Background technology
Wood plastic composite is to utilize vegetable fibre and thermoplastic resin to be main raw material, adds the prepared a kind of novel environment-friendly material of certain processing aid.This material can be alleviated the oil consumption, has used depleted vegetable fibre and reprocessed plastic(s) in a large number simultaneously, can alleviate modern society to consumption of petroleum resources, can reduce the consumption of timber resources again, is protection environment and the effective means that cuts down the consumption of energy.
In view of the plurality of advantages of wood plastic composite, its market growth is very fast in recent years, especially shows indoor article, building and Automobile Products etc.But then, fast the market requirement that increases is simultaneously to the demands for higher performance of wood plastic composite, for example because thermoplastic resin and vegetable fibre all belong to inflammable substance, so need carry out prepared wood plastic composite flame-retardant modified, and at the complex structure goods need extrude, machine-shaping mode beyond the mold pressing etc. etc.
In order to overcome the problems referred to above, usually the method for adding fire retardant in wood plastic composite is carried out flame-retardant modified, total institute is known, although the halogenated flame retardant flame retardant effect is better, but since its in when burning the amount of being fuming big, be easy to produce a large amount of toxic gases, increasing halogenated flame retardant is forbidden or is limited the use of.Therefore research and develop the halogen-free flame-retardant wood plastic composite trend that is inevitable, a kind of flame-resistant plastic-wood composite materials and preparation method thereof is disclosed in the Chinese patent application 200610039985.4, it is flame-retardant modified to adopt expansion type flame retardant ammonium polyphosphate, carbon forming agent and whipping agent etc. that polypropylene or polyethylene based wood-plastic composite material are carried out, but have that the fire retardant add-on is big, ammonium polyphosphate easily decomposes and shortcoming such as the easy moisture absorption of product under the processing temperature; Chinese patent application 200710072794.2 discloses a kind of flame-proof smoke-inhibiting wood-plastic composite material, and it is flame-retardant modified also to adopt p-poly-phenyl ethene such as expansion type flame retardant ammonium polyphosphate, starch or polyvinyl chloride to carry out, and still has above-mentioned shortcoming as expansion type flame retardant; In addition, Chinese patent application 200710173607.X discloses a kind of halogen-free flame-retardant wood-plastic composite material and preparation method thereof, same ammonium polyphosphate or the poly phosphate of adopting is as fire retardant, just it is at first with behind the dissolution with solvents fire retardant cellulosic material being soaked, prepare halogen-free flame-retardant wood-plastic composite material then, because it still uses expansion type flame retardant, and increased the step of handling fiber separately and make its practicality have a greatly reduced quality.
In addition, at present existing wood is moulded preparation technology mainly based on extrusion moulding, hot-forming and extruding shaping technique, be mainly used in and produce the sheet material based article, Injection moulded part for the molding structure complexity is subjected to very big restriction, subject matter is because the wood plastic composite of a large amount of wood powders of adding is mobile poor, product intensity is low, and visual appearance is poor.Although disclose injection-grade wood plastic composite and complete processing in the Chinese patent application 200710020012.7, but its prepared wood plastic composite melt flow rate (MFR) scope only is 0.3-1.0g/10min, and can only be used for polypropylene, high density polyethylene(HDPE) or polyvinyl chloride, its practical ranges is very limited.
On the basis of existing Composite Preparation equipment, injection system by high mixer carries out fire-retardant finish to vegetable fibre, make suitability for industrialized production have continuity and operability, and organic phosphorus flame retardant carry out the flame-retardant modified report that rarely has to injection-grade wood plastic composite.
Summary of the invention
Purpose of the present invention is primarily aimed at the deficiencies in the prior art, and a kind of halogen-free flameproof is provided, good fluidity, and product intensity height, visual appearance is good, is suitable for the vegetable fibre modified thermoplastic wood-plastic composite of injection moulding.
Another object of the present invention provides the preparation method of above-mentioned styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials.
To achieve these goals, the present invention adopts following technical scheme:
A kind of styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials, form by following component and mass percent:
Phenylethylene resin series: 25-60%
Vegetable fibre: 5-50%
Compatilizer: 0.5-20%
Toughner: 0-30%
Dispersion agent: 0.5-8%
Fire retardant and synergist: 5-40%
Oxidation inhibitor: 0-1%
In above-mentioned styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials, described phenylethylene resin series is general purpose polystyrene (GPPS), high-impact polystyrene (HIPS), styrene-maleic anhydride copolymer (SMA), acrylonitritrile-styrene resin (AS), copolymer of methyl methacrylatestyrene (MS), acrylonitrile-butadiene-styrene copolymer (ABS), vinyl cyanide-terpolymer EP rubber-styrol copolymer (AES), acrylonitrile acryloid styrene (ASA), MBS (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), the mixture of one or more in methyl methacrylate-terpolymer EP rubber-styrol copolymer (MES).
In above-mentioned styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials, described vegetable fibre is one or more the mixture in wood dust, shell powder, bamboo powder, straw powder, litter shell powder, other farm crop or the plant stem-leaf powder.
In above-mentioned styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials, described compatilizer is maleic anhydride graft HIPS (HIPS-g-MAH), maleic anhydride grafted ABS (ABS-g-MAH), maleic anhydride graft styrene-butadiene-styrene block copolymer (SBS-g-MAH), maleic anhydride graft hydrogenated styrene-butadiene-styrene block copolymers (SEBS-g-MAH), maleic anhydride graft polyolefine (PO-g-MAH), maleic anhydride graft polyolefin elastomer (POE-g-MAH), glycidyl methacrylate graft HIPS (HIPS-g-GMA), glycidyl methacrylate graft ABS (ABS-g-GMA), glycidyl methacrylate graft styrene-butadiene-styrene block copolymer (SBS-g-GMA), glycidyl methacrylate graft hydrogenated styrene-butadiene-styrene block copolymers (SEBS-g-GMA), glycidyl methacrylate graft polyolefine (PO-g-GMA), glycidyl methacrylate graft polyolefin elastomer (POE-g-GMA), the ethylene-acrylic acid resin copolymer, ethylene-acrylic acid copolymer (EAA), the ethylene-acrylic acid salt copolymer, ethylene-vinyl acetate copolymer (EVA), the mixture of one or more in the styrene-maleic anhydride copolymer (SMA).
In above-mentioned styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials, described toughner is styrene-butadiene-styrene block copolymer (SBS), oil-filled SBS, hydrogenated styrene-butadiene-styrene block copolymers (SEBS), ethylene-propylene rubber(EPR) (EPM), paracril (NBR), terpolymer EP rubber (EPDM), cis-1,4-polybutadiene rubber (BR), natural rubber (NR); styrene-butadiene rubber(SBR) (SBR); acrylic resin; ABS high glue powder; MBS (MBS); styrene-acrylonitrile copolymer acid butyl ester binary graft ethylene third glue; POE; ethylene-acrylic acid resin copolymer; EAA; ethylene-acrylic acid salt copolymer; the mixture of one or more among the EVA.
In above-mentioned styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials, described dispersion agent is a silane coupling agent, titanate coupling agent, the chromium cpd coupling agent, the aluminic acid lipoprotein coupling agent, boric acid fat coupling agent, zirconium coupling agent, the magnesium coupling agent, stearic acid or its salt, whiteruss, silicone oil, erucicamide, amine hydroxybenzene, N, N '-two ethylene stearylamides, the two amine hydroxybenzenes of ethylene, stearic amide, glycerine list olein, two glyceryl ether list oleins, modified glycerol three sour fat, mountain Yu acid amides, citric acid three (18) fat, the positive fourth fat of stearic acid, stearyl alcohol, single oleic acid (tetramethylolmethane glyceryl ether) fat, glyceryl monostearate, stearic acid two glyceryl ester, glycerol stearate, dibutyl phthalate (DBP), phthalic acid diethyl ester, o-phthalic acid dibutyl ester, the terephthalic acid dibutyl ester, oleic acid fourth fat, the hexanodioic acid dibutyl ester, the nonane diacid dibutyl ester, the sebacic acid dibutyl ester, the hot fat of tricresyl phosphate, Triphenyl phosphate (TPP), tricresyl phosphate benzyl fat, epoxy soybean oil, the hot fat of epoxystearic acid, hexanodioic acid propylene glycol polyester, sebacic acid propylene glycol polyester, poly-a-vinyl toluene, clorafin, alkylsulphonic acid benzene fat, fluid rubber, Resins, epoxy, resol, furane resin, polyester oil, polyester, polymeric amide, urethane, the mixture of one or more in the urea-formaldehyde resin.
In above-mentioned styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials, described fire retardant is that existing flame retardant effect has the organic phosphorus flame retardant of plasticization effect such as one or more the mixture in phosphoric acid ester, phosphonic acid ester, phosphorus oxide, phosphiinic acid ester and the microcosmic salt etc. again, wherein phosphoric acid ester comprise Resorcinol biphosphonate (RDP), dihydroxyphenyl propane two (phosphoric acid hexichol fat) (BAPP), the two diphenyl phosphoesters (BDP) of dihydroxyphenyl propane, triphenylphosphate (TPP), Tritolyl Phosphate (TCP), tributyl phosphate, triisopropyl phosphoric acid ester, trimethyl phosphate etc.; Phosphonic acid ester comprises dimethyl methyl phosphonate, alkylene phosphonic acid ester, acid amides phosphonic acid ester, annular phosphonate etc.; Phosphorus oxide comprises two (hydroxypropyl) phosphine oxides (FR-D) of normal-butyl, three hydroxypropyl phosphine oxides (FR-T), ring octyl group hydroxypropyl phosphine oxide (CODPPO), to two (22 cyanoethyl phosphine oxide methyl) tetramethyl-benzene (RF2699) etc.; Fire retarding synergist is organic class and the composite use of mineral-type, and wherein organic class comprises one or more mixture such as tetramethylolmethane, starch, Resins, epoxy, resol; Inorganic synergist comprises one or more the mixture in magnesium hydroxide, aluminium hydroxide, magnesium oxide, aluminum oxide, zinc borate, borax, barium metaborate, polynite, the zeolite; Fire retardant: fire retarding synergist=20~30: 1 (mass ratio).
In above-mentioned styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials, described oxidation inhibitor is phenols, phosphorous acid esters, contain one or more the mixture in thioesters class, the metal passivator etc.
The preparation method of styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials, its preparation comprises the steps:
Step 1: earlier with vegetable fibre 100~150 ℃ of oven dry 3~8 hours down, make the water ratio of vegetable fibre below 2%;
Step 2: in high mixer, utilize the injection system of high mixer, with organophosphorous fire retardant vegetable fibre, dispersion agent and fire retarding synergist are carried out the oil spout premix and handle, obtain fire-retardant plant fiber;
Step 3: even in high-speed mixer and mixing in proportion fire-retardant plant fiber and all the other each components, obtain Preblend;
Step 4: Preblend is joined extruding pelletization in the forcing machine, obtain the styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials.
Compared with prior art, the present invention has following beneficial effect:
At first, adopt injection system that vegetable fibre etc. is carried out fire-retardant finish.Because organic phosphorus flame retardant mostly is liquid greatly, it is better mobile under proper temperature, can utilize injection system that high mixer is joined with fire retardant vegetable fibre to be carried out fire-retardant finish, thereby give full play to the flame retardant effect of fire retardant;
Secondly, add organic class and mineral-type fire retarding synergist.Owing to scarcely contain oxygen element in the styrenic, so organic phosphorus flame retardant is limited to its flame retardant effect.The present invention discovers that the synergistic effect of mixture that organic class fire retarding synergist and mineral-type fire retarding synergist are composite and organophosphorus owner fire retardant is better, major cause is that organic class fire retarding synergist such as tetramethylolmethane, starch, resol, Resins, epoxy etc. have and becomes the carbon effect preferably, and mineral-type fire retarding synergist such as magnesium hydroxide and aluminium hydroxide itself have flame retardant effect, and what its cooling simultaneously and coverage effect had further replenished organic phosphorus flame retardant becomes carbon and coverage effect.
Once more, add the dispersion agent of optimizing.At organophosphorus is on the basis of plastification, further adds the dispersion agent of optimizing, and makes the mobile of wood plastic composite system further improve, thereby makes fire-retardant injection-grade wood plastic composite.
Comprehensive above characteristics, the styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials that makes the present invention make is compared with existing wood plastic composite, has characteristics such as Production Flow Chart is simple, the fire retardant consumption is less, halogen-free flameproof is effective, the molding mode scope is wide.Be applicable to various Injection moulded parts, as production electric equipment products shell, furniture, materials used in auto manufacturing, artwork, complex construction building product etc.
Embodiment
Further specify the present invention below in conjunction with embodiment, scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
Feed composition is counted by quality percentage:
ABS resin: 37.4%
100 order wood powders: 25%
ABS-g-MAH:5%
ABS high glue powder: 5%
Whiteruss: 1%
Dibutyl phthalate (DBP): 0.5%
N, N '-two ethylene stearylamides: 1%
RDP:15%
Resins, epoxy: 5%
3000 order super fine magnesium hydroxides: 5%
Antioxidant 1010: 0.1%
The preparation method is: (1) earlier with vegetable fibre 120 ℃ of oven dry 5 hours down, make the water ratio of vegetable fibre below 2%;
(2) in high mixer, utilize the injection system of high mixer, with fire retardant vegetable fibre, dispersion agent and fire retarding synergist are carried out the oil spout premix and handle, obtain fire-retardant plant fiber;
(3) even in high-speed mixer and mixing in proportion fire-retardant plant fiber and all the other each components, obtain Preblend;
(4) Preblend is joined extruding pelletization in the forcing machine, obtain the styrene-based non-halogen flame-retardant injection-grade wood plastic composite materials.
Above-mentioned wood plastic composite is as follows through the performance that detects:
Proportion 1.18g/cm
3
Tensile strength 34.3Mpa
Elongation 7.1%
Socle girder unnotched impact strength 187J/m
Flexural strength 55.6MPa
Modulus in flexure 3785Mpa
Melting index (200 ℃, 5 kilograms) 4.8g/10min
Flame retardant properties (UL-94, vertical) V-0@2.0mm
Embodiment 2
Feed composition is counted by quality percentage:
HIPS:39.4%
100 order bamboo powder: 25%
HIPS-g-MAH:5%
Oil-filled SBS:5%
Whiteruss: 1%
Silane coupling agent: 0.5%
N, N '-two ethylene stearylamides: 1%
TPP:13%
Tetramethylolmethane: 5%
3000 order super fine magnesium hydroxides: 5%
Antioxidant 1010: 0.1%
According to embodiment 1 described preparation technology, extruding pelletization obtains halogen-free flame-retardant type injection molding-class HIPS wood plastic composite.
Above-mentioned wood plastic composite is as follows through the performance that detects:
Proportion 1.17g/cm
3
Tensile strength 31.4Mpa
Elongation 8.1%
Socle girder unnotched impact strength 164J/m
Flexural strength 42.5MPa
Modulus in flexure 3367Mpa
Melting index (200 ℃, 5 kilograms) 5.2g/10min
Flame retardant properties (UL-94, vertical) V-0@2.0mm
Embodiment 3
Feed composition is counted by quality percentage:
AS resin: 37.9%
100 order bamboo powder: 25%
ABS-g-MAH:5%
ABS high glue powder: 5%
Whiteruss: 0.5%
Dibutyl phthalate (DBP): 0.5%
N, N '-two ethylene stearylamides: 1%
RDP:15%
Resol: 5%
3000 order magnesium hydroxides: 5%
Antioxidant 1010: 0.1%
According to embodiment 1 described preparation technology, extruding pelletization obtains halogen-free flame-retardant type injection molding-class AS wood plastic composite.
Above-mentioned wood plastic composite is as follows through the performance that detects:
Proportion 1.17g/cm
3
Tensile strength 45.9Mpa
Elongation 5.6%
Socle girder unnotched impact strength 145J/m
Flexural strength 65.8MPa
Modulus in flexure 5019Mpa
Melting index (200 ℃, 5 kilograms) 7.8g/10min
Flame retardant properties (UL-94, vertical) V-0@2.0mm
Embodiment 4
Feed composition is counted by quality percentage:
GPPS resin: 38.9%
100 order powdered rice hulls: 25%
SBS-g-MAH:5%
SBS:5%
Whiteruss: 0.5%
Dibutyl phthalate (DBP): 0.5%
N, N '-two ethylene stearylamides: 1%
BAPP:14%
Starch: 5%
3000 order aluminium hydroxides: 5%
Antioxidant 1010: 0.1%
According to embodiment 1 described preparation technology, extruding pelletization obtains halogen-free flame-retardant type injection molding-class GPPS wood plastic composite.
Above-mentioned wood plastic composite is as follows through the performance that detects:
Proportion 1.16g/cm
3
Tensile strength 40.8Mpa
Elongation 4.9%
Socle girder unnotched impact strength 158J/m
Flexural strength 47.9MPa
Modulus in flexure 4107Mpa
Melting index (200 ℃, 5 kilograms) 6.3g/10min
Flame retardant properties (UL-94, vertical) V-0@2.0mm.