CN103113677A - Halogen-free flame-retardant anti-mildew composite and preparation method thereof - Google Patents
Halogen-free flame-retardant anti-mildew composite and preparation method thereof Download PDFInfo
- Publication number
- CN103113677A CN103113677A CN2013100866334A CN201310086633A CN103113677A CN 103113677 A CN103113677 A CN 103113677A CN 2013100866334 A CN2013100866334 A CN 2013100866334A CN 201310086633 A CN201310086633 A CN 201310086633A CN 103113677 A CN103113677 A CN 103113677A
- Authority
- CN
- China
- Prior art keywords
- mass parts
- retardant
- ethylene
- flame
- bamboo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a halogen-free flame-retardant anti-mildew composite which is prepared by jointly melting and mixing the following raw materials in parts by weight: 100 parts of polypropylene and polyvinyl chloride, 40-50 parts of bamboo fiber powder, 5-6 parts of camphor wood powder, 5-6 parts of compatibilizer, 5-6 parts of flexibilizer, 30-40 parts of flame retardant and synergist, 4-6 parts of heat stabilizer, 4-6 parts of lubricant, 4-5 parts of oxygen inhibitor, and 0-1 parts of antioxidant by three times, and finally extruding and forming. The bamboo-plastic composite has excellent mechanical performance and flame retardance and anti-mildew properties.
Description
One, technical field
The present invention relates to a kind of bamboo-plastic composite material and preparation method thereof, specifically the anti-bamboo-plastic composite material and preparation method thereof that goes mouldy of a kind of halogen-free flameproof.
Two, background technology
Wood plastic composite (wood/plastic composite, be called for short " WPC ") is a kind of emerging circumstance friendly composite material that utilizes various discarded vegetable fibres and reclaiming plastics to make by compound, blend, modified technique technology.At present WPC is mainly used in the door and window, top board, template, floor, roof boarding, dividing plate of building field etc.The raw material of wood-plastic products comprises: various waste or used plastics (plastic wrapping, milk bag, waste or used plastics goods, TV shell etc.) and wood powder (rice husk of the scrap stock of wood working, sawdust, wood powder, crop, stalk etc.).Not only hardness is high for wood plastic product, easy coloring, easily processing, wear-resisting, water-absorbent is little, the plurality of advantages such as similar wood appearance is arranged, and can effectively solve " white pollution " problem that world forest resources lacks day by day and a large amount of waste or used plastics causes environment, good in to mould Dai Mu, to mould for steel novel environment friendly material, has good market application foreground.Studies show that: material of construction accounted for 80% of North America wood plastic composite aggregate demand to wood plastic composite with double-digit speed increment in from 2003 to 2010 in the market of North America; In West Europe, vehicle material has accounted for the over half of wood plastic composite demand, separately has material of construction to account for 30% market; In Japan, wood plastic composite on the floor, the application of the aspects such as wall and furniture is also day by day universal; In China, wood plastic composite has been widely used in packing, transportation, municipal administration, shipping vehicle, indoor door and window, floor, furniture, and the outdoor building finishing material etc.
Yet, meet naked light or when heating easy firing be the critical defect of WPC, this be due to xylon and Plastic Resin (in general-purpose plastics except PVC, polyethylene, polypropylene, ABS etc.) be inflammable material, directly application, particularly indoor, has the potential safety hazard of easy initiation fire.Thereby WPC is the requirement that is difficult to reach code for fire prevention design of interior decoration of buildings without fire-retardant finish, is in principle do not allow as relevant constructional ornamental material and directly use.
The fire retardant mechanism of WPC relates to that xylon is fire-retardant, plastic flame and the problems such as synergy both.At present, respectively xylon, plastic substrate are carried out the method for fire-retardant finish for general employing of technical study of wood plastic composite fire-retardant finish both at home and abroad.In the traditional polymer flame-retarded technology, a kind of method of comparative maturity is to adopt halogen flame (particularly bromine system) and antimonous oxide (Sb
2O
3) compatibility, be commonly called as " halogen-antimony collaboration system ".Yet the research report is arranged, and the split product of bromo phenyl ether (PBDPO) contains the dioxin violent in toxicity, and the smog that combustion processes produces is very large, and the personnel that very easily cause suffocate.Nowadays, European Union has prohibited the use halogen containing flame-retardant.The fire retardant mechanism of conventional halogen-free flame-retardant system (as aluminium hydroxide, magnesium hydroxide etc.) is to decompose to produce water when being heated, absorb heat and reach fire-retardant purpose, this based flame retardant can meet the requirement of environmental-protection flame-retardant, but amount of filler is large (need to reach 40% left and right) usually, cause the mixing and moulding mobility variation of WPC, affect Drawing abillity and physical and mechanical property.Adopt organo montmorillonite (OMMT) although wood plastic composite is carried out the flame-retardant modified report that also has, yet the consistency between polynite at present and resin matrix is difficult to have substantial improvement, and the fire-retardant index of OMMT modified composite material of woods and plastics still is difficult to by LOI and vertical combustion level estimate.
The flame-retardant wood-plastic composite material of the Intumescent Retardant System preparation take ammonium polyphosphate (APP) as main body is (as " flame-retardant wood-plastic composite material and preparation method thereof ", publication number CN1837278A), adopt APP as the fire retardant main body, take tetramethylolmethane (PER) or starch as the charcoal source, matrix material has possessed flame retardant resistance preferably, but the APP add-on is larger, and affects the mechanical property of flame retardant resistance wood plastic composite; Simultaneously, the APP price is more expensive, and production cost is improved.Similarly also have, publication number is the Chinese patent of CN101469082A, has reported a kind of water-soluble phosphorously and contain nitrogen combustion inhibitor, be used for the fire-retardant cellulose material, but the fire retardant addition is large, affected the goods physical and mechanical property, and flame retarding efficiency is more limited.Publication number is the Chinese patent of CN101812237A, adds the ammonium phosphate type fire retardant take ammonium hydrogen phosphate, primary ammonium phosphate as main body in the recycled plastic, but also fails fundamentally to address the above problem.Chinese patent (application number: 200710173607.X) adopt ammonium polyphosphate or poly phosphate as fire retardant, first with after the dissolution with solvents fire retardant, wood fibre being soaked, then prepare halogen-free flame-retardant wood-plastic composite material, and it still uses expansion type flame retardant, and has increased the step that wood fibre processes and make its practicality to have a greatly reduced quality.Existing research report, in vegetable fibre, contained Mierocrystalline cellulose, hemicellulose is polyol (PER is similar with adding), thereby under hot conditions with the APP reaction, serve as the effect of carbon source, thereby need not to add again " carbon forming agent ".
Although wood plastic composite by plastic overmold, still can cause wood plastic composite to go mouldy, rot for fungi provides good living environment owing to having filled a large amount of vegetable fibres under certain wet condition, thus reduction of service life.In addition, going mouldy to make wood plastic composite surface produce macroscopic mould spot, affects that it is attractive in appearance, and this can be very limited when WPC uses as outdoor goods.The Chen Juan of Guangdong Dimei Biological Technology Co., Ltd. etc. discloses " a kind of special weatherproof moldproof functional master batch for wood/plastic composite material and preparation method thereof " (publication number: CN102181090A), its composition comprises polyethylene, ZnO, N-trichloro-methylthio phthalimide, 4,5-two chloro-N-octyl group-3-isothiazolinone etc.South China Normal University's disclosed " a kind of long-acting mould-proof wood plastic composite material and preparation method thereof " (publication number: CN101767362A), its mildewproof additive is nano-ZnO or its composition of nano TiO 2, surface modification, produce the multilayer wood-plastic matrix material by coextrusion technology, preparation technology's more complicated improves production cost.The main body of considering wood plastic composite is vegetable fibre, can utilize the anti-mould and anti-moth characteristic of natural camphorwood powder, not only can reduce costs, and more environmental protection.
The wood plastic composite of reporting at present, its preparation technology is take extrusion moulding, compression molding as main, and for the production of plate, sheet material based article, because WPC has added a large amount of wood powders, add again a large amount of fire retardants and other processing aid, system mobility variation be can cause, thereby products appearance and use properties thereof had influence on.
In recent years, the flame retardant resistance modification of wood plastic composite more and more is subject to people's concern and attention.How improve the flame retardant properties of polymer matrix composite with fire retardant, and produce flue gas and toxic gas, the key issue that has become the novel material research and development and used when suppressing the burning of matrix material or cracking.
Three, summary of the invention
The present invention is poor in order to solve existing halogen-free flame-retardant wood plastic composite mildew-resistant sex change, and fire retardant APP addition ambassador production cost improves and causes the problem of Material Physics mechanical properties decrease, thereby a kind of anti-non-halogen flame-proof smoke-restraining bamboo-plastic composite material and preparation method thereof that goes mouldy is provided.
The anti-bamboo-plastic composite material that goes mouldy of a kind of halogen-free flameproof is comprised of each component of following mass fraction:
Polypropylene and polyvinyl chloride: 100 mass parts
Bamboo fibers powder: 40-50 mass parts
Camphorwood powder: 5-6 mass parts
Expanding material: 5-6 mass parts
Toughner: 5-6 mass parts
Fire retardant and synergist: 30-40 mass parts
Thermo-stabilizer: 4-6 mass parts
Lubricant: 4-6 mass parts
Oxygen inhibiting agent: 4-5 mass parts;
Oxidation inhibitor: 0-1 mass parts.
The polypropylene (PP) and the polyvinyl chloride (PVC) that reclaim all can use.PP to reclaiming requires melt flow rate (MFR) (MFR) to be not less than 0--3.The blend ratio of PP and PVC satisfies 1:1～1:3(mass ratio).
Described bamboo fibers powder median size 40-80 order; Described camphorwood powder, median size 60-100 order.
Described expanding material is comprised of main expanding material and auxiliary expanding material, wherein main expanding material is ethylene-vinyl acetate-vinyl chloride graft copolymer (EVA-g-PVC), and auxiliary expanding material is selected from grafting and comes one or more mixture in horse acid anhydrides polypropylene (MAH-g-PP), maleic anhydride stem grafting polyolefin elastomerics (MAH-g-POE), glycidyl methacrylate graft polypropylene (GMA-g-PP), ethylene-acrylic acid copolymer (EAA), ethylene-vinyl acetate copolymer (EVA).The mass ratio of main expanding material and auxiliary expanding material satisfies 1:2～3:1.When auxiliary expanding material was two or more mixing, ratio was any mutually.
Described toughner is selected from one or more the mixture in styrene-butadiene-styrene block copolymer (SBS), ethylene-propylene rubber(EPR) (EPR), paracril (NBR), terpolymer EP rubber (EPDM), cis-1,4-polybutadiene rubber (BR), natural rubber (NR), styrene-butadiene rubber(SBR) (SBR), Thermoplastic Elastomer, Olefinic (POE), chlorinatedpolyethylene (CPE), ethylene-acrylic acid copolymer (EAA), ethylene-vinyl acetate copolymer (EVA).When selecting two or more mixing, ratio is any mutually.
Described fire retardant is ammonium polyphosphate (APP, the polymerization degree 1000～4000); Described fire retarding synergist comprises organic and inorganic two classes, and organic synergist is selected from one or more the mixture in tetramethylolmethane, trimeric cyanamide, resol, epoxy resin; Inorganic synergist is selected from one or more the mixture in magnesium hydroxide, aluminium hydroxide, zinc borate, polynite (nano level), zeolite, organic and inorganic synergist can mix use, blending ratio is any, and the mass ratio of described fire retardant and fire retarding synergist satisfies 1:2～4:1.Wherein trimeric cyanamide, magnesium hydroxide, aluminium hydroxide have the effect of smoke suppressant concurrently; Zinc borate has mildew-proof function concurrently.
Described thermo-stabilizer is Ca-Zn composite heat stabilizer, and its effect is that blending resin polyvinyl chloride (PVC) component is played heat stabilization.
Described oxidation inhibitor is selected from one or more the mixture in antioxidant 1010, irgasfos 168, oxidation inhibitor 301 or oxidation inhibitor DSTP; When selecting two or more mixing, ratio is any mutually.
Described oxygen inhibiting agent is selected from trolamine, two carboxyphenyl propylamine, methyldiethanolamine, sodium bicarbonate etc.
Described lubricant is selected from one or more the mixture in stearic acid, calcium stearate, Zinic stearas, whiteruss, ethylene chloride wax, ethylene oxide wax, ethylene bis stearamide.When selecting two or more mixing, ratio is any mutually.
the preparation method of the anti-bamboo-plastic composite material that goes mouldy of above-mentioned halogen-free flameproof, comprise the bamboo fibers powder, the drying of camphorwood powder, flame-retardant modified granulation, blend granulation and extrusion moulding, described drying is with the bamboo fibers powder, camphorwood powder is dried to water ratio≤2%, difference with the prior art is: described flame-retardant modified granulation is the polypropylene with proportional quantity, polyvinyl chloride (PVC) RESINS, main expanding material, toughner, thermo-stabilizer, oxidation inhibitor, the part lubricant, fire retardant and synergist add in high-speed mixer, mix under 110-120 ℃, obtain compound, through the parallel equidirectional two-screw tablets press in 190-200 ℃ of extruding pelletization, obtain flame-retardant modified pellet, described blend granulation is the bamboo fibers powder of above-mentioned flame-retardant modified pellet, proportional quantity, camphorwood powder, auxiliary expanding material, surplus lubricant and oxygen inhibiting agent to be mixed to add to mix under 110-120 ℃ in high-speed mixer obtain secondary mixed material, and melt blending, extruding pelletization obtain the blend pellet under 170-195 ° of C in dual-screw pelletizer, described extrusion moulding is that the blend pellet is obtained this bamboo-plastic composite material goods through twin screw extruder in 150-195 ℃ of extrusion moulding.Determined the shape of goods by the shaping equipment of head.
Concrete operation step is as follows:
(1) first with bamboo fibers powder (40～80 order), camphorwood powder (60～100 order) vacuum drying 4～7 hours under 100～120 ° of C, make the water ratio of vegetable fibre lower than 2%;
(2) polypropylene, polyvinyl chloride (PVC) RESINS, main expanding material, toughner, thermo-stabilizer, oxidation inhibitor, part proportional quantity lubricant, fire retardant and the synergist with proportional quantity adds in high-speed mixer, under temperature 110-120 ° C, rotating speed 600～700r/min condition, mix 10～15min, above-mentioned compound is joined carry out melt blending, extruding pelletization in the parallel equidirectional two-screw tablets press, temperature is 190～200 ° of C, screw speed 80～120r/min obtains flame-retardant modified pellet (this is a melting mixing process);
(3) oxygen inhibiting agent of the bamboo fibers powder of above-mentioned flame-retardant modified pellet and proportional quantity and camphorwood powder, auxiliary expanding material, surplus proportional quantity lubricant and proportional quantity etc. is added high-speed mixer (mixing condition: 110～120 ° of C of temperature, rotating speed 700～800r/min), mixing time 15～25min obtains secondary mixed material; With secondary mixed material join wood mould melt blending in the special twin screw tablets press, extruding pelletization (processing condition: 170～195 ° of C of temperature, screw speed 180～200r/min) obtains blend pellet (this is second melting mixing process);
(4) the blend pellet is added wood mould and carry out (150～190 ° of C of extrusion temperature of melt blending extrusion moulding for the third time in the special twin screw forcing machine, screw speed 10～40r/min) namely obtains the anti-bamboo-plastic composite material goods that go mouldy of halogen-free flameproof by extruder head, cooling and shaping device.(this is three melting mixing processes);
Present method adopts twin screw " three step scorifications ", can effectively improve interface adhesion and consistency between different mixture resin and fluoropolymer resin and vegetable fibre, thereby improve mechanical property, flame retardant properties and the mildew-resistant sex change energy of matrix material.Simultaneously, the application adopts Ethlene vinylacetate vinylchloride graft copolymer (EVA-g-PVC) as main expanding material, the consistency between polyvinyl chloride, acrylic resin and vegetable fibre not only can be effectively improved, weathering resistance and the impelling strength of matrix material can be improved simultaneously.
As preparing wood plastic composite, the fire retardant main body compares take ammonium polyphosphate with existing, flame retardant type bamboo-plastic composite material of the present invention utilizes the flame retardancy of PVC, and minimizing APP consumption, at first improve the PP flame retardant effect by " three step scorifications ", next improves the consistency between each component of composite system, thereby effectively improves the flame retardant effect of this matrix material; And reduce the usage quantity of main ammonium polyphosphate flame retardant.This bamboo-plastic composite material is compared with existing wood plastic composite, has flame retardant properties good, and amount of smoke is little.Add camphorwood powder owing to forming at raw material, utilized the fire-retardant mildew-resistant synergy of zinc borate to make the gained bamboo-plastic composite material have the good natural anti-effect of going mouldy.Preparation technology of the present invention is relatively simple, and is applicable to suitability for industrialized production.
Four, embodiment
Further illustrate 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 according to the mass fraction:
Reclaim polypropylene: 50 mass parts
Waste polyvinyl chloride: 50 mass parts
Bamboo powder (80 order): 45 mass parts
Camphorwood powder (60 order): 5 mass parts
The EVA-g-PVC:2 mass parts
The MAH-g-PP:3 mass parts
The CPE:5 mass parts
Ammonium polyphosphate (polymerization degree 2000): 20 mass parts
Trimeric cyanamide: 5 mass parts
Magnesium hydroxide: 10 mass parts
Zinc borate: 3 mass parts
Ethylene oxide wax: 3 mass parts
Calcium stearate: 1 mass parts
Zinic stearas: 1 mass parts
Sodium bicarbonate: 5 mass parts
Calcium zinc heat stabilizer: 4.5 mass parts
Antioxidant 1010: 0.5 mass parts
Irgasfos 168: 0.5 mass parts
The preparation method is as follows:
(1) first with bamboo powder, camphorwood powder vacuum drying 6 hours under 100～120 ° of C, make the water ratio of fir powder and camphorwood powder all lower than 2%;
(2) with polypropylene, polyvinyl chloride (PVC) RESINS, main expanding material EVA-g-PVC, toughening agent C PE, thermo-stabilizer, antioxidant 1010, 168, the lubricant oxidation ethylene waxes, ammonium polyphosphate flame retardant and synergist trimeric cyanamide, magnesium hydroxide, zinc borates etc. add in high-speed mixer, at temperature 110-120 ° C, under rotating speed 600～700r/min condition, mix 10～15min, above-mentioned compound is added carry out melt blending in the parallel equidirectional two-screw tablets press, extruding pelletization, temperature is 190～200 ° of C, screw speed 80～120r/min, obtain flame-retardant modified pellet,
(3) bamboo fibers powder and camphorwood powder, auxiliary expanding material MAH-g-PP, lubricant stearic acid calcium, Zinic stearas and the oxygen inhibiting agent sodium bicarbonate with above-mentioned flame-retardant modified pellet and process drying treatment adds high-speed mixer (mixing condition: 110～120 ° of C of temperature, rotating speed 700～800r/min), mixing time 15～25min obtains secondary mixed material; With secondary mixed material join wood mould granulation in the special twin screw tablets press (processing condition: 170～195 ° of C of temperature, screw speed 180～200r/min) obtains the blend pellet; Add wood to mould in the special twin screw forcing machine above-mentioned blend pellet to melt extrude that (150～190 ° of C of extrusion temperature, screw speed 10～40r/min) namely obtain the anti-bamboo-plastic composite material goods that go mouldy of halogen-free flameproof by extruder head, shaping equipment.
The anti-bamboo-plastic composite material that goes mouldy of the halogen-free flameproof that this implementation method prepares adopts mechanical property, fungicidal properties and flame retardant properties to detect.The mechanical property detected result is as shown in table 1, and the fungicidal properties detected result is as shown in table 2, and the flame retardant properties detected result is as shown in table 3.Can be found out by the data results in table 1, table 2 and table 3, the anti-bamboo-plastic composite material mechanical property of going mouldy of the halogen-free flameproof that this implementation method obtains is good, and has good flame-retardant smoke inhibition and mildew-resistant characteristic.
Embodiment 2:
Feed composition is according to the mass fraction:
Reclaim polypropylene: 50 mass parts
Waste polyvinyl chloride: 50 mass parts
Bamboo powder (80 order): 45 mass parts
Camphorwood powder (60 order): 5 mass parts
The EVA-g-PVC:2.5 mass parts
The MAH-g-PP:3 mass parts
The EPDM:5 mass parts
Ammonium polyphosphate (polymerization degree 4000): 20 mass parts
Resol: 5 mass parts
Aluminium hydroxide: 10 mass parts
Zinc borate: 3 mass parts
Chlorinatedpolyethylene wax: 3 mass parts
The EBS:2 mass parts
Two carboxyphenyl propylamine: 5 mass parts
Calcium zinc heat stabilizer: 5 mass parts
Antioxidant 1010: 0.6 mass parts
Oxidation inhibitor DSTP:0.4 mass parts
According to the described preparation technology of embodiment 1, make the anti-bamboo-plastic composite material goods that go mouldy of halogen-free flameproof through extrusion moulding.
The anti-bamboo-plastic composite material that goes mouldy of the halogen-free flameproof that this implementation method prepares adopts mechanical property, fungicidal properties and flame retardant properties to detect.The mechanical property detected result is as shown in table 1, and the fungicidal properties detected result is as shown in table 2, and the flame retardant properties detected result is as shown in table 3.Can be found out by the data results in table 1, table 2 and table 3, the anti-bamboo-plastic composite material mechanical property of going mouldy of the halogen-free flameproof that this implementation method obtains is good, and has good flame-retardant smoke inhibition and mildew-resistant characteristic.
Embodiment 3:
Feed composition is according to the mass fraction:
Reclaim polypropylene: 50 mass parts
Waste polyvinyl chloride: 50 mass parts
Bamboo powder (80 order): 45 mass parts
Camphorwood powder (60 order): 5 mass parts
The EVA-g-PVC:2 mass parts
The MAH-g-PP:3 mass parts
The POE:5 mass parts
Ammonium polyphosphate (polymerization degree 4000): 20 mass parts
Epoxy resin: 5 mass parts
Zinc borate: 3 mass parts
Polynite (nano level): 10 mass parts
Stearic acid: 2.5 mass parts
Zinic stearas: 2.5 mass parts
Methyldiethanolamine: 5 mass parts
Calcium zinc heat stabilizer: 5 mass parts
Antioxidant 1010: 0.6 mass parts
Oxidation inhibitor 301:0.4 mass parts
According to the described preparation technology of embodiment 1, make the anti-bamboo-plastic composite material goods that go mouldy of halogen-free flameproof through extrusion moulding.
The anti-bamboo-plastic composite material that goes mouldy of the halogen-free flameproof that this implementation method prepares adopts mechanical property, fungicidal properties and flame retardant properties to detect.The mechanical property detected result is as shown in table 1, and the fungicidal properties detected result is as shown in table 2, and the flame retardant properties detected result is as shown in table 3.Can be found out by the data results in table 1, table 2 and table 3, the anti-bamboo-plastic composite material mechanical property of going mouldy of the halogen-free flameproof that this implementation method obtains is good, and has good flame-retardant smoke inhibition and mildew-resistant characteristic.
Table 1 mechanical property table
Remarks: mechanical property is with reference to QB/T4161-2011; Flexural strength, bending elastic modulus are according to the GB/T9341-2000 standard testing; Shock strength is according to the GB/T1043.1-2008 standard testing.
Table 2 fungicidal properties table
Remarks: mildew-resistant grade evaluation standard A STM G21-09:0-without mildew; 1-mildew area is less than 10%; 2-mould-growth coverage rate is 10～30%; 3-mould-growth coverage rate is 30～60%; 4-mould-growth wide coverage is in 60%.
Table 3 flame retardant properties table
Remarks: combustionproperty is measured according to the GB8624-2006 standard testing.
Claims (9)
1. the anti-bamboo-plastic composite material that goes mouldy of a halogen-free flameproof is comprised of each component of following mass fraction:
Polypropylene and polyvinyl chloride: 100 mass parts
Bamboo fibers powder: 40-50 mass parts
Camphorwood powder: 5-6 mass parts
Expanding material: 5-6 mass parts
Toughner: 5-6 mass parts
Fire retardant and synergist: 30-40 mass parts
Thermo-stabilizer: 4-6 mass parts
Lubricant: 4-6 mass parts
Oxygen inhibiting agent: 4-5 mass parts;
Oxidation inhibitor: 0-1 mass parts
The mass ratio that polypropylene and polyvinyl chloride mix is 1:1-1:3; Bamboo fibers powder median size 40-80 order; Camphorwood powder median size 60-100 order.
2. matrix material according to claim 1 is characterized in that:
Described expanding material is comprised of main expanding material and auxiliary expanding material, wherein main expanding material is ethylene-vinyl acetate-vinyl chloride graft copolymer, and auxiliary expanding material is selected from grafting and comes one or more mixture in horse acid anhydrides polypropylene, maleic anhydride stem grafting polyolefin elastomerics, glycidyl methacrylate graft polypropylene, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer; The mass ratio of main expanding material and auxiliary expanding material satisfies 1:2-3:1; When auxiliary expanding material was two or more mixing, ratio was any mutually.
3. matrix material according to claim 1 is characterized in that:
Described toughner is selected from one or more the mixture in styrene-butadiene-styrene block copolymer, ethylene-propylene rubber(EPR), paracril, terpolymer EP rubber, cis-1,4-polybutadiene rubber, natural rubber, styrene-butadiene rubber(SBR), Thermoplastic Elastomer, Olefinic, chlorinatedpolyethylene, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer; When selecting two or more mixing, ratio is any mutually.
4. matrix material according to claim 1 is characterized in that:
Described fire retardant is the ammonium polyphosphate of polymerization degree 1000-4000; Described fire retarding synergist comprises organic and inorganic two classes, and organic synergist is selected from one or more the mixture in tetramethylolmethane, trimeric cyanamide, resol, epoxy resin; Inorganic synergist is selected from one or more the mixture in magnesium hydroxide, aluminium hydroxide, zinc borate, polynite, zeolite, organic and inorganic synergist can mix use, blending ratio is any, and the mass ratio of described fire retardant and fire retarding synergist satisfies 1:2～4:1.
5. matrix material according to claim 1 is characterized in that:
Described thermo-stabilizer is Ca-Zn composite heat stabilizer.
6. matrix material according to claim 1 is characterized in that:
Described oxidation inhibitor is selected from one or more the mixture in antioxidant 1010, irgasfos 168, oxidation inhibitor 301 or oxidation inhibitor DSTP; When selecting two or more mixing, ratio is any mutually.
7. matrix material according to claim 1 is characterized in that:
Described lubricant is selected from one or more the mixture in stearic acid, calcium stearate, Zinic stearas, whiteruss, ethylene chloride wax, ethylene oxide wax, ethylene bis stearamide; When selecting two or more mixing, ratio is any mutually.
8. matrix material according to claim 1 is characterized in that:
Described oxygen inhibiting agent is selected from trolamine, two carboxyphenyl propylamine, methyldiethanolamine, sodium bicarbonate etc.
9. the preparation method of the anti-bamboo-plastic composite material that goes mouldy of halogen-free flameproof as claimed in claim 1, comprise the drying of bamboo fibers powder, camphorwood powder, flame-retardant modified granulation, blend granulation and extrusion moulding, it is characterized in that:
Described flame-retardant modified granulation is that the polypropylene of proportional quantity, polyvinyl chloride (PVC) RESINS, main expanding material, toughner, thermo-stabilizer, oxidation inhibitor, part lubricant, fire retardant and synergist are added in high-speed mixer, mix under 110-120 ℃, obtain compound, in 190-200 ℃ of extruding pelletization, obtain flame-retardant modified pellet through the parallel equidirectional two-screw tablets press; Described blend granulation is the bamboo fibers powder of above-mentioned flame-retardant modified pellet, proportional quantity, camphorwood powder, auxiliary expanding material, surplus lubricant and oxygen inhibiting agent to be mixed to add to mix under 110-120 ℃ in high-speed mixer obtain secondary mixed material, and melt blending, extruding pelletization obtain the blend pellet under 170-195 ° of C in dual-screw pelletizer; Described extrusion moulding is that the blend pellet is obtained this bamboo-plastic composite material goods through twin screw extruder in 150-195 ℃ of extrusion moulding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310086633.4A CN103113677B (en) | 2013-03-18 | 2013-03-18 | Halogen-free flame-retardant anti-mildew composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310086633.4A CN103113677B (en) | 2013-03-18 | 2013-03-18 | Halogen-free flame-retardant anti-mildew composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103113677A true CN103113677A (en) | 2013-05-22 |
| CN103113677B CN103113677B (en) | 2015-04-22 |
Family
ID=48412102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310086633.4A Active CN103113677B (en) | 2013-03-18 | 2013-03-18 | Halogen-free flame-retardant anti-mildew composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103113677B (en) |
Cited By (37)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242589A (en) * | 2013-05-23 | 2013-08-14 | 福建晟扬管道科技有限公司 | Polyvinyl chloride-polypropylene flame-resistant composite material |
| CN103289237A (en) * | 2013-06-20 | 2013-09-11 | 中塑联新材料科技湖北有限公司 | Processing modifier for polyvinyl chloride wood-plastic composites |
| CN103304846A (en) * | 2013-06-14 | 2013-09-18 | 北京理工大学 | Ammonium polyphosphate and aluminum hydroxide nano-composite and preparation method thereof |
| CN103342833A (en) * | 2013-06-14 | 2013-10-09 | 北京理工大学 | Ammonium polyphosphate-magnesium hydroxide nanometer compound and preparation method thereof |
| CN104151853A (en) * | 2014-08-22 | 2014-11-19 | 浙江圆德新材料科技有限公司 | Preparation method for regenerated wood plastic composite material |
| CN104403236A (en) * | 2014-12-22 | 2015-03-11 | 孙宝林 | PVC-PP (polyvinyl chloride-polypropylene) foamed composite floor material |
| CN104672694A (en) * | 2014-12-09 | 2015-06-03 | 刁国锋 | Fragrant health wood-plastic plate |
| CN104804451A (en) * | 2015-04-24 | 2015-07-29 | 江苏凡新新材料科技有限公司 | Light wood-plastic compound material for outdoor use |
| CN104893148A (en) * | 2015-05-29 | 2015-09-09 | 桐城市诚信木塑科技材料有限公司 | Wear-resistant flame-retardant floor slab |
| CN105111614A (en) * | 2015-08-26 | 2015-12-02 | 安徽北马科技有限公司 | Nontoxic environment-friendly high-flame-retardancy PVC (polyvinyl chloride) wood-plastic material |
| CN105295193A (en) * | 2015-10-22 | 2016-02-03 | 安徽大学 | Polypropylene-ethylene propylene diene monomer conductive composite material and preparation method thereof |
| CN105647013A (en) * | 2016-03-09 | 2016-06-08 | 苏州莱特复合材料有限公司 | PP and PVC alloy and preparation method thereof |
| CN105838089A (en) * | 2016-05-10 | 2016-08-10 | 中南林业科技大学 | Mould proofing and flame retarding integrated pill for bamboo-plastic composite material and preparation method of pills |
| CN106479207A (en) * | 2016-11-08 | 2017-03-08 | 佛山市炬业科技有限公司 | A kind of composite for making fungus-proof antisepsis door-plate and preparation method thereof |
| CN107163449A (en) * | 2017-07-15 | 2017-09-15 | 芜湖乾凯材料科技有限公司 | High-intensity wood moulding material and preparation method thereof |
| CN107556726A (en) * | 2017-08-22 | 2018-01-09 | 安徽悦尔伟塑料机械有限公司 | Flame retardant plastics based on nano imvite and preparation method thereof |
| CN107603182A (en) * | 2017-08-30 | 2018-01-19 | 海南职业技术学院 | A kind of moisture resistance indoor hardware fitting of salt tolerant and preparation method thereof |
| CN107759908A (en) * | 2017-11-27 | 2018-03-06 | 桂林市和鑫防水装饰材料有限公司 | A kind of Halogen Free Flame Retardant EPDM |
| CN107805401A (en) * | 2017-11-03 | 2018-03-16 | 苏州梅香雅筑工艺品有限公司 | A kind of anti-mildew flame-proof composite material of fan |
| CN107915952A (en) * | 2017-10-19 | 2018-04-17 | 安徽奥兹信息科技有限公司 | High-strength V R glasses housings and preparation method thereof |
| CN108129777A (en) * | 2018-01-08 | 2018-06-08 | 安徽以诺木塑板材科技有限公司 | A kind of high-performance Wood plastic boards and preparation method thereof |
| CN108250626A (en) * | 2018-01-30 | 2018-07-06 | 杭州中能管业有限公司 | A kind of biaxial tension self-reinforcing type PVC pipe and its manufacturing method |
| CN108250787A (en) * | 2018-01-08 | 2018-07-06 | 安徽以诺木塑板材科技有限公司 | A kind of Wood-plastic material and preparation method thereof |
| CN108314816A (en) * | 2018-01-24 | 2018-07-24 | 合肥尚涵装饰工程有限公司 | A kind of stadium fire-retardant matting materials of anti-skidding anti-pollution and preparation method thereof |
| CN108610651A (en) * | 2018-04-04 | 2018-10-02 | 东北林业大学 | A kind of bar denier wood/polyolefin flame-retardant composite material and preparation method |
| CN109385110A (en) * | 2018-10-08 | 2019-02-26 | 安徽大学 | Anti-mildew halogen-free flame-retardant bamboo-plastic composite material and preparation method thereof |
| CN109880232A (en) * | 2019-03-01 | 2019-06-14 | 苏州华盖信息科技有限公司 | A kind of function additive compounds cooperative flame retardant polypropylene material with nano-oxide |
| CN110003677A (en) * | 2019-04-24 | 2019-07-12 | 安徽大学 | A kind of halogen-free polypropylene flame redardant wood plastic composite and preparation method thereof |
| CN110317466A (en) * | 2019-08-07 | 2019-10-11 | 福建六正新材料科技有限公司 | Fire-retardant mould proof bamboo-plastic plate of one kind and preparation method thereof |
| CN110938259A (en) * | 2019-11-29 | 2020-03-31 | 安徽霖园外新材料有限公司 | Mildew-proof flame-retardant bamboo-plastic composite material and preparation method thereof |
| CN111070824A (en) * | 2019-12-02 | 2020-04-28 | 广州康森新材料科技有限公司 | Halogen-free flame-retardant wood-plastic co-extrusion composite material and preparation method thereof |
| CN111561120A (en) * | 2020-06-02 | 2020-08-21 | 浙江云木新材股份有限公司 | Environment-friendly flame-retardant integrated wall surface and preparation process thereof |
| CN112063192A (en) * | 2020-09-02 | 2020-12-11 | 阜南县德盛隆工艺家具有限公司 | Bamboo composite board preparation technology |
| CN114797513A (en) * | 2022-04-11 | 2022-07-29 | 云南磷化集团有限公司 | Preparation method of label protective film for laboratory reagent bottle |
| CN114874637A (en) * | 2022-06-07 | 2022-08-09 | 临沂大学 | Environment-friendly degradable modified polyvinyl chloride composite material and preparation method and application thereof |
| CN115160694A (en) * | 2022-07-27 | 2022-10-11 | 长虹美菱股份有限公司 | Water pan material for refrigerator and preparation method thereof |
| CN115782330A (en) * | 2022-10-25 | 2023-03-14 | 安徽森泰木塑集团股份有限公司 | Wood-plastic co-extrusion floor and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698749A (en) * | 2009-11-03 | 2010-04-28 | 北京林业大学 | Wood-plastic composite material and prepration method thereof |
| CN102617915A (en) * | 2012-04-01 | 2012-08-01 | 安徽国风木塑科技有限公司 | Anti-mildew halogen-free flame-retardant smoke-suppression wood-plastic composite material and preparation method thereof |
-
2013
- 2013-03-18 CN CN201310086633.4A patent/CN103113677B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698749A (en) * | 2009-11-03 | 2010-04-28 | 北京林业大学 | Wood-plastic composite material and prepration method thereof |
| CN102617915A (en) * | 2012-04-01 | 2012-08-01 | 安徽国风木塑科技有限公司 | Anti-mildew halogen-free flame-retardant smoke-suppression wood-plastic composite material and preparation method thereof |
Cited By (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242589A (en) * | 2013-05-23 | 2013-08-14 | 福建晟扬管道科技有限公司 | Polyvinyl chloride-polypropylene flame-resistant composite material |
| CN103342833B (en) * | 2013-06-14 | 2016-03-02 | 北京理工大学 | A kind of ammonium polyphosphate and hydroxide nanoparticle mixture and preparation method thereof |
| CN103304846A (en) * | 2013-06-14 | 2013-09-18 | 北京理工大学 | Ammonium polyphosphate and aluminum hydroxide nano-composite and preparation method thereof |
| CN103342833A (en) * | 2013-06-14 | 2013-10-09 | 北京理工大学 | Ammonium polyphosphate-magnesium hydroxide nanometer compound and preparation method thereof |
| CN103289237A (en) * | 2013-06-20 | 2013-09-11 | 中塑联新材料科技湖北有限公司 | Processing modifier for polyvinyl chloride wood-plastic composites |
| CN104151853A (en) * | 2014-08-22 | 2014-11-19 | 浙江圆德新材料科技有限公司 | Preparation method for regenerated wood plastic composite material |
| CN104151853B (en) * | 2014-08-22 | 2016-06-08 | 浙江圆德新材料科技有限公司 | A kind of preparation method of Recycled Wood-Plastic Composite |
| CN104672694A (en) * | 2014-12-09 | 2015-06-03 | 刁国锋 | Fragrant health wood-plastic plate |
| CN104403236A (en) * | 2014-12-22 | 2015-03-11 | 孙宝林 | PVC-PP (polyvinyl chloride-polypropylene) foamed composite floor material |
| CN104804451A (en) * | 2015-04-24 | 2015-07-29 | 江苏凡新新材料科技有限公司 | Light wood-plastic compound material for outdoor use |
| CN104804451B (en) * | 2015-04-24 | 2017-04-12 | 江苏凡新新材料科技有限公司 | Light wood-plastic compound material for outdoor use |
| CN104893148A (en) * | 2015-05-29 | 2015-09-09 | 桐城市诚信木塑科技材料有限公司 | Wear-resistant flame-retardant floor slab |
| CN105111614A (en) * | 2015-08-26 | 2015-12-02 | 安徽北马科技有限公司 | Nontoxic environment-friendly high-flame-retardancy PVC (polyvinyl chloride) wood-plastic material |
| CN105295193A (en) * | 2015-10-22 | 2016-02-03 | 安徽大学 | Polypropylene-ethylene propylene diene monomer conductive composite material and preparation method thereof |
| CN105647013A (en) * | 2016-03-09 | 2016-06-08 | 苏州莱特复合材料有限公司 | PP and PVC alloy and preparation method thereof |
| CN105838089B (en) * | 2016-05-10 | 2018-04-06 | 中南林业科技大学 | A kind of bamboo-plastic composite material mildew-proof flame retarded integrated pill and preparation method thereof |
| CN105838089A (en) * | 2016-05-10 | 2016-08-10 | 中南林业科技大学 | Mould proofing and flame retarding integrated pill for bamboo-plastic composite material and preparation method of pills |
| CN106479207A (en) * | 2016-11-08 | 2017-03-08 | 佛山市炬业科技有限公司 | A kind of composite for making fungus-proof antisepsis door-plate and preparation method thereof |
| CN107163449A (en) * | 2017-07-15 | 2017-09-15 | 芜湖乾凯材料科技有限公司 | High-intensity wood moulding material and preparation method thereof |
| CN107556726A (en) * | 2017-08-22 | 2018-01-09 | 安徽悦尔伟塑料机械有限公司 | Flame retardant plastics based on nano imvite and preparation method thereof |
| CN107603182A (en) * | 2017-08-30 | 2018-01-19 | 海南职业技术学院 | A kind of moisture resistance indoor hardware fitting of salt tolerant and preparation method thereof |
| CN107603182B (en) * | 2017-08-30 | 2019-12-03 | 海南职业技术学院 | A kind of moisture resistance indoor hardware fitting of salt tolerant and preparation method thereof |
| CN107915952A (en) * | 2017-10-19 | 2018-04-17 | 安徽奥兹信息科技有限公司 | High-strength V R glasses housings and preparation method thereof |
| CN107805401A (en) * | 2017-11-03 | 2018-03-16 | 苏州梅香雅筑工艺品有限公司 | A kind of anti-mildew flame-proof composite material of fan |
| CN107759908A (en) * | 2017-11-27 | 2018-03-06 | 桂林市和鑫防水装饰材料有限公司 | A kind of Halogen Free Flame Retardant EPDM |
| CN108129777A (en) * | 2018-01-08 | 2018-06-08 | 安徽以诺木塑板材科技有限公司 | A kind of high-performance Wood plastic boards and preparation method thereof |
| CN108250787A (en) * | 2018-01-08 | 2018-07-06 | 安徽以诺木塑板材科技有限公司 | A kind of Wood-plastic material and preparation method thereof |
| CN108314816A (en) * | 2018-01-24 | 2018-07-24 | 合肥尚涵装饰工程有限公司 | A kind of stadium fire-retardant matting materials of anti-skidding anti-pollution and preparation method thereof |
| CN108250626A (en) * | 2018-01-30 | 2018-07-06 | 杭州中能管业有限公司 | A kind of biaxial tension self-reinforcing type PVC pipe and its manufacturing method |
| CN108250626B (en) * | 2018-01-30 | 2020-04-10 | 杭州中能管业有限公司 | Biaxial stretching self-reinforced PVC (polyvinyl chloride) pipe and manufacturing method thereof |
| CN108610651B (en) * | 2018-04-04 | 2020-05-12 | 东北林业大学 | Badam/polyolefin flame-retardant composite material and preparation method thereof |
| CN108610651A (en) * | 2018-04-04 | 2018-10-02 | 东北林业大学 | A kind of bar denier wood/polyolefin flame-retardant composite material and preparation method |
| CN109385110A (en) * | 2018-10-08 | 2019-02-26 | 安徽大学 | Anti-mildew halogen-free flame-retardant bamboo-plastic composite material and preparation method thereof |
| CN109880232A (en) * | 2019-03-01 | 2019-06-14 | 苏州华盖信息科技有限公司 | A kind of function additive compounds cooperative flame retardant polypropylene material with nano-oxide |
| CN110003677A (en) * | 2019-04-24 | 2019-07-12 | 安徽大学 | A kind of halogen-free polypropylene flame redardant wood plastic composite and preparation method thereof |
| CN110317466A (en) * | 2019-08-07 | 2019-10-11 | 福建六正新材料科技有限公司 | Fire-retardant mould proof bamboo-plastic plate of one kind and preparation method thereof |
| CN110938259A (en) * | 2019-11-29 | 2020-03-31 | 安徽霖园外新材料有限公司 | Mildew-proof flame-retardant bamboo-plastic composite material and preparation method thereof |
| CN111070824A (en) * | 2019-12-02 | 2020-04-28 | 广州康森新材料科技有限公司 | Halogen-free flame-retardant wood-plastic co-extrusion composite material and preparation method thereof |
| CN111561120A (en) * | 2020-06-02 | 2020-08-21 | 浙江云木新材股份有限公司 | Environment-friendly flame-retardant integrated wall surface and preparation process thereof |
| CN112063192A (en) * | 2020-09-02 | 2020-12-11 | 阜南县德盛隆工艺家具有限公司 | Bamboo composite board preparation technology |
| CN114797513A (en) * | 2022-04-11 | 2022-07-29 | 云南磷化集团有限公司 | Preparation method of label protective film for laboratory reagent bottle |
| CN114874637A (en) * | 2022-06-07 | 2022-08-09 | 临沂大学 | Environment-friendly degradable modified polyvinyl chloride composite material and preparation method and application thereof |
| CN114874637B (en) * | 2022-06-07 | 2023-01-13 | 临沂大学 | Environment-friendly degradable modified polyvinyl chloride composite material and preparation method and application thereof |
| CN115160694A (en) * | 2022-07-27 | 2022-10-11 | 长虹美菱股份有限公司 | Water pan material for refrigerator and preparation method thereof |
| CN115160694B (en) * | 2022-07-27 | 2024-02-02 | 长虹美菱股份有限公司 | Water pan material for refrigerator and preparation method thereof |
| CN115782330A (en) * | 2022-10-25 | 2023-03-14 | 安徽森泰木塑集团股份有限公司 | Wood-plastic co-extrusion floor and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103113677B (en) | 2015-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103113677B (en) | Halogen-free flame-retardant anti-mildew composite and preparation method thereof | |
| CN102617915B (en) | Anti-mildew halogen-free flame-retardant smoke-suppression wood-plastic composite material and preparation method thereof | |
| CN101143952B (en) | Flame-proof smoke-inhibiting wood-plastic composite material | |
| CN104327530B (en) | Preparation method of flame-retardant and antistatic wood-plastic composite material | |
| CN102181166B (en) | High-efficiency flame retardant wood plastics composite and preparation method thereof | |
| CN101831112B (en) | Halogen-free flame-retardant type injection molding-class polyolefin wood plastic composite material and preparation method thereof | |
| CN110041612B (en) | Halogen-free flame-retardant polypropylene composite material compatibilized by oligomeric silsesquioxane and synergistic effect and preparation method thereof | |
| CN103554626B (en) | A kind of fretting map polyethylene based wood-plastic composite material and preparation method thereof | |
| CN100341813C (en) | Non-halogen flame-resistant sandwich materials with polyethylene for fire-proof aluminium plastic plate and production thereof | |
| CN111138716B (en) | Flame retardant and wood-plastic composite material | |
| CN102702766B (en) | Microcapsulated red phosphorus flame-retardant wood/plastic composite material and preparation method thereof | |
| CN103113685B (en) | A kind of light flame-retardant wood plastic composite and preparation method and purposes | |
| CN103172918A (en) | Low-smoke halogen-free flame-retardant cable material and preparation method thereof | |
| CN103194075A (en) | Inorganic nanometer fire-retardant wood-plastic composite material and preparation method thereof | |
| CN111070824A (en) | Halogen-free flame-retardant wood-plastic co-extrusion composite material and preparation method thereof | |
| CN107936410A (en) | A kind of halogen-free flame-retardant wood-plastic composite material and preparation method thereof | |
| CN108659263A (en) | A kind of modified calcium carbonate and its application in PVC wood plastic clad plate | |
| CN105566811A (en) | Composite halogen-free flame-retardant smoke suppression agent of PVC wood-plastic composite material and preparation method and application of agent | |
| CN104448574A (en) | Environment-friendly weather-resistant flame-retardant PP material and preparation method thereof | |
| CN101161719B (en) | Special material for injection grade non-halogen flame-retardant wire plug and preparation method thereof | |
| CN105315690A (en) | Microcellular foaming flame-retardant wood-plastic composite and preparation method thereof | |
| CN103509263A (en) | Environment-friendly adding type polyethylene flame-retardant masterbatch and preparation method thereof | |
| CN116376154B (en) | Halogen-free flame-retardant PP hard floor and preparation method thereof | |
| CN109385110A (en) | Anti-mildew halogen-free flame-retardant bamboo-plastic composite material and preparation method thereof | |
| CN104073011A (en) | Antiflaming wood plastic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |