CN114854130B - High-impact-resistance halogen-free flame-retardant polypropylene composite material and preparation method thereof - Google Patents
High-impact-resistance halogen-free flame-retardant polypropylene composite material and preparation method thereof Download PDFInfo
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- CN114854130B CN114854130B CN202210604386.1A CN202210604386A CN114854130B CN 114854130 B CN114854130 B CN 114854130B CN 202210604386 A CN202210604386 A CN 202210604386A CN 114854130 B CN114854130 B CN 114854130B
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- -1 polypropylene Polymers 0.000 title claims abstract description 197
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 193
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 193
- 239000003063 flame retardant Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 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 description 32
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 48
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 41
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 7
- 239000002086 nanomaterial Substances 0.000 claims abstract description 6
- 239000000155 melt Substances 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 16
- 238000001694 spray drying Methods 0.000 claims description 16
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 12
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 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 description 9
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000000806 elastomer Substances 0.000 claims description 7
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical group C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 claims description 3
- 238000013016 damping Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 15
- 239000007921 spray Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- ACRQLFSHISNWRY-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-phenoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=CC=CC=C1 ACRQLFSHISNWRY-UHFFFAOYSA-N 0.000 description 1
- ORYGKUIDIMIRNN-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5-(2,3,4,5-tetrabromophenoxy)benzene Chemical compound BrC1=C(Br)C(Br)=CC(OC=2C(=C(Br)C(Br)=C(Br)C=2)Br)=C1Br ORYGKUIDIMIRNN-UHFFFAOYSA-N 0.000 description 1
- CWZVMVIHYSYLSI-UHFFFAOYSA-N 1,3-dibromo-5-[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]sulfonyl-2-(2,3-dibromopropoxy)benzene Chemical compound C1=C(Br)C(OCC(Br)CBr)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(OCC(Br)CBr)C(Br)=C1 CWZVMVIHYSYLSI-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene 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
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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 invention relates to the technical field of high polymer materials, in particular to a high impact resistance halogen-free flame retardant polypropylene composite material and a preparation method thereof. The high impact resistance halogen-free flame retardant polypropylene composite material is prepared from the following components: 100 parts of polypropylene, 20-30 parts of nano material, 20-30 parts of impact modifier, 1-5 parts of nano silica sol modified by silane coupling agent and 20-30 parts of halogen-free flame retardant. The polypropylene composite material provided by the invention not only has high impact resistance and halogen-free flame retardance, but also has a good damping effect, and can well play a role in damping and noise reduction.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high impact resistance halogen-free flame retardant polypropylene composite material and a preparation method thereof.
Background
Polypropylene is a polymer obtained by addition polymerization of propylene, and is a white wax-like material having a transparent and light appearance and a density of 0.89 to 0.91g/cm 3 Inflammable, and has melting point of 165 deg.c, softening at 155 deg.c, use temperature range of-30-140 deg.c, acid, alkali, salt and other organic solvent corrosion resistance below 80 deg.c, and high temperature and oxidation decomposition.
Since the industrial production of polypropylene was first realized by Montecatini, italy, 1957, polypropylene yield has been rapidly developed, and polypropylene has become one of the most rapid-growing and most active products for new varieties in five general synthetic resins. The polypropylene has better comprehensive performance, such as easily available raw materials, low price, no toxicity and no smell; good processability, high strength and low relative density; the heat resistance, the abrasion resistance, the solvent resistance and the electrical insulation are all excellent. The method is widely applied to the fields of automobiles, building materials, household appliances and the like, and the application range of the method is continuously expanded even in the fields of medical treatment, sanitation, biology and the like.
However, polypropylene is extremely flammable. Meanwhile, the polypropylene product has the defects of large brittleness (especially at low temperature) and low notch impact strength, and the problems of poor damping effect and poor noise and vibration reduction capability in the use process of the polypropylene material are also existed, which prevent the development and application of the polypropylene material in the application field.
Flame retardant modification of polypropylene is currently classified into halogen flame retardant and halogen-free flame retardant, wherein the halogen flame retardant is environment-friendly (accords with European RoHS) and non-environment-friendly (does not accord with European RoHS), and the halogen-free flame retardant is environment-friendly at present. The halogen environment-friendly flame retardant mainly comprises tetrabromobisphenol A, octabromoether, octabromobisphenol S ether, brominated epoxy resin, brominated polystyrene, chlorinated polyethylene, decabromodiphenylethane and the like; halogen-containing non-environment-friendly flame retardants currently include pentabromodiphenyl ether, octabromodiphenyl ether and the like; there are nitrogen-phosphorus intumescent halogen-free flame retardants commonly used at present as halogen-free environment-friendly flame retardants.
However, at present, the halogen-containing flame-retardant modified polypropylene or halogen-free flame-retardant modified polypropylene has the greatest defect that the mechanical property, particularly the impact resistance of the material is most obviously reduced due to the introduction of the flame retardant. In order to avoid the reduction of impact performance, the polypropylene and the flame retardant are directly added with an elastomer for toughening, and the polypropylene and the flame retardant are melt-extruded and blended by a one-step method. Among the commonly used elastomers are ethylene-octene copolymers (POE), triisopropylene rubbers (EPDM), styrene-butadiene-styrene terpolymers (SBS), etc. The main defects of the existing one-step method are that a large amount of elastomer is needed to improve the impact performance, so that the tensile strength, the bending strength and the like of the material are obviously reduced, and the amount of flame retardant is increased due to the introduction of a large amount of elastomer, so that the cost is increased.
CN102532688A discloses a high-strength, high-toughness and flame-retardant polypropylene material, a preparation method and application thereof, comprising the following components in parts by weight: 20 to 50 parts of polypropylene, 0.1 to 10 parts of toughening agent, 1 to 10 parts of compatilizer, 16 to 22 parts of compound flame retardant, 0.2 to 0.4 part of antioxidant, 0.1 to 0.4 part of light stabilizer and 30 to 50 parts of glass fiber. The polypropylene material prepared by the invention has higher tensile strength, flexural modulus and impact strength, and good flame retardance, and is the most suitable material for engineering plastic building templates.
CN114031842a discloses an impact-resistant halogen-free flame retardant polypropylene composition, a preparation method and application thereof. The halogen-free flame retardant polypropylene composition comprises the following components in parts by weight: 65-85 parts of polypropylene, 5-10 parts of polyvinylidene fluoride, 3-10 parts of compatilizer, 5-12 parts of flexibilizer, 5-9 parts of halogen-free flame retardant and 0-5 parts of lubricant; the average molecular weight of the polyvinylidene fluoride is 20-31 ten thousand. The invention uses the blend of polyvinylidene fluoride and polypropylene as the resin matrix of the halogen-free flame retardant polypropylene composition, obtains excellent flame retardant property under the condition of less halogen-free flame retardant, greatly improves the impact resistance of the halogen-free flame retardant polypropylene composition, and has the cantilever beam notch impact strength more than or equal to 24kJ/m at normal temperature 2 The notch impact strength of the cantilever beam at low temperature is more than or equal to 2.0kJ/m 2 。
CN112175310a discloses a phosphorus-containing flame-retardant rigid polypropylene material and a preparation method thereof; the phosphorus-containing flame-retardant rigid polypropylene material comprises the following components in parts by weight: 100 parts by mass of polypropylene grafted phosphorus-containing flame retardant, 5-20 parts by mass of toughening agent and 0.5-1.5 parts by mass of composite antioxidant; the phosphorus-containing flame-retardant rigid polypropylene material prepared by grafting the flame retardant on the polypropylene molecular chain ensures that the polypropylene molecules have flame retardance, solves the problems that the dispersion uniformity of the flame retardant is difficult to ensure, the loss of flame retardant components is difficult to avoid and the long-term flame retardant performance of a product is directly influenced, and the grafted flame retardant contains a large number of benzene rings on the molecules, so that the introduction of the flame retardant improves the rigidity of the polypropylene.
Although the above polypropylene material has improved flame retardancy, toughness and impact resistance to some extent, it has been found that the damping effect thereof is not improved in use, which becomes a serious problem in impeding the development of polypropylene materials. The loss factor of polypropylene is only 0.05-0.08, and in daily application, the material can play a role in shock absorption and noise reduction when the loss factor is more than 0.1.
Disclosure of Invention
The invention aims to provide a high impact resistance halogen-free flame retardant polypropylene composite material and a preparation method thereof. The polypropylene composite material provided by the invention not only has high impact resistance and halogen-free flame retardance, but also has a good damping effect, and can well play a role in damping and noise reduction.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the high-impact-resistance halogen-free flame-retardant polypropylene composite material is prepared from the following components:
further, the silane coupling agent modified nano silica sol is obtained by mixing nano silica sol and a silane coupling agent, adding water, and performing ultrasonic dispersion and spray drying.
Further, the mass of the solid content of the nano silica sol and the dosage of the silane coupling agent are 1g: 0.8-2.2 mmol.
Further, the nano silica sol is nano silica sol with solid content of 25-35%, and the particle size of the nano silica sol is 20-40 nm.
Further, the polypropylene comprises polypropylene I and polypropylene II, wherein the polypropylene I is polypropylene with a melt index of 180-350 g/10min, and the polypropylene II is polypropylene with a melt index of 1300-1500 g/10 min; the mass ratio of the polypropylene I to the polypropylene II is 10: 90-90: 10.
further, the method comprises the steps of,
the impact modifier is polyethylene octene co-elastomer;
the silane coupling agent is gamma-aminopropyl triethoxysilane;
the nano material is nano montmorillonite;
the halogen-free flame retardant is piperazine pyrophosphate flame retardant.
The invention also provides a preparation method of the high impact resistance halogen-free flame retardant polypropylene composite material, wherein the preparation method comprises the following steps:
1) Mixing and stirring an impact modifier and a nano material to obtain a mixture;
2) Adding polypropylene into the mixture to obtain a premix;
3) Uniformly mixing the premix, the nano silica sol modified by the silane coupling agent and the halogen-free flame retardant, and then carrying out melt extrusion to obtain the high-impact-resistance halogen-free flame retardant polypropylene composite material.
Further, in the step 3), the nano silica sol modified by the silane coupling agent is obtained by mixing the nano silica sol and the silane coupling agent, adding water, and performing ultrasonic dispersion and spray drying.
Further, the ultrasonic dispersion time is 10-20 min.
Further, in the step 2), the polypropylene is prepared by mixing polypropylene I and polypropylene II according to a mass ratio of 10: 90-90: 10, wherein the polypropylene I is polypropylene with a melt index of 180-350 g/10min, and the polypropylene II is polypropylene with a melt index of 1300-1500 g/10 min.
Compared with the prior art, the invention has the following advantages:
the polypropylene composite material provided by the invention not only has high impact resistance and halogen-free flame retardance, but also has a good damping effect, and can well play a role in damping and noise reduction.
Detailed Description
The following are specific embodiments of the present invention, which are described in order to further illustrate the invention, not to limit the invention.
In the following examples and comparative examples, the impact modifier was a polyethylene octene co-elastomer (POE) in which the octene content was 35% to 40%. In the POE used in the invention, only the content of the octene is limited, the specific limitation on the block distribution type and the components is not needed, and all products which are commercially available and have the octene content within the set range can meet the requirements of the invention.
The halogen-free flame retardant is a piperazine pyrophosphate flame retardant, the brand of the halogen-free flame retardant is 5001, and the manufacturer is Guangdong Shunde same-path new material technology Co.
Example 1
The high impact resistance halogen-free flame retardant polypropylene composite material of the embodiment is prepared from the following components:
wherein the polypropylene comprises polypropylene I and polypropylene II, and the mass ratio of the polypropylene I to the polypropylene II is 10:90, wherein the polypropylene I is polypropylene with a melt index of 180g/10min, and the polypropylene II is polypropylene with a melt index of 1300g/10 min; the octene content in POE was 35%.
The preparation method comprises the following steps:
1. preparation of Polypropylene particles
Polypropylene I with the melt index of 180g/10min and polypropylene II with the melt index of 1300g/10min are mixed according to the mass ratio of 10: and (3) granulating the mixture by a double screw after 90 blending, and controlling the temperature of the screw to be 130-155 ℃ for granulating to obtain polypropylene particles.
2. Preparation of silane coupling agent modified nano silica sol
Mixing nano silica sol with solid content of 25% and particle size of 20nm with gamma-aminopropyl triethoxy silane coupling agent (the mass of the solid content of the nano silica sol and the dosage of the gamma-aminopropyl triethoxy silane coupling agent are 1g:0.8 mmol), adding a proper amount of water as a solvent, performing ultrasonic dispersion for 10min, performing spray drying, controlling the air inlet temperature of a spray dryer within 115-125 ℃, controlling the air outlet temperature of the spray dryer within 65-75 ℃, and collecting solid dry powder in a cyclone separator after spray drying to obtain the nano silica sol modified by the silane coupling agent.
3. Preparation of Polypropylene composite material
1) Mixing and stirring 20 parts by weight of POE and 20 parts by weight of nano montmorillonite to obtain a mixture;
2) Adding 100 parts by weight of polypropylene particles into the mixture obtained in the step 1) to obtain a premix;
3) Mixing 1 part by weight of the premix compound obtained in the step 2) and the nano silica sol modified by the silane coupling agent with 20 parts by weight of the halogen-free flame retardant in a high-speed mixer for 10 minutes, and carrying out melt extrusion granulation in a double-screw extruder, wherein the melt extrusion temperature is controlled at 170-200 ℃, so as to obtain the high-impact-resistance halogen-free flame retardant polypropylene composite material.
Example 2
The high impact resistance halogen-free flame retardant polypropylene composite material of the embodiment is prepared from the following components:
wherein the polypropylene comprises polypropylene I and polypropylene II, and the mass ratio of the polypropylene I to the polypropylene II is 90:10, wherein the polypropylene I is polypropylene with a melt index of 350g/10min, and the polypropylene II is polypropylene with a melt index of 1500g/10 min; the octene content in POE was 40%.
The preparation method comprises the following steps:
1. preparation of Polypropylene particles
Polypropylene I with the melt index of 350g/10min and polypropylene II with the melt index of 1500g/10min are mixed according to the mass ratio of 90:10, granulating by double screws after blending, and controlling the temperature of the screws at 130-155 ℃ to obtain polypropylene particles.
2. Preparation of silane coupling agent modified nano silica sol
Mixing nano silica sol with solid content of 35% and particle size of 40nm with gamma-aminopropyl triethoxy silane coupling agent (the mass of the solid content of the nano silica sol and the dosage of the gamma-aminopropyl triethoxy silane coupling agent are 1g:2.2 mmol), adding a proper amount of water as a solvent, performing ultrasonic dispersion for 20min, performing spray drying, controlling the air inlet temperature of a spray dryer within 115-125 ℃, controlling the air outlet temperature of the spray dryer within 65-75 ℃, and collecting solid dry powder in a cyclone separator after spray drying to obtain the nano silica sol modified by the silane coupling agent.
3. Preparation of Polypropylene composite material
1) Mixing and stirring 30 parts by weight of POE and 30 parts by weight of nano montmorillonite to obtain a mixture;
2) Adding 100 parts by weight of polypropylene particles into the mixture obtained in the step 1) to obtain a premix;
3) Mixing 5 parts by weight of the premix compound obtained in the step 2), 5 parts by weight of the nano silica sol modified by the silane coupling agent and 30 parts by weight of the halogen-free flame retardant in a high-speed mixer for 10 minutes, and carrying out melt extrusion granulation in a double-screw extruder, wherein the melt extrusion temperature is controlled at 170-200 ℃, so as to obtain the high-impact-resistance halogen-free flame retardant polypropylene composite material.
Example 3
The high impact resistance halogen-free flame retardant polypropylene composite material of the embodiment is prepared from the following components:
wherein the polypropylene comprises polypropylene I and polypropylene II, and the mass ratio of the polypropylene I to the polypropylene II is 50:50, wherein the polypropylene I is polypropylene with a melt index of 200g/10min, and the polypropylene II is polypropylene with a melt index of 1400g/10 min; the octene content in POE was 38%.
The preparation method comprises the following steps:
1. preparation of Polypropylene particles
Polypropylene I with a melt index of 200g/10min and polypropylene II with a melt index of 1400g/10min are mixed according to a mass ratio of 50:50, granulating by double screws after blending, and granulating by controlling the temperature of the screws at 130-155 ℃ to obtain polypropylene particles.
2. Preparation of silane coupling agent modified nano silica sol
Mixing nano silica sol with solid content of 28% and particle size of 32nm with gamma-aminopropyl triethoxy silane coupling agent (the mass of the solid content of the nano silica sol and the dosage of the gamma-aminopropyl triethoxy silane coupling agent are 1g:1.5 mmol), adding a proper amount of water as a solvent, performing ultrasonic dispersion for 15min, performing spray drying, controlling the air inlet temperature of a spray dryer within 115-125 ℃, controlling the air outlet temperature of the spray dryer within 65-75 ℃, and collecting solid dry powder in a cyclone separator after spray drying to obtain the nano silica sol modified by the silane coupling agent.
3. Preparation of Polypropylene composite material
1) Mixing and stirring 25 parts by weight of POE and 25 parts by weight of nano montmorillonite to obtain a mixture;
2) Adding 100 parts by weight of polypropylene particles into the mixture obtained in the step 1) to obtain a premix;
3) 3 parts by weight of premix compound obtained in the step 2), 3 parts by weight of nano silica sol modified by a silane coupling agent and 25 parts by weight of halogen-free flame retardant are mixed in a high-speed mixer for 10 minutes, and are subjected to melt extrusion granulation in a double-screw extruder, wherein the melt extrusion temperature is controlled at 170-200 ℃, so that the high impact resistance halogen-free flame retardant polypropylene composite material is obtained.
Example 4
The high impact resistance halogen-free flame retardant polypropylene composite material of the embodiment is prepared from the following components:
wherein the polypropylene comprises polypropylene I and polypropylene II, and the mass ratio of the polypropylene I to the polypropylene II is 30:70, wherein the polypropylene I is polypropylene with a melt index of 300g/10min, and the polypropylene II is polypropylene with a melt index of 1350g/10 min; the octene content in POE was 37%.
The preparation method comprises the following steps:
1. preparation of Polypropylene particles
Polypropylene I with the melt index of 300g/10min and polypropylene II with the melt index of 1350g/10min are mixed according to the mass ratio of 30:70, granulating by a double screw after blending, and granulating by controlling the temperature of the screw at 130-155 ℃ to obtain polypropylene particles.
2. Preparation of silane coupling agent modified nano silica sol
Mixing nano silica sol with solid content of 32% and particle size of 36nm with gamma-aminopropyl triethoxy silane coupling agent (the mass of the solid content of the nano silica sol and the dosage of the gamma-aminopropyl triethoxy silane coupling agent are 1g:1.6 mmol), adding a proper amount of water as a solvent, performing ultrasonic dispersion for 18min, performing spray drying, controlling the air inlet temperature of a spray dryer within 115-125 ℃, controlling the air outlet temperature of the spray dryer within 65-75 ℃, and collecting solid dry powder in a cyclone separator after spray drying to obtain the nano silica sol modified by the silane coupling agent.
3. Preparation of Polypropylene composite material
1) Mixing and stirring 22 parts by weight of POE and 22 parts by weight of nano montmorillonite to obtain a mixture;
2) Adding 100 parts by weight of polypropylene particles into the mixture obtained in the step 1) to obtain a premix;
3) Mixing 2 parts by weight of premix compound obtained in the step 2), 2 parts by weight of nano silica sol modified by a silane coupling agent and 22 parts by weight of halogen-free flame retardant in a high-speed mixer for 10 minutes, and carrying out melt extrusion granulation in a double-screw extruder, wherein the melt extrusion temperature is controlled at 170-200 ℃, so as to obtain the high-impact-resistance halogen-free flame retardant polypropylene composite material.
Example 5
The high impact resistance halogen-free flame retardant polypropylene composite material of the embodiment is prepared from the following components:
wherein the polypropylene comprises polypropylene I and polypropylene II, and the mass ratio of the polypropylene I to the polypropylene II is 25:75, wherein the polypropylene I is polypropylene with a melt index of 260g/10min, and the polypropylene II is polypropylene with a melt index of 1430g/10 min; the octene content in POE was 39%.
The preparation method comprises the following steps:
1. preparation of Polypropylene particles
Polypropylene I with a melt index of 260g/10min and polypropylene II with a melt index of 1430g/10min are mixed according to a mass ratio of 25:75, granulating by double screws, wherein the temperature of the screws is controlled between 130 ℃ and 155 ℃ for granulating, and obtaining polypropylene particles.
2. Preparation of silane coupling agent modified nano silica sol
Mixing nano silica sol with solid content of 31% and particle size of 27nm with gamma-aminopropyl triethoxy silane coupling agent (the mass of the solid content of the nano silica sol and the dosage of the gamma-aminopropyl triethoxy silane coupling agent are 1g:1.3 mmol), adding a proper amount of water as a solvent, performing ultrasonic dispersion for 14min, performing spray drying, controlling the air inlet temperature of a spray dryer within 115-125 ℃, controlling the air outlet temperature of the spray dryer within 65-75 ℃, and collecting solid dry powder in a cyclone separator after spray drying to obtain the nano silica sol modified by the silane coupling agent.
3. Preparation of Polypropylene composite material
1) Mixing and stirring 26 parts by weight of POE and 28 parts by weight of nano montmorillonite to obtain a mixture;
2) Adding 100 parts by weight of polypropylene particles into the mixture obtained in the step 1) to obtain a premix;
3) 4.2 parts by weight of premix compound obtained in the step 2), nano silica sol modified by a silane coupling agent and 27 parts by weight of halogen-free flame retardant are mixed in a high-speed mixer for 10 minutes, and are subjected to melt extrusion granulation in a double-screw extruder, wherein the melt extrusion temperature is controlled at 170-200 ℃, so that the high impact resistance halogen-free flame retardant polypropylene composite material is obtained.
Comparative example 1
The polypropylene composite material of the comparative example is prepared from the following components:
wherein, the polypropylene is polypropylene with a melt index of 180g/10 min; the octene content in POE was 35%.
The preparation method comprises the following steps:
1) Mixing and stirring 20 parts by weight of POE and 20 parts by weight of nano montmorillonite to obtain a mixture;
2) Adding 100 parts by weight of polypropylene into the mixture obtained in the step 1) to obtain a premix;
3) Mixing the premix obtained in the step 2) with 20 parts by weight of halogen-free flame retardant in a high-speed mixer for 10 minutes, and carrying out melt extrusion granulation in a double-screw extruder, wherein the melt extrusion temperature is controlled at 170-200 ℃, so as to obtain the polypropylene composite material.
Comparative example 2
This comparative example is identical to comparative example 1, except that the polypropylene used is a polypropylene having a melt index of 1300g/10 min.
Comparative example 3
The polypropylene composite material of the comparative example is prepared from the following components:
wherein the polypropylene comprises polypropylene I and polypropylene II, and the mass ratio of the polypropylene I to the polypropylene II is 10:90, wherein the polypropylene I is polypropylene with a melt index of 180g/10min, and the polypropylene II is polypropylene with a melt index of 1300g/10 min; the octene content in POE was 35%.
The preparation method comprises the following steps:
1. preparation of Polypropylene particles
Polypropylene I with the melt index of 180g/10min and polypropylene II with the melt index of 1300g/10min are mixed according to the mass ratio of 10: and (3) granulating the mixture by a double screw after 90 blending, and controlling the temperature of the screw to be 130-155 ℃ for granulating to obtain polypropylene particles.
2. Preparation of Polypropylene composite material
1) Mixing and stirring 20 parts by weight of POE and 20 parts by weight of nano montmorillonite to obtain a mixture;
2) Adding 100 parts by weight of polypropylene particles into the mixture obtained in the step 1) to obtain a premix;
3) Spray drying nanometer silica sol with solid content of 25% and particle size of 20nm, controlling the air inlet temperature of a spray dryer within 115-125 ℃, controlling the air outlet temperature of the spray dryer within 65-75 ℃, and collecting solid dry powder in a cyclone separator after spray drying to obtain nanometer silica sol powder; mixing 1 part by weight of the premix compound, the nano silica sol powder obtained in the step 2) and 20 parts by weight of the halogen-free flame retardant in a high-speed mixer for 10 minutes, and carrying out melt extrusion granulation in a double-screw extruder, wherein the melt extrusion temperature is controlled at 170-200 ℃, so as to obtain the polypropylene composite material.
Test examples
The test example examined the properties of the polypropylene composite materials prepared in the above examples and comparative examples. The specific method comprises the following steps:
the method comprises the following steps: the polypropylene composite materials prepared in the above examples and comparative examples were injection molded, respectively, to obtain test bars, and the following properties were examined. The detection method of each performance is as follows:
flame retardant properties: the test was carried out according to UL-94 vertical burning, the sample size being 125X103X 3.0mm;
tensile strength: the stretching speed was 50mm/min according to ISO 527-2-2016;
cantilever beam notch impact strength at normal temperature: testing according to ISO 180-2000 standard;
notched impact strength of cantilever beam at low temperature: placing the sample bar at the temperature of minus 20 ℃ for 24 hours, and testing according to the ISO 180-2000 standard;
damping performance test: cutting test sample bars into square shapes of 100mm multiplied by 10mm, wherein the thickness of a sample is 4mm, the dynamic mechanical performance is tested, the test temperature is in the range of-79 ℃ to 100 ℃, the test mode is in a double cantilever mode, the heating rate is 3 ℃/min, the maximum force amplitude is 2N, the maximum displacement amplitude is 20 mu m, the maximum load is 5 to 10N, and the test frequency is 10Hz.
The test results are shown in Table 1:
TABLE 1 Performance test results
As can be seen from the test results, compared with the polypropylene composite material prepared by the comparative example, the polypropylene composite material prepared by the invention not only has better flame retardant property, but also has excellent mechanical property, and the damping effect is obviously improved.
Claims (6)
1. The high-impact-resistance halogen-free flame-retardant polypropylene composite material is characterized by being prepared from the following components:
100 parts by weight of polypropylene
20 to 30 parts by weight of nano material
20 to 30 parts by weight of impact modifier
1 to 5 weight portions of silane coupling agent modified nano silica sol
20-30 parts by weight of halogen-free flame retardant;
the silane coupling agent modified nano silica sol is obtained by mixing nano silica sol and a silane coupling agent, adding water, and performing ultrasonic dispersion and spray drying;
the polypropylene comprises polypropylene I and polypropylene II, wherein the polypropylene I is polypropylene with a melt index of 180-350 g/10min, and the polypropylene II is polypropylene with a melt index of 1300-1500 g/10 min; the mass ratio of the polypropylene I to the polypropylene II is 10: 90-90: 10;
the nano material is nano montmorillonite.
2. The high impact resistance halogen-free flame retardant polypropylene composite material according to claim 1, wherein the solid content mass of the nano silica sol and the dosage of the silane coupling agent are 1g: 0.8-2.2 mmol.
3. The high impact resistance halogen-free flame retardant polypropylene composite material according to claim 2, wherein the nano silica sol is a nano silica sol with a solid content of 25-35% and a particle size of 20-40 nm.
4. A high impact halogen-free flame retardant polypropylene composite material as claimed in any one of claims 1 to 3, wherein,
the impact modifier is polyethylene octene co-elastomer;
the silane coupling agent is gamma-aminopropyl triethoxysilane;
the halogen-free flame retardant is piperazine pyrophosphate flame retardant.
5. A method for preparing the high impact resistance halogen-free flame retardant polypropylene composite material according to any one of claims 1 to 4, wherein the preparation method comprises the following steps:
1) Mixing and stirring an impact modifier and a nano material to obtain a mixture;
2) Adding polypropylene into the mixture to obtain a premix;
3) Uniformly mixing premix, nano silica sol modified by a silane coupling agent and a halogen-free flame retardant, and then carrying out melt extrusion to obtain a high-impact-resistance halogen-free flame retardant polypropylene composite material;
in the step 3), the nano silica sol modified by the silane coupling agent is obtained by mixing the nano silica sol and the silane coupling agent, adding water, and performing ultrasonic dispersion and spray drying.
6. The method according to claim 5, wherein the ultrasonic dispersion is carried out for 10 to 20 minutes.
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