CN114410010B - Flame-retardant polypropylene material and preparation method thereof - Google Patents
Flame-retardant polypropylene material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 130
- 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 97
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 67
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 67
- -1 polypropylene Polymers 0.000 title claims abstract description 65
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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 32
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000004033 plastic Substances 0.000 claims abstract description 8
- 229920003023 plastic Polymers 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 239000003963 antioxidant agent Substances 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 239000000347 magnesium hydroxide Substances 0.000 claims description 17
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000004611 light stabiliser Substances 0.000 claims description 13
- PVKCVCDTYNNNOG-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrobromide Chemical compound [Br-].NC1=NC(N)=[NH+]C(N)=N1 PVKCVCDTYNNNOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 11
- 239000012745 toughening agent Substances 0.000 claims description 11
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical group CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920005633 polypropylene homopolymer resin Polymers 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 46
- 230000000694 effects Effects 0.000 abstract description 28
- 239000001569 carbon dioxide Substances 0.000 abstract description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 23
- 238000001179 sorption measurement Methods 0.000 abstract description 19
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 231100000252 nontoxic Toxicity 0.000 abstract description 6
- 230000003000 nontoxic effect Effects 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 46
- 230000000052 comparative effect Effects 0.000 description 28
- 238000012360 testing method Methods 0.000 description 8
- 239000000155 melt Substances 0.000 description 6
- 229920005606 polypropylene copolymer Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 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
- C08L23/14—Copolymers of propene
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant polypropylene material and a preparation method thereof, and belongs to the technical field of plastic materials. The modified magnesium hydroxide without organic halogen is used as a halogen-free flame retardant and matched with a specific flame retardant synergist to be used as a flame retardant system, so that the flame retardant polypropylene material is more nontoxic and environment-friendly, can realize excellent synergistic flame retardant effect, and has carbon dioxide adsorption effect; the product has moderate density and good mechanical property, and can be suitable for various application ranges. The invention also discloses a preparation method of the flame-retardant polypropylene material and application of the flame-retardant polypropylene material in preparation of plastic parts of automobiles or household appliances.
Description
Technical Field
The invention relates to the technical field of plastic materials, in particular to a flame-retardant polypropylene material and a preparation method thereof.
Background
Polypropylene is used as one of general plastics, and has wide application in modern industry due to its wide source and low cost, and is widely used in the fields of articles for daily use, electronic and electric appliances, transportation, building materials, etc. However, because of its low oxygen index, the heat of combustion is high, and once ignited, it is extremely prone to fire. Therefore, flame retardant modification of polypropylene is necessary to increase the safety and expand the range of use. The flame retardant adopted by the polypropylene at present is mainly a traditional halogen-containing flame retardant, and although the flame retardant has good flame retardant effect, a large amount of toxic smoke can be generated during combustion, so that serious pollution is caused. The use of such flame retardants in some european and american countries is currently severely limited due to environmental and safety concerns. In view of the above, the development of a novel flame retardant which is nontoxic, efficient and environment-friendly has great practical significance.
With the development of modern industrial level, the carbon dioxide emission amount caused by human activities is increasing, and the increase of the carbon dioxide content in the atmosphere causes remarkable greenhouse effect and causes global climate change. In order to cope with the above, countries around the world have been proceeding to reduce emissions of greenhouse gases. Means for reducing carbon dioxide emissions, firstly carbon sequestration, and secondly carbon offset. The method of solidifying and sealing the carbon dioxide by utilizing the reaction of the carbon dioxide and the compound containing calcium or magnesium has a certain theoretical basis, but is not applied on a large scale at present.
CN1465618A discloses a magnesium hydroxide halogen-free flame retardant polypropylene composite material, in order to ensure the flame retardant effect, the magnesium hydroxide has a higher adding proportion, and the application range of the material is limited by a larger density. Therefore, the prior art also adopts a flame-retardant system composed of magnesium hydroxide and other flame retardants to be compounded with polypropylene, but the materials have the defects of poor toughness and other mechanical properties which are difficult to adjust. The application range of the current environment-friendly low-halogen/halogen-free flame-retardant polypropylene material is relatively limited, and no more universal material exists. In addition, research results on carbon-adsorbed modified polypropylene materials have remained blank so far.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide a flame-retardant polypropylene material, which takes modified magnesium hydroxide as a main body of a flame retardant, is low-carbon and environment-friendly, can realize excellent flame-retardant effect when being matched with a flame-retardant synergist, and has the effect of adsorbing carbon dioxide; the product has moderate density and good mechanical property, and can be suitable for various application ranges.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the flame-retardant polypropylene material comprises the following components in parts by weight:
50-80 parts of polypropylene resin, 20-40 parts of halogen-free flame retardant, 1-3 parts of flame retardant synergist and 0.5-2 parts of processing aid;
the halogen-free flame retardant is magnesium hydroxide coated and modified by a silane coupling agent, and the particle size is 0.5-5 mu m;
the flame retardant synergist is a mixture of melamine hydrobromide and aluminum hypophosphite; the mass ratio of the melamine hydrobromide to the aluminum hypophosphite is 1:5 to 1:2.
the inventor finds that although the magnesium hydroxide has certain flame retardance, the magnesium hydroxide always needs to be added with a larger content in the material to realize the flame retardant effect of V-2 grade or above, meanwhile, the magnesium hydroxide has poor compatibility with a polypropylene resin matrix, is easy to generate agglomeration phenomenon in the processing process, cannot exert actual synergistic effect with a flame retardant synergist, and also can cause poor mechanical property of a final product; the magnesium hydroxide coated and modified by the silane coupling agent has the advantages that the surface is subjected to grafting modification, so that the compatibility of the halogen-free flame retardant and the polypropylene resin is greatly improved, meanwhile, the halogen-free flame retardant can be always kept in a uniformly dispersed state in the processing process, when the magnesium hydroxide is matched with two components of the flame retardant synergist to form a flame retardant system, the magnesium hydroxide does not contain organic halogen components, compared with the traditional composite flame retardant, the magnesium hydroxide is more nontoxic and environment-friendly, the flame retardant effect is also obviously improved, and meanwhile, the magnesium hydroxide is alkaline, can adsorb and react with carbon dioxide, and has the following reaction formula:
Mg(OH) 2 +CO 2 →MgCO 3 +H 2 O
at a particular modified clad thickness (in the prior art,in order to ensure the uniformity and the dispersibility of the coated product, the average grain diameter of the obtained coated magnesium hydroxide product is at least more than 0.5 mu m, the magnesium hydroxide can realize the normal adsorption effect, and when the magnesium hydroxide is used as a halogen-free flame retardant to be blended with polypropylene, the finally prepared flame retardant polypropylene material also has a certain carbon dioxide adsorption capacity and has a certain carbon dioxide adsorption capacity to CO after 30 days at normal temperature 2 The adsorption rate of the catalyst reaches more than 1.7 percent, and the maximum adsorption rate can be close to 4 percent; the part injection molded by the product has good flame retardant effect and can realize carbon adsorption.
Meanwhile, the inventor also screens two components of the flame retardant synergist, and when one of the two components is deficient or the content is too low, the synergistic flame retardance of the product is greatly reduced.
In addition, the inventor optimizes the addition proportion of the halogen-free flame retardant and the flame retardant synergist, if the addition amount of the halogen-free flame retardant is too small, the product cannot realize the expected flame retardant effect, and if the addition amount is too large, the density of the product is too high, and the larger mechanical property change is caused, so that the application range is influenced; if the addition amount of the flame retardant synergist is too large, although a certain flame retardant effect can be improved, the cost is also obviously improved, meanwhile, the mechanical property of the product is also reduced, and if the addition amount of the flame retardant synergist is too small, the flame retardant effect is reduced.
The modified magnesium hydroxide without organic halogen is used as a halogen-free flame retardant and matched with a specific flame retardant synergist to be used as a flame retardant system, so that the flame retardant polypropylene material is more nontoxic and environment-friendly, can realize excellent synergistic flame retardant effect, and has carbon dioxide adsorption effect; the product has moderate density and good mechanical property, and can be suitable for various application ranges.
Preferably, the polypropylene resin is at least one of homo-polypropylene resin and co-polypropylene resin; the polypropylene resin has a melt flow rate of 5 to 60g/10min at 230 ℃ under a load of 2.16kg according to astm d 1238.
As the polypropylene material contains a certain weight of halogen-free flame retardant, the polypropylene resin used has proper fluidity to ensure the uniformity of each component in the processing process of the product and the mechanical properties such as impact strength, flexural modulus and the like of the finished product after the processing is finished; on the other hand, the impact strength (toughness) of the polypropylene copolymer resin is higher, the flexural modulus (rigidity) of the polypropylene copolymer resin is higher, and the density of the product can be further reduced by introducing a proper amount of the polypropylene copolymer resin, and the polypropylene copolymer resin can be further used in a wider range by combining and collocating the polypropylene copolymer resin according to different actual demands.
Preferably, the components of the flame-retardant polypropylene material also comprise 0-10 parts of toughening agent;
more preferably, the toughening agent is POE having a melt flow rate of 0.5 to 2g/10min at 190℃under a load of 2.16kg according to ASTMD 1238.
The toughness of the product can be further improved by adding the toughening agent, so that the toughness of the matrix can be regulated and controlled according to actual conditions so as to meet application requirements.
Preferably, the particle size of the halogen-free flame retardant is 0.5-2.5 mu m, and the average particle size D50 is less than or equal to 1.5 mu m;
the inventor finds that the halogen-free flame retardant with the preferable particle size has the best dispersing effect in the product processing process, and can realize the best carbon dioxide adsorption effect and flame retardant effect.
Preferably, the processing aid is at least one of an antioxidant, a light stabilizer and a lubricant;
more preferably, the antioxidant is at least one of hindered phenol type antioxidant and phosphite type antioxidant;
more preferably, the light stabilizer is a hindered amine light stabilizer;
more preferably, the lubricant is erucamide;
more preferably, the processing aid is a mixture of hindered phenolic antioxidant, phosphite antioxidant, hindered amine light stabilizer and erucamide, and m (hindered phenolic antioxidant: phosphite antioxidant: hindered amine light stabilizer: erucamide) = (0.8-1.2): (0.8-1.2).
The invention also aims at providing a preparation method of the flame-retardant polypropylene material, which comprises the following steps: and uniformly mixing the polypropylene resin, the toughening agent, the halogen-free flame retardant, the flame retardant synergist and the processing aid, adding the mixture into a double-screw extruder, and performing melt extrusion granulation and drying treatment to obtain the flame retardant polypropylene material.
The preparation method of the flame-retardant polypropylene material has simple operation steps and low equipment requirement, and can realize industrialized mass production.
Preferably, the temperature conditions of the twin-screw extruder during melt extrusion are as follows: the temperature of the first area is 100-120 ℃, the temperature of the second area is 190-210 ℃, the temperature of the third area is 210-230 ℃, the temperature of the fourth area is 210-230 ℃, the temperature of the fifth area is 210-230 ℃, the temperature of the sixth area is 210-230 ℃, the temperature of the seventh area is 210-230 ℃, the temperature of the eighth area is 210-230 ℃, and the temperature of the ninth area is 210-230 ℃.
Preferably, the host rotation speed of the double-screw extruder in melt extrusion is 250-600 rpm, and the length-diameter ratio of the screw is 40:1.
The invention also aims to provide the application of the flame-retardant polypropylene material in preparing plastic parts of automobiles or household appliances.
When the polypropylene material is applied to household appliances or automobile parts, the polypropylene material has the requirements of basic rigid structural mechanics (in general, the bending modulus is more than or equal to 1700 MPa) and light weight (the density is less than or equal to 1.2 g/cm) 3 ) And toughness requirements, more importantly, the flame-retardant polypropylene material provided by the invention has good flame retardant property, and is good in mechanical property (comprising flexural modulus and impact strength), moderate in density, safe, environment-friendly and nontoxic, good in flame retardant effect and carbon dioxide adsorption effect, and especially suitable for household appliances and automobile plastic part products with high comprehensive performance requirements.
The invention has the beneficial effects that the invention provides a flame-retardant polypropylene material, the product takes modified magnesium hydroxide without organic halogen as a halogen-free flame retardant and a specific flame-retardant synergist as a flame-retardant system, is more nontoxic and environment-friendly, can realize excellent flame-retardant effect of synergistic effect, and has carbon dioxide adsorption effect; the product has moderate density and good mechanical property, and can be suitable for various application ranges. The invention also provides a preparation method of the flame-retardant polypropylene material and application of the flame-retardant polypropylene material in preparation of plastic parts of automobiles or household appliances.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and is intended to be construed in detail, not as limiting the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments involved in the practice of the present invention are common reagents and instruments unless otherwise specified.
In the examples, the melt mass flow rates of the polypropylene resin and the toughening agent were measured according to astm d1238 using a weight of 2.16kg and at a temperature of 230 ℃/190 ℃, respectively.
Examples 1 to 5
In one embodiment of the flame retardant polypropylene material and the preparation method thereof, the components of the flame retardant polypropylene material are shown in table 1.
The preparation method of the flame-retardant polypropylene material comprises the following steps:
mixing polypropylene resin, a toughening agent, a halogen-free flame retardant, a flame retardant synergist and a processing aid in a high-speed mixer for 3min to uniformity, adding the mixture into a main feeding port of a double-screw extruder, and performing melt extrusion granulation and drying treatment to obtain the flame retardant polypropylene material;
the temperature conditions of the double-screw extruder during melt extrusion are as follows: first region temperature 120 ℃, second region temperature 190 ℃, third region temperature 210 ℃, fourth region temperature 210 ℃, fifth region temperature 210 ℃, sixth region temperature 230 ℃, seventh region temperature 230 ℃, eighth region temperature 230 ℃, and ninth region temperature 230 ℃;
the rotating speed of the main machine of the double-screw extruder is 350rpm, and the length-diameter ratio of the screw is 40:1.
The polypropylene resin 1 is a copolymerized polypropylene resin, and is produced by the medium sand petrochemical industry and is of EP548RQ model, and the melt mass flow rate of the polypropylene resin is 28g/10min;
the polypropylene resin 2 is a homopolymerized polypropylene resin, and is a 1100N model product produced by Shenhuaining coal, and the melt mass flow rate of the polypropylene resin is 12g/10min;
the toughening agent is POENGAGE 7467 model product produced by the Dow company, and the melt mass flow rate of the toughening agent is 1.2g/10min;
the halogen-free flame retardant is modified magnesium hydroxide coated by a silane coupling agent, aitemag 12 products produced by Jiangsu Ai Teke company, the particle size is 0.5-2.5 mu m, and the average particle size (D50) is 1.2 mu m;
the flame retardant synergist is a mixture of melamine hydrobromide and aluminum hypophosphite; the mass ratio of the melamine hydrobromide to the aluminum hypophosphite is 2:5;
the melamine hydrobromide is M-108MHB produced by Shanghai power company; the aluminum hypophosphite is produced by the Australian chemical company;
the processing aid comprises an antioxidant, a light stabilizer and a lubricant;
the antioxidant is a commercially available hindered phenol antioxidant and a commercially available phosphite antioxidant;
the light stabilizer is a commercially available hindered amine light stabilizer;
the erucamide is commercially available erucamide;
the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant to the hindered amine light stabilizer to the erucamide is as follows: m (hindered phenol antioxidant: phosphite antioxidant: hindered amine light stabilizer: erucic acid amide) =1:1:1:1.
Example 6
The only difference between this embodiment and embodiment 1 is that: in the flame retardant synergist, the mass ratio of melamine hydrobromic acid salt to aluminum hypophosphite is 1:5;
example 7
The only difference between this embodiment and embodiment 1 is that: the halogen-free flame retardant is Aitemag 10 produced by Jiangsu Ai Teke company, the particle size is 1.0-2.5 mu m, and the average particle size (D50) is 1.5 mu m;
example 8
The only difference between this embodiment and embodiment 1 is that: the halogen-free flame retardant is Aitemag 55 produced by Jiangsu Ai Teke company, the particle size is 3.0-5.0 mu m, and the average particle size (D50) is 3.5 mu m;
comparative examples 1 to 5
The composition of the flame retardant polypropylene material of this comparative example is shown in Table 2. The preparation of the products described in each comparative example was the same as in example 1.
The bromine-antimony flame retardant is a mixture of RDT-3 produced by Wei Dong chemical company and antimony white produced by Authority chemical industry in a mass ratio of 3:1;
comparative example 6
The difference between this comparative example and example 1 is only that: the particle size of the halogen-free flame retardant is 4-10 mu m;
comparative example 7
The difference between this comparative example and example 1 is only that: in the flame retardant synergist, the mass ratio of melamine hydrobromic acid salt to aluminum hypophosphite is 10.5:0.5;
comparative example 8
The difference between this comparative example and example 1 is only that: the mass ratio of melamine hydrobromide to aluminum hypophosphite in the flame retardant synergist is 1:9.
Comparative example 9
The comparative example differs from example 1 only in that the halogen-free flame retardant is uncoated modified magnesium hydroxide.
TABLE 1
TABLE 2
| The components are in parts by weight | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 10 | Comparative example 11 |
| Polypropylene resin 1 | 71 | 71 | 41 | 81 | 61 | 71 | 71 |
| Toughening agent | 8 | 8 | 8 | 8 | 8 | 8 | 8 |
| Halogen-free flame retardant | 21 | 50 | 10 | 20 | 10 | 50 | |
| Bromine-antimony flame retardant | 20 | ||||||
| Flame retardant synergist | 0.2 | 1 | 1 | 1 | 11 | 1 | 1 |
| Processing aid | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 |
Effect example 1
The products obtained in each example and comparative example were tested for density, flexural modulus, notched Izod impact strength, flame retardance and carbon dioxide adsorption:
(1) Flexural modulus test: the flexural modulus of the material was tested using ISO178-2010, flexural rate 2mm/min;
(2) Testing the notch impact strength of the cantilever beam: testing the impact strength of a cantilever beam notch of a material by adopting ISO180-2000, wherein the impact pendulum capacity of the A-type notch is 5.5J;
(3) Density testing: the density of the material was tested using ISO 1183-1-2004;
(4) Flame retardancy: according to UL94-2018 standard, each product is molded into a vertical combustion spline of 100 x 10 x 1.6mm for vertical combustion test;
(5) Carbon dioxide adsorption test: 3g of each product is weighed and placed in a closed container with the volume of 1L, 1.98g of pure carbon dioxide is introduced, the container is sealed, the container is placed at the constant temperature of 23 ℃ for 30 days, each product is taken out, the weight of each product is weighed again, and the carbon dioxide adsorption rate (%) = product weight gain mass (g)/product mass 3 (g) x 100% before testing of the product.
The test results are shown in Table 3.
TABLE 3 Table 3
As shown in the table, the flame retardant polypropylene material prepared by each embodiment of the invention can reach the flame retardant grade above V-2 level, the carbon dioxide adsorption rate can also reach above 1.7%, and the highest carbon dioxide adsorption rate can reach nearly 4%; the product has moderate density and can be maintained at 1-1.2 g/cm 3 In the range, the comprehensive mechanical properties are excellent, the flexural modulus is more than 1700MPa, and the impact strength is more than 20KJ/m 2 The method comprises the steps of carrying out a first treatment on the surface of the In contrast, the product obtained in comparative example 1 contained insufficient amounts of flame retardant synergism in the components, which were absentThe method has an effective flame-retardant function; the product of comparative example 2, although having a flame retardant rating of V-1, has not only a deteriorated bending modulus compared to the product of example 1, but also little carbon dioxide adsorption effect because the halogen-free flame retardant is not contained in the components; the product obtained in the comparative example 9 contains magnesium hydroxide, but the product is not modified at all, and can not have obvious flame retardant effect under the condition of the same additive content; the percentages and actual contents of the halogen-free flame retardants in comparative examples 3, 4, 10 and 11 are too large and too small, respectively, which causes a wide variation in the product density, greatly reduces the application range, and the products of comparative examples 4 and 10 having too small halogen-free flame retardants cannot exert an effective flame retardant effect, as compared with example 1; as can be seen from the comparison of the performances of the products in the example 2 and the comparative example 5, the improper proportion of the halogen-free flame retardant and the flame retardant synergist can cause the weakening of the mechanical properties of the products, so that the obtained products have better flame retardance but can not meet the application requirements of the actual mechanical properties; as can be seen from comparison of the properties of the products of example 1, example 7, example 8 and comparative example 6, the size of the particle size of the halogen-free flame retardant in the product directly affects the mechanical properties and carbon dioxide adsorption properties of the product, and the product can have excellent mechanical properties and carbon dioxide adsorption properties only when the particle size of the halogen-free flame retardant is in the range of 0.5 to 5. Mu.m, preferably 0.5 to 2.5. Mu.m, and D50 is less than or equal to 1.5. Mu.m. From the properties of the products of comparative examples 7-8, it is known that in order to maintain the flame retardant property of the products, the components of the flame retardant synergist are not necessary to contain melamine hydrobromide and aluminum hypophosphite; when the ratio of the two is improper, the ideal flame retardant property cannot be obtained.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The flame-retardant polypropylene material is characterized by comprising the following components in parts by weight:
50-80 parts of polypropylene resin, 20-40 parts of halogen-free flame retardant, 1-3 parts of flame retardant synergist, 0.5-2 parts of processing aid and 0-10 parts of toughening agent;
the halogen-free flame retardant is magnesium hydroxide coated and modified by a silane coupling agent, and the particle size is 0.5-5 mu m;
the flame retardant synergist is a mixture of melamine hydrobromide and aluminum hypophosphite; the mass ratio of the melamine hydrobromide to the aluminum hypophosphite is 1:5~2:5.
2. the flame retardant polypropylene material of claim 1, wherein the polypropylene resin is at least one of a homo-polypropylene resin and a co-polypropylene resin.
3. The flame retardant polypropylene material according to claim 1, wherein the halogen-free flame retardant has a particle size of 0.5 to 2.5 μm and an average particle size D50 of 1.5 μm or less.
4. The flame retardant polypropylene material of claim 1, wherein the processing aid is at least one of an antioxidant, a light stabilizer, and a lubricant.
5. The flame retardant polypropylene material according to claim 4, wherein the antioxidant is at least one of a hindered phenol type antioxidant and a phosphite type antioxidant; the light stabilizer is a hindered amine light stabilizer; the lubricant is erucamide.
6. The method for preparing the flame retardant polypropylene material according to any one of claims 1 to 5, comprising the steps of: and uniformly mixing the polypropylene resin, the toughening agent, the halogen-free flame retardant, the flame retardant synergist and the processing aid, adding the mixture into a double-screw extruder, and performing melt extrusion granulation and drying treatment to obtain the flame retardant polypropylene material.
7. The method for preparing the flame retardant polypropylene material according to claim 6, wherein the temperature conditions of the twin screw extruder during melt extrusion are as follows: the temperature of the first area is 100-120 ℃, the temperature of the second area is 190-210 ℃, the temperature of the third area is 210-230 ℃, the temperature of the fourth area is 210-230 ℃, the temperature of the fifth area is 210-230 ℃, the temperature of the sixth area is 210-230 ℃, the temperature of the seventh area is 210-230 ℃, the temperature of the eighth area is 210-230 ℃ and the temperature of the ninth area is 210-230 ℃; the main machine rotating speed of the double-screw extruder in melt extrusion is 250-600 rpm, and the length-diameter ratio of the screw is 40:1.
8. The use of a flame retardant polypropylene material according to any one of claims 1 to 5 for the preparation of plastic parts for automobiles or household appliances.
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