CN101412830A - Non-halogen flame-retardant polypropylene composite material and preparation thereof - Google Patents
Non-halogen flame-retardant polypropylene composite material and preparation thereof Download PDFInfo
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- CN101412830A CN101412830A CNA200810203878XA CN200810203878A CN101412830A CN 101412830 A CN101412830 A CN 101412830A CN A200810203878X A CNA200810203878X A CN A200810203878XA CN 200810203878 A CN200810203878 A CN 200810203878A CN 101412830 A CN101412830 A CN 101412830A
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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
-
- 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
Abstract
The invention provides a 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 aid, 1 to 10 portions of toughening agent, 10 to 40 portions of flame retardant, 1 to 5 portions of glass fiber compatibilizer and 5 to 30 portions of glass fiber. The invention also provides a method for preparing the material. The material has the flame retardancy up to 1.6mm V0, the tensile strength higher than or equal to 50 MPa, the flexural modulus higher than or equal to 3,000 MPa, the notched impact strength more than or equal to 8KJ/m<2>, the shrinkage between 4 and 6 per thousand, the heat distortion temperature higher than or equal to 140 DEG C, as well as the other technical indexes up to or exceeding the standard of flame-retardant acrylonitrile-butadiene-styrene copolymer materials. As the material uses the phosphorus-nitrogen flame retardant containing no halogen, the flame-retardant effect of the material completely reaches UL94-V0 grade.
Description
Technical field
The present invention relates to a kind of 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
Acrylonitrile-butadiene-styrene copolymer (ABS) plastics are engineering plastics of a kind of excellent property.The acrylonitrile-butadiene-styrene copolymer resin is the terpolymer of polyacrylonitrile (A), divinyl (B) and vinylbenzene (S), is the thermoplastic engineering plastic of the exploitation forties in 20th century.It introduces rigidity and the resistance to chemical reagents that vinyl cyanide has kept acrylonitrile-butadiene-styrene copolymer, the divinyl of introducing has improved the snappiness and the shock resistance of acrylonitrile-butadiene-styrene copolymer, and the vinylbenzene of introducing has been optimized the gloss and the processing fluidity of acrylonitrile-butadiene-styrene copolymer.Because these characteristics make that acrylonitrile-butadiene-styrene copolymer has obtained using widely.Its good electrical property, chemical stability and shock resistance and become electric elements, household electrical appliances, computer and instrument first-selection plastics one of.Yet the oxygen index of acrylonitrile-butadiene-styrene copolymer resin is 18 only, and burning easily in air produces a large amount of dense smoke and toxic gas during burning.Therefore, many electronic apparatus industry and automotive industry propose strict fire-retardant requirement to employed plastics.
Commercialization fire-retardant acrylonitrile-butadiene diene-styrene copolymer product almost all adopts halogen containing flame-retardant at present, halogen flame flame retarding efficiency height, and addition is few, and is less to the mechanical property influence of material.But along with the progress of society and the enhancing of environmental protection consciousness, the drawback secondary pollution of Halogen material (smog during burning, the heavy corrosion problem of distributing and causing thus of poison gas) runs in the opposite direction with the demand of society.1986, the polybromodiphenyl ether that contains in the product that the burning of brominated system produces was at first found in Europe, and two Ben Bing dioxs of tetrabromo and the two phenylpropyl alcohol furans of tetrabromo etc. belong to carcinogenic substance.Therefore, the non-halogen of flame retarded polymeric material is following development trend.Existing commercialization halogen-free flameproof acrylonitrile-butadiene-styrene copolymer is to adopt organophosphate as fire retardant, flame retardant properties can only reach UL94 V-2 rank, and other halogen-free flameproof acrylonitrile-butadiene-styrene copolymer product of UL94 V-0 level remains a world-famous puzzle so far.
At present, flame retardant properties reaches other polypropylene halogen-free flameproof product of UL94 V-0 level and has realized industrialization, but because the polypropylene employing is expansion type flame retardant, addition is big, particularly the influence of impact property is very big to the polypropylene mechanical property, therefore press for a kind of polypropylene composite material, its mechanical property can match in excellence or beauty with acrylonitrile-butadiene-styrene copolymer under the prerequisite that does not reduce flame retardant properties.
Summary of the invention
The purpose of this invention is to provide a kind of polypropylene composite material, it has high flame resistance and mechanical property concurrently.
In order to achieve the above object, technical scheme of the present invention provides a kind of 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;
Glass compatilizer 1-5;
Glass fibre 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 glass 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 preferably 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 ditertiary butyl p cresol, 1,3,5-trimethylammonium-2,4,6-three (3, the 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, the mixture of one or several in 2 '-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 glass fibre is preferably alkali free glass fibre.
The present invention also provides the preparation method of above-mentioned 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 35-45:1 with polypropylene, thermo-stabilizer, processing aid, toughner, fire retardant, glass compatilizer in length-to-diameter ratio in proportion, glass fibre adds from the side feeding, at 170-240 ℃ of extruding pelletization.
Because halogen-free intumescent flame-retardant polypropylene is after having added a large amount of powder fire retardants, mechanical property particularly notch shock performance greatly reduces, and adopt glass fibre to strengthen its mechanical property is greatly improved.
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 〉=50MPa, modulus in flexure 〉=3000MPa, notched Izod impact strength 〉=8KJ/m
2, shrinking percentage is 4～6 ‰, heat-drawn wire 〉=140 ℃, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
Be 150,000 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) (trade(brand)name Irganox 1010 for benzene, 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, alkali free glass fibre 5 weight parts add from the side feeding, at 170 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 55MPa, and flexural strength (ISO178-93) is 80MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3300MPa, and notched Izod impact strength (ISO180-93) is 9KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 145 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 2
Copolymer 10 weight part, fire retardant tetramethylolmethane 40 weight parts, glass compatilizer maleic anhydride grafted polyethylene 5 weight parts that with molecular weight are 150,000 polypropylene 12 weight parts, thermo-stabilizer dihydroxyphenyl propane 2 weight parts, processing aid glyceryl monostearate 1 weight part, toughner vinylbenzene and divinyl in proportion are that melting mixing is disperseed in the twin screw extruder of 35:1 in length-to-diameter ratio, alkali free glass fibre 30 weight parts add from the side feeding, at 240 ℃ of extruding pelletizations.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, lower shrinking percentage and higher heat-drawn wire, its flame retardant properties can reach 2.0mm V0, tensile strength (ISO527/2-93) is 58MPa, and flexural strength (ISO178-93) is 85MPa, and elongation at break (ISO527/2-93) is 4%, modulus in flexure (ISO178-93) is 3300MPa, and notched Izod impact strength (ISO180-93) is 9KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 143 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 3
Multipolymer 5 weight parts, fire retardant dipentaerythritol 25 weight parts, glass compatilizer fumaric acid graft polypropylene 3 weight parts that with molecular weight are 150,000 polypropylene 50 weight parts, thermo-stabilizer bisphenol-c 1 weight part, processing aid Tristearoylglycerol 0.5 weight part, toughner vinylbenzene and divinyl in proportion are that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 57MPa, and flexural strength (ISO178-93) is 87MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3600MPa, and notched Izod impact strength (ISO180-93) is 9KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 140 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 4
Be 200,000 polypropylene 50 weight parts, thermo-stabilizer 2 in proportion with molecular weight, 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, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, lower shrinking percentage and higher heat-drawn wire, its flame retardant properties can reach 2.5mm V0, tensile strength (ISO527/2-93) is 60MPa, and flexural strength (ISO178-93) is 88MPa, and elongation at break (ISO527/2-93) is 4%, modulus in flexure (ISO178-93) is 3900MPa, and notched Izod impact strength (ISO180-93) is 10KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 147 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 5
Be 100,000 polypropylene 50 weight parts, 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 in proportion with molecular weight in length-to-diameter ratio be that melting mixing is disperseed in the twin screw extruder of 40:1, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, lower shrinking percentage and higher heat-drawn wire, its flame retardant properties can reach 1.6mmV0, tensile strength (ISO527/2-93) is 53MPa, and flexural strength (ISO178-93) is 78MPa, and elongation at break (ISO527/2-93) is 6%, modulus in flexure (ISO178-93) is 3000MPa, and notched Izod impact strength (ISO180-93) is 11KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 142 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 6
Be 150,000 polypropylene 50 weight parts, 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 in proportion with molecular weight in length-to-diameter ratio be that melting mixing is disperseed in the twin screw extruder of 40:1, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 59MPa, and flexural strength (ISO178-93) is 85MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3400MPa, and notched Izod impact strength (ISO180-93) is 8KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～7 ‰, (ISO75/1-93 1.82MPa) is 143 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 7
Be 150,000 polypropylene 50 weight parts, 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 in proportion with molecular weight in length-to-diameter ratio be that melting mixing is disperseed in the twin screw extruder of 40:1, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, lower shrinking percentage and higher heat-drawn wire, its flame retardant properties can reach 2.8mm V0, tensile strength (ISO527/2-93) is 61MPa, and flexural strength (ISO178-93) is 90MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3800MPa, and notched Izod impact strength (ISO180-93) is 11KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 143 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 8
Be 150,000 polypropylene 50 weight parts, 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 in proportion with molecular weight in length-to-diameter ratio be that melting mixing is disperseed in the twin screw extruder of 40:1, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 53MPa, and flexural strength (ISO178-93) is 82MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3500MPa, and notched Izod impact strength (ISO180-93) is 8KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 141 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 9
Be 150,000 polypropylene 50 weight parts, 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 in proportion with molecular weight in length-to-diameter ratio be that melting mixing is disperseed in the twin screw extruder of 40:1, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 50MPa, and flexural strength (ISO178-93) is 75MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3000MPa, and notched Izod impact strength (ISO180-93) is 9KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 140 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 10
Be 150,000 polypropylene 50 weight parts, 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 in proportion with molecular weight in length-to-diameter ratio be that melting mixing is disperseed in the twin screw extruder of 40:1, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 58MPa, and flexural strength (ISO178-93) is 88MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3700MPa, and notched Izod impact strength (ISO180-93) is 9KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 142 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 11
Be hot diphenyl ester 1 weight part of 150,000 polypropylene 50 weight parts, 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 in proportion with molecular weight in length-to-diameter ratio be that melting mixing is disperseed in the twin screw extruder of 40:1, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, lower shrinking percentage and higher heat-drawn wire, its flame retardant properties can reach 3.2mm V0, tensile strength (ISO527/2-93) is 65MPa, and flexural strength (ISO178-93) is 100MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 4500MPa, and notched Izod impact strength (ISO180-93) is 14KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～5 ‰, (ISO75/1-93 1.82MPa) is 149 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 12
Be 150,000 polypropylene 50 weight parts, thermo-stabilizer 1 in proportion with molecular weight, 3,5-trimethylammonium-2,4,6-three (3, the 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, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 51MPa, and flexural strength (ISO178-93) is 81MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3100MPa, and notched Izod impact strength (ISO180-93) is 9KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 144 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 13
Be 150,000 polypropylene 50 weight parts, thermo-stabilizer 2 in proportion with molecular weight, 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, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 58MPa, and flexural strength (ISO178-93) is 85MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3500MPa, and notched Izod impact strength (ISO180-93) is 10KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 140 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 14
Be 150,000 polypropylene 50 weight parts, 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 in proportion with molecular weight in length-to-diameter ratio be that melting mixing is disperseed in the twin screw extruder of 40:1, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, lower shrinking percentage and higher heat-drawn wire, its flame retardant properties can reach 2.5mm V0, tensile strength (ISO527/2-93) is 58MPa, and flexural strength (ISO178-93) is 87MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3500MPa, and notched Izod impact strength (ISO180-93) is 9KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 142 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 15
Be 150,000 polypropylene 50 weight parts, thermo-stabilizer in proportion with molecular weight 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 be that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 53MPa, and flexural strength (ISO178-93) is 82MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3200MPa, and notched Izod impact strength (ISO180-93) is 9KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 141 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 16
Be 150,000 polypropylene 50 weight parts, thermo-stabilizer in proportion with molecular weight 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 be that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, lower shrinking percentage and higher heat-drawn wire, its flame retardant properties can reach 2.8mm V0, tensile strength (ISO527/2-93) is 63MPa, and flexural strength (ISO178-93) is 98MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 4100MPa, and notched Izod impact strength (ISO180-93) is 11KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～5 ‰, (ISO75/1-93 1.82MPa) is 146 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Embodiment 17
Be 150,000 polypropylene 50 weight parts, thermo-stabilizer in proportion with molecular weight 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 be that melting mixing is disperseed in the twin screw extruder of 40:1 in length-to-diameter ratio, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, lower shrinking percentage and higher heat-drawn wire, its flame retardant properties can reach 2.0mm V0, tensile strength (ISO527/2-93) is 60MPa, and flexural strength (ISO178-93) is 88MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3900MPa, and notched Izod impact strength (ISO180-93) is 10KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 143 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
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, the 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, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products has the excellent fire retardant effect, good comprehensive mechanical properties, lower shrinking percentage and higher heat-drawn wire, its flame retardant properties can reach 2.5mm V0, tensile strength (ISO527/2-93) is 59MPa, and flexural strength (ISO178-93) is 92MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3700MPa, and notched Izod impact strength (ISO180-93) is 10KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 141 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
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, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 52MPa, and flexural strength (ISO178-93) is 78MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3100MPa, and notched Izod impact strength (ISO180-93) is 10KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 143 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
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, alkali free glass fibre 20 weight parts add from the side feeding, at 200 ℃ of extruding pelletizations.
The said products 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 (ISO527/2-93) is 58MPa, and flexural strength (ISO178-93) is 82MPa, and elongation at break (ISO527/2-93) is 5%, modulus in flexure (ISO178-93) is 3500MPa, and notched Izod impact strength (ISO180-93) is 9KJ/m
2, injection moulding shrinking percentage (ASTM D-955) is 4～6 ‰, (ISO75/1-93 1.82MPa) is 141 ℃ to heat-drawn wire, and the other technologies index meets or exceeds fire-retardant acrylonitrile-butadiene diene-styrene copolymer standard of materials.
Claims (14)
1. a 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;
Glass compatilizer 1-5;
Glass fibre 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 glass 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 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 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 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, the 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, the mixture of one or several in 2 '-methylene bis (4-ethyl-6 tert.-butyl phenol).
5. a kind of 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 halogen-free flame retardant polypropylene composite material as claimed in claim 1 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 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 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 halogen-free flame retardant polypropylene composite material as claimed in claim 1 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 halogen-free flame retardant polypropylene composite material as claimed in claim 1 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 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 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 halogen-free flame retardant polypropylene composite material as claimed in claim 1 is characterized in that, described glass fibre is an alkali free glass fibre.
14. the preparation method of a kind of 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 35-45:1 with polypropylene, thermo-stabilizer, processing aid, toughner, fire retardant, glass compatilizer in length-to-diameter ratio in proportion, glass fibre adds from the side feeding, at 170-240 ℃ of extruding pelletization.
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