CN101418099A - Natural fiber reinforcement halogen-free flame retardant polypropylene composite material and preparation method thereof - Google Patents
Natural fiber reinforcement halogen-free flame retardant polypropylene composite material and preparation method thereof Download PDFInfo
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- CN101418099A CN101418099A CNA2008102038775A CN200810203877A CN101418099A CN 101418099 A CN101418099 A CN 101418099A CN A2008102038775 A CNA2008102038775 A CN A2008102038775A CN 200810203877 A CN200810203877 A CN 200810203877A CN 101418099 A CN101418099 A CN 101418099A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention provides a natural fiber reinforced halogen-free flame-retardant polypropylene composite material, which is characterized by consisting of the following raw materials in weight portion: 82.5 to 12 portions of polypropylene, 0.3 to 2 portions of heat stabilizer, 0.2 to 1 portion of processing assistant, 1 to 10 portions of toughening agent, 10 to 40 portions of flame retardant, 1 to 5 portions of compatilizer, and 5 to 30 portions of natural fiber. The invention also provides a method for preparing the material. The composite material has the advantages that the composite material has excellent flame-retardant effect and excellent comprehensive mechanical property; the flame-retardant property of the composite material can reach 1.6mm V0; the tensile strength is more than or equal to 60MPa; the bending modulus is more than or equal to 4,000MPa; the gap impact strength is more than or equal to 10KJ/m<2>; the shrinkage ratio is between 4 and 6 per thousand; the heat distortion temperature is more than or equal to 140 DEG C; and the composite material is a novel environment-friendly material, and has no safety and health problems of glass fibers.
Description
Technical field
The present invention relates to a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material and preparation method thereof, be specifically related to polypropylene composite material that is used for field of household appliances and preparation method thereof, belong to technical field of polymer materials with high flame retardant, low-shrinkage and good comprehensive mechanical property.
Background technology
Polypropylene (PP) is one of five big general-purpose plastics, and density is 0.90g/cm
3Performance is good, proportion is little, be easy to advantages such as machine-shaping because of it has, thereby is widely used in automotive industry, household electrical appliance, textile industry, electronic instrument industry etc.But, because the limiting oxygen index(LOI) of acrylic resin is very low, have only 18, belong to inflammable material, can't satisfy the service requirements in certain material fire prevention field, be subjected to certain restriction when making it be applied to above-mentioned field.Continuous enhancing along with people's environmental consciousness requires acrylic resin to be beneficial to environmental protection flame retardant, and the physical strength height, to satisfy service requirements.
People have done a large amount of effort when producing environment-friendly flame-proof polypropylene in the prior art.Common polypropylene flame redardant mainly is to adopt the method for adding bromide fire retardant to produce, but Recent study shows, bromide fire retardant can produce a kind of carcinogenic surrounding material in combustion processes, so European Union requires all electric appliance and electronic products all need meet the RoHS instruction, guarantees not contain materials such as pentabromo-ether, eight bromo ether, nine bromo-ethers in the electronic product.And halogen-free expansion fire retardant is not halogen-containing environmental protection fire retarding agent, can accomplish environmental protection, safe, nontoxic, thereby will become the main flow of fire retardant material in the coming years, satisfies the requirement of Environmental Safety.
But simple halogen-free anti-flaming polypropylene material mechanical property is relatively poor, need carry out enhancing modified to it and just can reach service requirements.The multiple producd fibers reinforced plastics method that exists wherein much is to use frangible fiber at present, and for example: glass fibre adds other mixture of ingredients with predetermined Cutting Length.The equipment that is used for these technologies needs several nonstandard parts of blended that are used for.Recently, the focus of fortifying fibre is transferred to several natural cellulosic fibres from glass fibre.As toughener, though the specific tenacity of these fibers is 50%-80% of glass fibre, specific modulus surpasses glass fibre.Other advantage comprises low cost, low density, renewable and biodegradable.They are adding the wearing and tearing in man-hour still less, and the operator is exposed to the open air in potential danger and health problem.In addition, natural fiber itself becomes charcoal more intense, does not have the wick effect in the glass fibre, to the polyacrylic fire-retardant good synergistic effect that plays.
Summary of the invention
The purpose of this invention is to provide natural fiber reinforced polypropylene compound material of a kind of not brominated, halogen-free environmental and preparation method thereof.
In order to achieve the above object, technical scheme of the present invention provides a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material, it is characterized in that, is made up of following raw material in weight part:
Polypropylene 82.5-12;
Thermo-stabilizer 0.3-2;
Processing aid 0.2-1;
Toughner 1-10;
Fire retardant 10-40;
Compatilizer 1-5;
Natural fiber 5-30;
Wherein, described thermo-stabilizer is the mixture class of phenols, amine, phosphorous acid esters, acryl functional group and monothioester or a kind of or its mixture in the calixarene kind thermo-stabilizer;
Described processing aid is a kind of or its mixture in low molecule ester class, metallic soap class, stearic acid complex ester class and the amides processing aid;
Described toughner is the multipolymer of vinylbenzene and divinyl, ethene-styrene-propene terpolymer, ethylene-propylene-butadiene terpolymer, hydrogenant ethylene-butadiene-styrene multipolymer, the styrene-butadiene-styrene triblock copolymer, hydrogenant styrene-butadiene-styrene triblock copolymer, ethene-α-ethylene-octene copolymer, ethene and acrylonitrile copolymer, the multipolymer of acrylonitrile-butadiene-styrene (ABS), a kind of or its mixture in ethylene-propylene diene copolymer or the urethane;
Said fire retardant is a P-N type halogen-free environment-friendly type expanding fire retardant;
Described compatilizer is the polar monomer graftomer, wherein polymeric matrix is a polyethylene, polypropylene, ethene-α-ethylene-octene copolymer, the multipolymer of vinylbenzene and divinyl, ethene-styrene-propene terpolymer, ethylene-propylene-butadiene terpolymer, a kind of or its mixture in ethylene-acrylate copolymer and the ethylene-acrylate-glycidyl methacrylate copolymer, polar monomer is a maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride, the vinyl Succinic anhydried, vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, a kind of or its mixture in methyl methacrylate and the glytidyl methacrylate.
Further, to be preferably molecular weight be 10-20 ten thousand polypropylene to described polypropylene.
Described P-N type halogen-free environment-friendly type expanding fire retardant is one or several the mixture among ammonium polyphosphate, tetramethylolmethane, dipentaerythritol, many tetramethylolmethanes, zinc borate, zinc acetate and the trimeric cyanamide.
Described phenols thermo-stabilizer is preferably dihydroxyphenyl propane, bisphenol-c, 2,6-ditertbutylparacresol, 1,3,5-trimethylammonium-2,4,6-three (3.5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) Three methyl Benzene and 2,2 '-one or several mixture in the methylene bis (4-ethyl-6 tert.-butyl phenol).
Described amine thermo-stabilizer is preferably one or several the mixture in diphenyl-para-phenylene diamine, diphenyl-para-phenylene diamine, 4-hydroxy-dodecanoic acid anilide and the 4-hydroxyl octadecanoic acid anilide.
Described phosphorous acid ester type thermal stabilizing agent is preferably one or several the mixture in trisnonyl phenyl phosphite, triphenyl phosphite and the hot diphenyl ester of phosphorous acid.
The mixture type thermal stabilizing agent of described acryl functional group and monothioester is preferably Tyox B.
Described calixarene kind thermo-stabilizer is preferably to tertiary butyl cup [4] aromatic hydrocarbons, to tertiary butyl cup [6] aromatic hydrocarbons and to one or several the mixture in tertiary butyl cup [8] aromatic hydrocarbons.
Described low molecule ester class processing aid is preferably one or several the mixture in butyl stearate, glyceryl monostearate and the Tristearoylglycerol.
Described metallic soap class processing aid is preferably one or several the mixture in calcium stearate, Zinic stearas, Magnesium Stearate and the lead stearate.
Described stearic acid complex ester class processing aid is preferably one or several the mixture in Tripolyglycerol monostearates, Polyglycerine monostearate and.
Described amides processing aid is preferably one or several the mixture in amine hydroxybenzene, stearylamide and the ethylene bis stearamide.
Described natural fiber is preferably annual fiber or bark fiber.Described annual fiber is preferably flax, hemp, jute, sisal hemp or kenaf.
The present invention also provides the preparation method of above-mentioned a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material, it is characterized in that, concrete steps are:
Be that melting mixing is disperseed in the twin screw extruder of 40-50:1 with polypropylene, thermo-stabilizer, processing aid, toughner, fire retardant, compatilizer in length-to-diameter ratio in proportion, short restriction of natural fiber adds from the side feeding, at 170-240 ℃ of extruding pelletization.
Natural fiber Derby modulus surpasses glass fibre, therefore natural fiber enhanced polypropylene material has very high Young's modulus. in addition, natural fiber itself is owing to be rich in hydroxyl, therefore become charcoal very strong, can play the effect of halogen-free flame retardants char-forming agent, there is not the wick effect in the glass fibre, to the polyacrylic fire-retardant good synergistic effect that plays yet.Therefore the natural fiber enhanced polypropylene has good mechanical performance and flame retardant effect.
Product of the present invention has the excellent fire retardant effect, good comprehensive mechanical properties, lower shrinking percentage and higher heat-drawn wire, its flame retardant properties can reach 1.6mm V0, tensile strength 〉=60MPa, modulus in flexure 〉=4000MPa, notched Izod impact strength 〉=10KJ/m
2, shrinking percentage is 4～6 ‰, heat-drawn wire 〉=140 ℃, and the other technologies index meets or exceeds glass fiber flame retardant Reinforced Polypropylene standard.
Embodiment
Specify the present invention below in conjunction with embodiment.
Embodiment 1
Be 100,000 polypropylene 82.5 weight parts in proportion with molecular weight, thermo-stabilizer 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene (trade(brand)name Irganox1010, produce by Switzerland Ciba stock company) 0.3 weight part, processing aid butyl stearate 0.2 weight part, toughner ethylene-propylene-butadiene terpolymer 1 weight part, fire retardant ammonium polyphosphate 10 weight parts, glass compatilizer glytidyl methacrylate (GMA) graft polypropylene 1 weight part is that melting mixing is disperseed in the twin screw extruder of 45:1 in length-to-diameter ratio, flax fiber 5 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 170-180 ℃, two district 180-190 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 140 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 62MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 6%, injection moulding shrinking percentage (ASTM D-955) 4～6%, flexural strength (ISO178-93) 90MPa, modulus in flexure (ISO178-93) 4200MPa, notched Izod impact strength (ISO180-93) 10KJ/m
2, combustionproperty (UL94) V0.
Embodiment 2
Be 200,000 polypropylene 12 weight parts in proportion with molecular weight, thermo-stabilizer dihydroxyphenyl propane 2 weight parts, processing aid glyceryl monostearate 1 weight part, copolymer 10 weight part of toughner vinylbenzene and divinyl, fire retardant tetramethylolmethane 40 weight parts, glass compatilizer maleic anhydride grafted polyethylene 5 weight parts are that melting mixing is disperseed in the twin screw extruder of 35:1 in length-to-diameter ratio, hemp fibre 30 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 200-210 ℃, two district 210-220 ℃, three district 220-230 ℃, four district 230-240 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 140 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 58MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 5%, injection moulding shrinking percentage (ASTM D-955) 4～7%, flexural strength (ISO178-93) 85MPa, modulus in flexure (ISO178-93) 4000MPa, notched Izod impact strength (ISO180-93) 9KJ/m
2, combustionproperty (UL94) V0.
Embodiment 3
Be 150,000 polypropylene 41 weight parts in proportion with molecular weight, thermo-stabilizer bisphenol-c 0.3 weight part, processing aid Tristearoylglycerol 0.2 weight part, copolymer 10 weight part of toughner vinylbenzene and divinyl, fire retardant dipentaerythritol 21.5 weight parts, glass compatilizer fumaric acid graft polypropylene 2 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, jute fibre 25 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 140 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 65MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 7%, injection moulding shrinking percentage (ASTM D-955) 5～6%, flexural strength (ISO178-93) 95MPa, modulus in flexure (ISO178-93) 4300MPa, notched Izod impact strength (ISO180-93) 12KJ/m
2, combustionproperty (UL94) V0.
Embodiment 4
Be 150,000 polypropylene 41 weight parts in proportion with molecular weight, thermo-stabilizer 2,6-ditertbutylparacresol 1 weight part, processing aid calcium stearate 0.5 weight part, toughner ethene-styrene-propene terpolymer 5 weight parts, many tetramethylolmethane 25 weight parts of fire retardant, glass compatilizer methylene-succinic acid grafted ethene-α-ethylene-octene copolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, sisal fibers 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 142 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 61MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 3%, injection moulding shrinking percentage (ASTM D-955) 5～7%, flexural strength (ISO178-93) 92MPa, modulus in flexure (ISO178-93) 4100MPa, notched Izod impact strength (ISO180-93) 11KJ/m
2, combustionproperty (UL94) V0.
Embodiment 5
Be 150,000 polypropylene 40 weight parts in proportion with molecular weight, thermo-stabilizer diphenyl-para-phenylene diamine 1 weight part, processing aid Zinic stearas 0.5 weight part, toughner hydrogenant ethylene-butadiene-styrene multipolymer 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer citraconic acid graft phenylethene and butadienecopolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, kenaf 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 145 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 66MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 4%, injection moulding shrinking percentage (ASTM D-955) 5～7%, flexural strength (ISO178-93) 96MPa, modulus in flexure (ISO178-93) 4500MPa, notched Izod impact strength (ISO180-93) 14KJ/m
2, combustionproperty (UL94) V0.
Embodiment 6
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer diphenyl-para-phenylene diamine 1 weight part, processing aid Magnesium Stearate 0.5 weight part, toughner styrene-butadiene-styrene triblock copolymer 5 weight parts, fire retardant zinc acetate 25 weight parts, glass compatilizer citraconic anhydride grafted ethene-styrene-propene multipolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, Cortex Mori fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 140 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 64MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 5%, injection moulding shrinking percentage (ASTM D-955) 5～6%, flexural strength (ISO178-93) 93MPa, modulus in flexure (ISO178-93) 4300MPa, notched Izod impact strength (ISO180-93) 11KJ/m
2, combustionproperty (UL94) V0.
Embodiment 7
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer 4-hydroxy-dodecanoic acid anilide 1 weight part, processing aid lead stearate 0.5 weight part, toughner hydrogenant ethylene-butadiene-styrene multipolymer 5 weight parts, fire retardant trimeric cyanamide 25 weight parts, glass compatilizer vinyl Succinic anhydried grafted ethene-propylene-butadiene terpolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, paper mulberry bark fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 138 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 60MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 6%, injection moulding shrinking percentage (ASTM D-955) 5～6%, flexural strength (ISO178-93) 91MPa, modulus in flexure (ISO178-93) 4000MPa, notched Izod impact strength (ISO180-93) 9KJ/m
2, combustionproperty (UL94) V0.
Embodiment 8
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer 4-hydroxyl octadecanoic acid anilide 1 weight part, processing aid Tripolyglycerol monostearates 0.5 weight part, toughner styrene-butadiene-styrene triblock copolymer 5 weight parts, fire retardant zinc borate 25 weight parts, acrylic acid-grafted ethylene-acrylate copolymer 3 weight parts of glass compatilizer are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 143 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 65MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 3%, injection moulding shrinking percentage (ASTM D-955) 5～6%, flexural strength (ISO178-93) 93MPa, modulus in flexure (ISO178-93) 4400MPa, notched Izod impact strength (ISO180-93) 11KJ/m
2, combustionproperty (UL94) V0.
Embodiment 9
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer trisnonyl phenyl phosphite 1 weight part, processing aid Polyglycerine monostearate 0.5 weight part, toughner ethene and acrylonitrile copolymer 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer methacrylic acid grafted ethylene-acrylate-glycidyl methacrylate copolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 139 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 61MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 6%, injection moulding shrinking percentage (ASTM D-955) 4～6%, flexural strength (ISO178-93) 88MPa, modulus in flexure (ISO178-93) 4200MPa, notched Izod impact strength (ISO180-93) 13KJ/m
2, combustionproperty (UL94) V0.
Embodiment 10
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer triphenyl phosphite 1 weight part, processing aid 0.5 weight part, toughner acrylonitrile-butadiene-styrene copolymer 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer methyl acrylate grafted polyethylene 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 142 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 61MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 5%, injection moulding shrinking percentage (ASTM D-955) 4～6%, flexural strength (ISO178-93) 89MPa, modulus in flexure (ISO178-93) 4300MPa, notched Izod impact strength (ISO180-93) 11KJ/m
2, combustionproperty (UL94) V0.
Embodiment 11
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, hot diphenyl ester 1 weight part of thermo-stabilizer phosphorous acid, processing aid amine hydroxybenzene 0.5 weight part, toughner ethylene-propylene diene copolymer 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer ethyl propenoate grafted polyethylene 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 143 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 66MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 6%, injection moulding shrinking percentage (ASTM D-955) 4～6%, flexural strength (ISO178-93) 96MPa, modulus in flexure (ISO178-93) 4300MPa, notched Izod impact strength (ISO180-93) 11KJ/m
2, combustionproperty (UL94) V0.
Embodiment 12
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer 1,3,5-trimethylammonium-2,4,6-three (3.5-di-tert-butyl-4-hydroxyl benzyl) Three methyl Benzene 1 weight part, processing aid stearylamide 0.5 weight part, toughner urethane 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer methyl methacrylate-grafted polyethylene 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 142 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 65MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 7%, injection moulding shrinking percentage (ASTM D-955) 4～6%, flexural strength (ISO178-93) 90MPa, modulus in flexure (ISO178-93) 4200MPa, notched Izod impact strength (ISO180-93) 15KJ/m
2, combustionproperty (UL94) V0.
Embodiment 13
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer 2,2 '-methylene bis (4-ethyl-6 tert.-butyl phenol), 1 weight part, processing aid ethylene bis stearamide 0.5 weight part, toughner ethene-α-ethylene-octene copolymer 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer glytidyl methacrylate grafted polyethylene 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 145 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 67MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 6%, injection moulding shrinking percentage (ASTMD-955) 4～6%, flexural strength (ISO178-93) 90MPa, modulus in flexure (ISO178-93) 4600MPa, notched Izod impact strength (ISO180-93) 13KJ/m
2, combustionproperty (UL94) V0.
Embodiment 14
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer Tyox B 1 weight part, processing aid calcium stearate 0.5 weight part, toughner ethene-styrene-propene terpolymer 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer methylene-succinic acid grafted ethene-α-ethylene-octene copolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 134 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 60MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 4%, injection moulding shrinking percentage (ASTM D-955) 4～6%, flexural strength (ISO178-93) 93MPa, modulus in flexure (ISO178-93) 4200MPa, notched Izod impact strength (ISO180-93) 12KJ/m
2, combustionproperty (UL94) V0.
Embodiment 15
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer is to tertiary butyl cup [4] aromatic hydrocarbons 1 weight part, processing aid calcium stearate 0.5 weight part, toughner ethene-styrene-propene terpolymer 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer methylene-succinic acid grafted ethene-α-ethylene-octene copolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 143 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 65MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 6%, injection moulding shrinking percentage (ASTM D-955) 4～6%, flexural strength (ISO178-93) 92MPa, modulus in flexure (ISO178-93) 4400MPa, notched Izod impact strength (ISO180-93) 13KJ/m
2, combustionproperty (UL94) V0.
Embodiment 16
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer is to tertiary butyl cup [6] aromatic hydrocarbons 1 weight part, processing aid calcium stearate 0.5 weight part, toughner ethene-styrene-propene terpolymer 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer methylene-succinic acid grafted ethene-α-ethylene-octene copolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 143 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 65MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 6%, injection moulding shrinking percentage (ASTM D-955) 5～7%, flexural strength (ISO178-93) 97MPa, modulus in flexure (ISO178-93) 4600MPa, notched Izod impact strength (ISO180-93) 14KJ/m
2, combustionproperty (UL94) V0.
Embodiment 17
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer is to tertiary butyl cup [8] aromatic hydrocarbons 1 weight part, processing aid calcium stearate 0.5 weight part, toughner ethene-styrene-propene terpolymer 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer methylene-succinic acid grafted ethene-α-ethylene-octene copolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 141 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 63MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 6%, injection moulding shrinking percentage (ASTM D-955) 4～6%, flexural strength (ISO178-93) 88MPa, modulus in flexure (ISO178-93) 4400MPa, notched Izod impact strength (ISO180-93) 13KJ/m
2, combustionproperty (UL94) V0.
Embodiment 18
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer dihydroxyphenyl propane 0.5 weight part and 1,3,5-trimethylammonium-2,4,6-three (3.5-di-tert-butyl-4-hydroxyl benzyl) Three methyl Benzene 0.5 weight part, processing aid is to the tertiary butyl [4] calixarene 0.25 weight part with to the tertiary butyl [6] calixarene 0.25 weight part, toughner ethene-styrene-propene terpolymer 5 weight parts, fire retardant zinc borate 25 weight parts, glass compatilizer maleic anhydride grafted polyethylene 2 weight parts and maleic anhydride inoculated polypropylene 1 weight part are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 144 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 58MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 3%, injection moulding shrinking percentage (ASTM D-955) 4～6%, flexural strength (ISO178-93) 90MPa, modulus in flexure (ISO178-93) 3600MPa, notched Izod impact strength (ISO180-93) 8KJ/m
2, combustionproperty (UL94) V0.
Embodiment 19
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer diphenyl-para-phenylene diamine 0.5 weight part and triphenyl phosphite 0.5 weight part, processing aid amine hydroxybenzene 0.25 weight part and stearylamide 0.25 weight part, toughner ethylene-propylene-butadienecopolymer 2.5 weight parts and styrene-butadiene-styrene triblock copolymer 2.5 weight parts, fire retardant zinc borate 5 weight parts and zinc acetate 20 weight parts, glass compatilizer methylene-succinic acid grafted ethene-α-ethylene-octene copolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 142 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 63MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 6%, injection moulding shrinking percentage (ASTM D-955) 5～8%, flexural strength (ISO178-93) 95MPa, modulus in flexure (ISO178-93) 4000MPa, notched Izod impact strength (ISO180-93) 11KJ/m
2, combustionproperty (UL94) V0.
Embodiment 20
Be 150,000 polypropylene 50 weight parts in proportion with molecular weight, thermo-stabilizer diphenyl-para-phenylene diamine 0.5 weight part and diphenyl-para-phenylene diamine's 0.5 weight part, processing aid calcium stearate 0.25 weight part and butyl stearate 0.25 weight part, toughner ethene and acrylonitrile copolymer 2.5 weight parts and acrylonitrile-butadiene-styrene copolymer 2.5 weight parts, fire retardant ammonium polyphosphate 20 weight parts and tetramethylolmethane 5 weight parts, glass compatilizer methylene-succinic acid grafted ethene-α-ethylene-octene copolymer 3 weight parts are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, flax fiber 20 weight parts add from the side feeding, extruding pelletization, its expressing technique is: a district 180-190 ℃, two district 190-200 ℃, three district 190-200 ℃, four district 190-200 ℃, screw speed 350-400r/min, feeding frequency 10-25Hz, vacuum tightness-0.04-0.07MPa.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, its heat-drawn wire is 141 ℃ of (ISO75/1-93,1.82MPa), tensile strength is 63MPa (ISO527/2-93), elongation at break (ISO527/2-93) is 4%, injection moulding shrinking percentage (ASTM D-955) 4～6%, flexural strength (ISO178-93) 90MPa, modulus in flexure (ISO178-93) 4100MPa, notched Izod impact strength (ISO180-93) 11KJ/m
2, combustionproperty (UL94) V0.
Claims (15)
1. a natural fiber reinforcement halogen-free flame retardant polypropylene composite material is characterized in that, is made up of following raw material in weight part:
Polypropylene 82.5-12;
Thermo-stabilizer 0.3-2;
Processing aid 0.2-1;
Toughner 1-10;
Fire retardant 10-40;
Compatilizer 1-5;
Natural fiber 5-30;
Wherein, described thermo-stabilizer is the mixture class of phenols, amine, phosphorous acid esters, acryl functional group and monothioester or a kind of or its mixture in the calixarene kind thermo-stabilizer;
Described processing aid is a kind of or its mixture in low molecule ester class, metallic soap class, stearic acid complex ester class and the amides processing aid;
Described toughner is the multipolymer of vinylbenzene and divinyl, ethene-styrene-propene terpolymer, ethylene-propylene-butadiene terpolymer, hydrogenant ethylene-butadiene-styrene multipolymer, the styrene-butadiene-styrene triblock copolymer, hydrogenant styrene-butadiene-styrene triblock copolymer, ethene-α-ethylene-octene copolymer, ethene and acrylonitrile copolymer, the multipolymer of acrylonitrile-butadiene-styrene (ABS), a kind of or its mixture in ethylene-propylene diene copolymer or the urethane;
Said fire retardant is a P-N type halogen-free environment-friendly type expanding fire retardant;
Described compatilizer is the polar monomer graftomer, wherein polymeric matrix is a polyethylene, polypropylene, ethene-α-ethylene-octene copolymer, the multipolymer of vinylbenzene and divinyl, ethene-styrene-propene terpolymer, ethylene-propylene-butadiene terpolymer, a kind of or its mixture in ethylene-acrylate copolymer and the ethylene-acrylate-glycidyl methacrylate copolymer, polar monomer is a maleic anhydride, fumaric acid, methylene-succinic acid, citraconic acid, citraconic anhydride, the vinyl Succinic anhydried, vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, a kind of or its mixture in methyl methacrylate and the glytidyl methacrylate.
2. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1 is characterized in that, described polypropylene is that molecular weight is 10-20 ten thousand polypropylene.
3. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1, it is characterized in that described P-N type halogen-free environment-friendly type expanding fire retardant is one or several the mixture among ammonium polyphosphate, tetramethylolmethane, dipentaerythritol, many tetramethylolmethanes, zinc borate, zinc acetate and the trimeric cyanamide.
4. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1 is characterized in that, described phenols thermo-stabilizer is dihydroxyphenyl propane, bisphenol-c, 2,6-ditertbutylparacresol, 1,3,5-trimethylammonium-2,4,6-three (3.5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) Three methyl Benzene and 2,2 '-one or several mixture in the methylene bis (4-ethyl-6 tert.-butyl phenol).
5. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1, it is characterized in that described amine thermo-stabilizer is one or several the mixture in diphenyl-para-phenylene diamine, diphenyl-para-phenylene diamine, 4-hydroxy-dodecanoic acid anilide and the 4-hydroxyl octadecanoic acid anilide.
6. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1, it is characterized in that described phosphorous acid ester type thermal stabilizing agent is one or several the mixture in the hot diphenyl ester of trisnonyl phenyl phosphite, triphenyl phosphite and phosphorous acid.
7. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1 is characterized in that, the mixture type thermal stabilizing agent of described acryl functional group and monothioester is a Tyox B.
8. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1, it is characterized in that described calixarene kind thermo-stabilizer is to tertiary butyl cup [4] aromatic hydrocarbons, to tertiary butyl cup [6] aromatic hydrocarbons and to one or several the mixture in tertiary butyl cup [8] aromatic hydrocarbons.
9. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1, it is characterized in that described low molecule ester class processing aid is one or several the mixture in butyl stearate, glyceryl monostearate and the Tristearoylglycerol.
10. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1, it is characterized in that described metallic soap class processing aid is one or several the mixture in calcium stearate, Zinic stearas, Magnesium Stearate and the lead stearate.
11. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1, it is characterized in that described stearic acid complex ester class processing aid is one or several the mixture in Tripolyglycerol monostearates, Polyglycerine monostearate and.
12. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1 is characterized in that, described amides processing aid is one or several the mixture in amine hydroxybenzene, stearylamide and the ethylene bis stearamide.
13. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1 is characterized in that, described natural fiber is annual fiber or bark fiber.
14. a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 13 is characterized in that, described annual fiber is flax, hemp, jute, sisal hemp or kenaf.
15. the preparation method of a kind of natural fiber reinforcement halogen-free flame retardant polypropylene composite material as claimed in claim 1 is characterized in that, concrete steps are:
Be that melting mixing is disperseed in the twin screw extruder of 40-50:1 with polypropylene, thermo-stabilizer, processing aid, toughner, fire retardant, compatilizer in length-to-diameter ratio in proportion, short restriction of natural fiber adds from the side feeding, at 170-240 ℃ of extruding pelletization.
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