mechanical property and the flame retardant property of the material are good, the flame retardant property is influenced to a certain extent when the part is too large, and the mechanical property is influenced when the part is too small. Specifically, the polypropylene comprises at least one of homo-polypropylene, random copolymerization polypropylene or block copolymerization polypropylene; more preferably, the melt index of the polypropylene is 5-30g/10min; the melt index is within this range, and the fluidity and processability of the matrix resin are good.
The compatibilizer comprises at least one of maleic anhydride grafted polypropylene, maleic anhydride grafted EPDM, and maleic anhydride grafted ethylene-octene copolymer;
the odor removing agent is a reactive odor removing agent, and the reactive odor removing agent comprises epoxy resin;
the main flame retardant comprises ammonium polyphosphate;
the secondary flame retardant comprises a phosphite antioxidant;
the char-forming agent comprises pentaerythritol;
the lubricant comprises at least one of EBS and PETS.
By adopting the design, an intumescent flame retardant system is formed by the main flame retardant, the auxiliary flame retardant and the charring agent, the PP material is synergistically hindered, and meanwhile, the nylon resin and the montmorillonite can also be used as good charring agents of the PP resin, so that the charring effect is further improved, and the flame retardant effect is improved; the material odor and VOC are effectively reduced through the compounding of the low-odor compatilizer and the deodorant; the addition of the primary antioxidant and the secondary antioxidant can also improve the long-term thermal stability of the PP material; the montmorillonite modified low-odor in-situ microfiber reinforced halogen-free flame retardant polypropylene composite material prepared by the micro-nano lamination co-extrusion process is environment-friendly, low in odor, small in flame retardant addition amount, good in flame retardant property and high in mechanical property.
As shown in fig. 2, based on the same inventive concept, the embodiment of the present application further provides a method for preparing a polypropylene composite material, where the polypropylene composite material is the polypropylene composite material described above; the method comprises the following steps:
s0, preparing quaternary ammonium salt modified montmorillonite according to the method, and drying necessary components;
s1, premixing all components of the polypropylene composite material to obtain a premix;
s2, performing first extrusion granulation on the premix to obtain master batches;
specifically, in this embodiment, the premix is added into a main feeding port of a twin-screw extruder, and at a temperature of 220 to 245 ℃, the screw rotation speed is 300 to 500r/min, and the extruder is granulated and dried to obtain master batches;
and S3, carrying out second extrusion granulation on the master batch by using a micro-nano laminated co-extrusion device to obtain the polypropylene composite material.
The master batch is added into a micro-nano laminated co-extrusion device, the processing temperature of an extruder is 220-245 ℃, the rotating speed of a screw is 300-500 r/min, and the rotating speed of a melt pump is properly adjusted, so that the polypropylene composite material can be prepared.
It should be noted that, as shown in fig. 1, the micro-nano laminated co-extrusion device includes a four-layer distributor 4, two sides of the four-layer distributor 4 are respectively connected with a left single-screw extruder 1 and a right single-screw extruder 2, an outlet of the four-layer distributor 4 is connected with a four-layer multiplier 5, an outlet of the four-layer multiplier 5 is connected with a three-layer distributor 6, an outlet of the three-layer distributor 6 is provided with a neck ring 7, and a traction roller 8 is arranged below the neck ring 7; melt pumps 3 are arranged between the left single-screw extruder 1, the right single-screw extruder 2 and the four-layer distributor 4.
The preparation method of the polypropylene composite material is one of the preparation methods of the polypropylene composite materials, specific components in the preparation method of the polypropylene composite material can refer to the above embodiments, and the preparation method of the polypropylene composite material adopts part or all of the technical schemes of the above embodiments, so that the polypropylene composite material at least has all the beneficial effects brought by the technical schemes of the above embodiments, and details are not repeated herein.
Based on the same inventive concept, the embodiment of the present application further provides a member, at least part of the material of which comprises the polypropylene composite material as described above.
Specifically, the member may be an essential part in the fields of electronic and electric appliances, automobiles, textiles, building materials and the like.
The component is an application of the polypropylene composite material, the specific components of the component can refer to the above embodiment, and since the component adopts part or all of the technical solutions of the above embodiment, at least all the beneficial effects brought by the technical solutions of the above embodiment are achieved, and no further description is given here.
The present application is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. The experimental methods without specifying specific conditions in the following examples were generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the usual international standards, to the conventional conditions or to the conditions recommended by the manufacturer.
It should be noted that the following examples and comparative examples were originally embodied as follows:
the polypropylene resin is produced by petrochemical industry of Korean in Wuhan, and is provided with a mark K7227H; the low odor compatibilizer is a low VOC compatibilizer maleic anhydride grafted polypropylene that is easy to produce, brand CMG5071; the deodorant is epoxy resin produced by the Lanxing chemical industry, and the brand is 0191; the nylon resin is PA6 with 2.45 viscosity produced in Yuanization, and is named as YH400; the main flame retardant is ammonium polyphosphate APP produced by Shandong national chemical Co., ltd, and the molecular formula is H12N3O4P; the auxiliary main combustion agent is melamine cyanurate MCA produced by Qingdao Haimai chemical Limited, and the molecular formula is C3H10N6O7P2; the char-forming agent is pentaerythritol ester produced by Guangzhou Xijia chemical company Limited, brand PER; montmorillonite is according to patent CN 104530774B, patentee; hubei polymerization ] modified montmorillonite containing ester-based quaternary ammonium salt self-made by the method; the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester produced by Pasf chemical industry, and the mark is 1010; the auxiliary antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite produced by basf chemical industry; antioxidant TH-168'; tris (2, 4-di-tert-butylphenyl) phosphite; tris (2, 4-di-tert-butylphenyl) phosphite; tris (2, 4-di-tert-butyl) phosphite, brand 168; the lubricant is EBS manufactured by Kao corporation, and is brand EB-FF.
Example 1
The montmorillonite modified low-odor in-situ microfiber reinforced halogen-free polypropylene composite material is composed of the following components in parts by weight:
the montmorillonite modified low-odor in-situ microfiber reinforced halogen-free flame retardant polypropylene composite material and the preparation method thereof comprise the following steps:
(a) Preparing quaternary ammonium salt modified montmorillonite;
(b) Fully and uniformly mixing the dried PP resin and other raw materials by a high-speed mixer according to the weight ratio to obtain a premix;
(c) Adding the premix into a main feeding port of a double-screw extruder, granulating by the extruder at the temperature of 220-245 ℃ and the screw rotating speed of 300-500 r/min, and drying to obtain the PP master batch;
(d) The master batch is added into a multi-layer extruder 1 and a multi-layer extruder 2, the processing temperature of the extruders is 220-245 ℃, the rotating speed of a screw is 300-500 r/min, and the rotating speed of a melt pump is properly adjusted, so that the PP material can be prepared.
Example 2
The montmorillonite modified low-odor in-situ microfiber reinforced halogen-free polypropylene composite material is composed of the following components in parts by weight:
the preparation method of this example is the same as example 1.
Example 3
The montmorillonite modified low-odor in-situ microfiber reinforced halogen-free polypropylene composite material is composed of the following components in parts by weight:
the preparation method of this example is the same as example 1.
Example 4
The montmorillonite modified low-odor in-situ microfiber reinforced halogen-free polypropylene composite material is composed of the following components in parts by weight:
the preparation method of this example is the same as example 1.
Comparative example 1
The composition of the comparative example was the same as example 1, and the preparation method of the comparative example included:
(a) Preparing quaternary ammonium salt modified montmorillonite;
(b) Fully and uniformly mixing the dried PP resin and other raw materials by a high-speed mixer according to the weight ratio to obtain a premix;
(c) Adding the premix into a main feeding port of a double-screw extruder, granulating by the extruder at the temperature of 220-245 ℃ and the screw rotating speed of 300-500 r/min, and drying to obtain the PP material.
Comparative example 2
The composition of this comparative example was the same as example 2 and the preparation method of this comparative example was the same as comparative example 1.
Comparative example 3
The composition of this comparative example was the same as example 3 and the preparation method of this comparative example was the same as comparative example 1.
Comparative example 4
The composition of this comparative example was the same as example 4 and the preparation method of this comparative example was the same as comparative example 1.
Relevant experiments and effect data:
the 4 example materials were cut and injection molded, and the 4 comparative examples were injection molded directly, with the test data for the properties of the specimens as shown in the following table:
the polypropylene composite material prepared by the embodiment of the invention has high mechanical property, low smell and good flame retardance compared with a comparative example, and mainly because the in-situ microfiber is formed in a polypropylene resin matrix by a nylon dispersion phase after the micro-nano lamination co-extrusion technology is adopted, so that the polypropylene is reinforced, toughened and synergistic in flame retardance; with the increase of the nylon content, the number of formed in-situ micro-fibers is increased, the mechanical property is increased, the flame retardant property is improved, and the melt index is increased.
Various embodiments of the present application may exist in a range of forms; it is to be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the application; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within the stated range, such as 1, 2, 3, 4, 5, and 6, for example, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the range so indicated.
In the present application, unless otherwise specified, the use of directional words such as "upper" and "lower" specifically refer to the orientation of the figures in the drawings. In addition, in the description of the present specification, the terms "include", "includes" and the like mean "including but not limited to". In this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. As used herein, "at least one" means one or more, "a plurality" means two or more. "at least one," "at least one of the following," or similar expressions, refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A polypropylene composite, wherein the polypropylene composite has a composition comprising: polypropylene resin, nylon resin, a flame-retardant system, montmorillonite and an auxiliary agent;
wherein the nylon resin is distributed in the polypropylene resin in a fibrous shape.
2. The polypropylene composite of claim 1, wherein the montmorillonite is an ester-containing quaternary ammonium salt modified montmorillonite.
3. The polypropylene composite according to claim 1 or 2, wherein the auxiliary agent comprises: a compatibilizer, an antioxidant, and a lubricant.
4. The polypropylene composite of claim 3, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant; and/or
The primary antioxidant comprises at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine;
the secondary antioxidant comprises a phosphite antioxidant.
5. The polypropylene composite of claim 3, further comprising an odor scavenger.
6. The polypropylene composite of claim 5, wherein the flame retardant system is an intumescent flame retardant system comprising a primary flame retardant, a secondary flame retardant, and a char former.
7. The polypropylene composite according to claim 6, wherein the polypropylene composite comprises the following components in parts by mass: 40-70 parts of polypropylene resin, 1-5 parts of low-odor compatilizer, 0.5-2.0 parts of deodorant, 5-20 parts of nylon resin, 10-15 parts of main flame retardant, 5-10 parts of auxiliary flame retardant, 2-6 parts of char forming agent, 1-6 parts of montmorillonite, 0.2-0.4 part of main antioxidant, 0.2-0.4 part of auxiliary antioxidant and 0.3-0.6 part of lubricant.
8. The polypropylene composite of claim 6, wherein the polypropylene comprises at least one of homo polypropylene, random co-polypropylene, or block co-polypropylene; and/or
The melt index of the polypropylene is 5-30g/10min; and/or
The compatibilizer comprises at least one of maleic anhydride grafted polypropylene, maleic anhydride grafted EPDM, and maleic anhydride grafted ethylene-octene copolymer; and/or
The deodorant is a reactive deodorant, and the reactive deodorant comprises epoxy resin; and/or
The main flame retardant comprises ammonium polyphosphate; and/or
The auxiliary flame retardant comprises at least one of melamine polyphosphate, melamine cyanurate and triphenyl phosphate; and/or
The char-forming agent comprises pentaerythritol; and/or
The lubricant comprises at least one of EBS and PETS.
9. A method for preparing a polypropylene composite, wherein the polypropylene composite is the polypropylene composite according to any one of claims 1 to 8; the method comprises the following steps:
premixing the components of the polypropylene composite material to obtain a premix;
performing first extrusion granulation on the premix to obtain master batches;
and carrying out second extrusion granulation on the master batch by using a micro-nano laminated co-extrusion device to obtain the polypropylene composite material.
10. A component, characterized in that at least part of the material of the component comprises a polypropylene composite according to any one of claims 1 to 8.
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