CN105315690A - Microcellular foaming flame-retardant wood-plastic composite and preparation method thereof - Google Patents
Microcellular foaming flame-retardant wood-plastic composite and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a microcellular foaming flame-retardant wood-plastic composite and a preparation method thereof and belongs to the technical field of preparation of composites. The microcellular foaming flame-retardant wood-plastic composite consists of 40-250 parts of plant fibers, 80-120 parts of polyolefin plastic, 26-100 parts of a flame retardant, 1-10 parts of a compatilizer and 1-5 parts of a lubricant. The preparation method comprises the following steps: placing weighed plant fibers/modified plant fibers, a flame retardant and a compatilizer into a high-speed mixer for hot-blending; when the temperature is reduced to be below the ordinary temperature, throwing weighed plastic and a lubricant into the high-speed mixer to be re-mixed so as to obtain a mixed material; throwing the well mixed materials into a double-screw extruder for melt extrusion and granulation, and performing injection molding to obtain the microcellular foaming flame-retardant wood-plastic composite. The microcellular foaming flame-retardant wood-plastic composite prepared by the method has a microcellular foaming during combustion, and is low in hot release rate, small in smoke production and environmentally friendly; the microcellular foaming flame-retardant wood-plastic composite is endowed with efficient flame retardancy, maintains favorable mechanical property and is wide in application.
Description
Technical field
The present invention relates to a kind of matrix material and preparation method, be specifically related to a kind of expansion type flame-retarding wood plastic composite and the preparation method with microporous foam effect, belong to technical field of composite preparation.
Background technology
Wood plastic composite is as timber, sisal hemp, bagasse, rice chaff, bamboo powder etc. join in thermoplastics using the form such as powdery, threadiness as weighting material, through the class advanced composite material that melt-processed compound obtains by vegetable fibre.Compared with traditional wood materials, it has attractive in appearance, water-fast, Anti-moth-eating, the advantage such as corrosion-resistant, not easy to crack, is widely used in making timber substitute products, as various packing material, pallet, warehouse pallet etc., or make outdoor building materials, and as: fence, flower garden handrail, wall dunnage, grape trellis etc.; Also for communal facility, as: park tables and chairs, floor, refuse container etc.In addition, wood plastic composite great majority adopt Resource recovery to be prepared from, and is conducive to economizing on resources and environment protection.
Require low to fire resistance when wood plastic composite uses as wrapped product, outdoor building materials or communal facility, even not requirement, less to the research of the fire retardant performance of wood plastic composite at present.But in recent years; along with the quick growth of economy and living standards of the people improve constantly; add that urban population sharply expands, buildings large-scale, story height stratification, equipment be complicated, the development trend of stored goods densification; building fire frequently occurs; cause serious loss of life and personal injury and property damage, cause heavy loss to society and individual.
In recent years, adopting expansion type flame retardant to give the good flame retardant properties of wood plastic composite is the flame-retardant modified development trend of wood plastic composite.Expansion type flame retardant (IFR), the earliest among frie retardant coating, is a kind of eco-friendly fire retardant, has Halogen, low cigarette, low toxicity, the advantages such as non-corrosiveness, receive the extensive concern of people.Expansion type flame retardant mainly plays fire retardation by cohesion fire retardant mechanism, it under high temperature action, can formed very thick foamed char by fire retardant material surface, the circulation of isolated heat and oxygen, early stage by fire end in burning, thus obtain good flame retardant effect.
But because wood plastic composite wood powder content is higher, expansion type flame retardant is difficult to effectively form microporous foam structure, reduce the flame retardant effect of wood plastic composite.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, provides a kind of microporous foam flame-retardant wood-plastic composite and preparation method, has microporous foam effect, effectively can improve the flame retardant properties of wood plastic composite, and have good mechanical property.
In order to solve the problem, the technical solution adopted in the present invention is:
A kind of microporous foam flame-retardant wood-plastic composite, is made up of the component of following weight part: 40 ~ 250 parts, vegetable fibre, polyolefin plastics 80 ~ 120 parts, fire retardant 26 ~ 100 parts, compatilizer 1 ~ 10 part, lubricant 1 ~ 5 part.
Described vegetable fibre is any ratio mixing of one or more in wood powder, bagasse, rice chaff, bamboo powder, sawdust, sisal hemp; The particle of sponge is 40 ~ 200 orders.
Described vegetable fibre also can adopt the vegetable fibre of modification, its method of modifying be 5 parts of tributyl phosphates are mixed with 10% aqueous dispersions, spray in stir plant fibre surface, at putting into 60 DEG C dry, obtain tributyl phosphate modified plant fibers.
Described polyolefin plastics be in high density polyethylene(HDPE), Low Density Polyethylene one or both arbitrarily than mixture.
Described fire retardant is made up of 2.5 ~ 10 parts of red phosphorus, 10 ~ 30 parts of ammonium polyphosphates, 3.5 ~ 10.5 parts of trimeric cyanamides, 2.5 ~ 10 parts of zinc borates, 5 ~ 30 parts of inorganic hydroxides, 2.5 ~ 10 parts of iron rust.
Described inorganic hydroxide be in aluminium hydroxide, magnesium hydroxide one or both arbitrarily than mixture.
Described compatilizer by a kind of molecular weight be 40000 ~ 500000 polyolefin graft copolymer and a kind of molecular weight be 1000 ~ 5000 polyolefin-wax graft copolymer form in the ratio of 7:0 ~ 0:7.
Described polyolefine is one or both any ratio mixing in high density polyethylene(HDPE), Low Density Polyethylene; Polyolefin-wax be in polyethylene wax, EVA wax one or both arbitrarily than mixture.
The monomer that the polyolefin graft copolymer stated and polyolefin-wax graft copolymer adopt is one or more graft copolymers in maleic anhydride, glycidyl methacrylate, vinylbenzene, methyl methacrylate, butyl acrylate.
Described lubricant be in stearic acid, washing powder, tributyl phosphate one or more arbitrarily than mixture; Wherein tributyl phosphate is flame retardant type softening agent.
A preparation method for microporous foam fire-retardant polyolefin based wood plastic composite material, comprises the steps:
(1) vegetable fibre taken, fire retardant and compatilizer are put into high-speed mixer, mixed 5 minutes of heat at 100 DEG C, under treating that temperature is down to normal temperature, the plastics taken, lubricant to be put in high-speed mixer remix 10 minutes, the material that must mix;
(2) material mixed that step (1) obtains is put into barrel zone temperature is 150 ~ 200 DEG C, die temperature is 150 ~ 180 DEG C, screw speed is carry out in the twin screw extruder of 60 ~ 200r/min melt extruding granulation, then injection molding is adopted, i.e. obtained microporous foam flame-retardant wood-plastic composite.
A kind of preparation method of microporous foam fire-retardant polyolefin based wood plastic composite material, plastics and compatilizer are comprised the steps: to be pre-mixed evenly in two roller mill, add vegetable fibre subsequently successively, fire retardant, lubricant are further evenly mixing, be put in mould hot-forming, i.e. obtained microporous foam flame-retardant wood-plastic composite.
A kind of preparation method of microporous foam fire-retardant polyolefin based wood plastic composite material, it is characterized in that, plastics and compatilizer are comprised the steps: to be pre-mixed evenly on Banbury mixer, subsequently again by proportioning by further evenly mixing in Banbury mixer to itself and vegetable fibre, fire retardant, lubricant, then be put in mould hot-forming, i.e. obtained microporous foam flame-retardant wood-plastic composite.
The invention has the beneficial effects as follows:
(1) in the present invention's formula containing iron rust, not only can fire retardant, can also as smoke suppressant; The simple science of preparation method, energy-conserving and environment-protective.
(2) the microporous foam type flame-retardant wood-plastic composite material prepared by the present invention adopts Intumscent Flame Retardant System, has microporous foam effect, effectively can improve the flame retardant properties of wood plastic composite.Test shows: polyvinyl microporous foam type flame-retardant wood-plastic composite material, evenly heat rate of release is from 210kW/m
2be reduced to 107kW/m
2, extended to 66s by the time of lighting from unmodified 27s, add 39s, oxygen index is increased to 31.4 from 21.8; And the Char Residues Structure of fretting map can be formed in combustion processes, this layer of charcoal has certain mechanical strength, difficult drop-off, can stop the diffusion spreading and burn of flame well.
(3) compared with the blank wood plastic composite of non-capacity increasing modifying, the microporous foam type flame-retardant wood-plastic composite material prepared by the present invention adopts efficient compatilizer, under the condition keeping good flame retardant effect, maintain good mechanical property.The 11.9MPa of the tensile strength of the microporous foam flame-retardant wood-plastic composite of polyvinyl never modified composite material of woods and plastics is increased to 29.8MPa, the 4.3kJ/m of shock strength never modified composite material of woods and plastics
2be increased to 10.1kJ/m
2.
Embodiment
Be described in further details the present invention below by example, these examples are only used for the present invention is described, do not limit the scope of the invention.
embodiment 1
A kind of wood plastic composite of microporous foam flame retardant effect, by vegetable fibre, plastics, fire retardant, compatilizer, lubricant forms, its proportioning is as follows: 100 parts of vinyons, 100 parts of wood powders, fire retardant is by 5 parts of red phosphorus, 20 parts of ammonium polyphosphates, 7 parts of trimeric cyanamides, 5 parts of zinc borates, 20 parts of inorganic hydroxides, 5 parts of iron rust compositions, add 7 parts of polyethylene and maleic anhydride, the graft copolymer of methyl methacrylate and butyl acrylate and 2 parts of polyethylene waxs and maleic anhydride, the graft copolymer of methyl methacrylate and butyl acrylate, lubricant is by 5 parts of flame retardant type softening agent, 1 part of stearic acid and 1 part of washing powder composition,
Preparation method comprises the steps:
(1) 5 parts of tributyl phosphates are mixed with the aqueous dispersions of 10%, spray the wood powder surface in stirring, drying at putting into 60 DEG C, obtaining the wood powder of tributyl phosphate modification;
(2) plastics taken, compatilizer are put into mixing 10 minutes of 180 DEG C of mills, obtain mixing uniform polymeric matrix, then add vegetable fibre mixing 5 minutes, continue to add fire retardant and mixing 15 minutes of lubricant, obtain mixing uniform matrix material;
(3) the hot batch mixing that step (2) obtains is put into the vulcanizing press hot pressing 5 minutes of 190 DEG C, then transfer in the vulcanizing press under normal temperature and cold pressing 5 minutes, be i.e. obtained microporous foam flame-retardant wood-plastic composite.After tested, the wood plastic composite evenly heat rate of release prepared is 144kW/m
2, burning time is 51s, and oxygen index is 29.3, tensile strength 29.3MPa, shock strength 8.3kJ/m
2.
embodiment 2
A kind of wood plastic composite of microporous foam flame retardant effect, by vegetable fibre, plastics, fire retardant, compatilizer, lubricant forms, its proportioning is as follows: 100 parts of vinyons, 25 parts of rice chaff, fire retardant is by 5 parts of red phosphorus, 20 parts of ammonium polyphosphates, 7 parts of trimeric cyanamides, 5 parts of zinc borates, 20 parts of inorganic hydroxides, 5 parts of iron rust compositions, add 7 parts of polyethylene and maleic anhydride, the graft copolymer of methyl methacrylate and butyl acrylate and 2 parts of polyethylene waxs and maleic anhydride, the graft copolymer of methyl methacrylate and butyl acrylate, lubricant is by 5 parts of flame retardant type softening agent, 1 part of stearic acid and 1 part of washing powder composition,
Preparation method comprises the steps:
(1) plastics taken, compatilizer are put into 200 DEG C of Banbury mixeies mixing 5 minutes, obtain mixing uniform polymeric matrix, again by proportioning by polymeric matrix and mixing 15 minutes of vegetable fibre, continue to add fire retardant and mixing 5 minutes of lubricant, obtain mixing uniform matrix material;
(2) the hot batch mixing that step (1) obtains is put into the vulcanizing press hot pressing 10 minutes of 190 DEG C, then transfer in the vulcanizing press under normal temperature and cold pressing 3 minutes, be i.e. obtained microporous foam flame-retardant wood-plastic composite.After tested, the wood plastic composite evenly heat rate of release prepared is 152kW/m
2, burning time is 65s, and oxygen index is 27.9, tensile strength 26.8MPa, shock strength 10.0kJ/m
2.
embodiment 3
A kind of wood plastic composite of microporous foam flame retardant effect, be made up of vegetable fibre, plastics, fire retardant, compatilizer, lubricant, its proportioning is as follows: 100 parts of vinyons, 100 parts of wood powders, fire retardant is made up of 10 parts of red phosphorus, 30 parts of ammonium polyphosphates, 10.5 parts of trimeric cyanamides, 7.5 parts of zinc borates, 30 parts of inorganic hydroxides, 7.5 parts of iron rust, adds the graft copolymer of 7 parts of polyethylene and maleic anhydride, methyl methacrylate and butyl acrylate and the graft copolymer of 2 parts of polyethylene waxs and maleic anhydride, methyl methacrylate and butyl acrylate.Lubricant is made up of 5 parts of flame retardant type softening agent, 1 part of stearic acid and 1 part of washing powder;
Preparation method comprises the steps:
(1) 5 parts of tributyl phosphates are mixed with the aqueous dispersions of 10%, spray the wood powder surface in stirring, drying at putting into 60 DEG C, obtaining the wood powder of tributyl phosphate modification;
(2) plastics taken, compatilizer are put into mixing 8 minutes of 190 DEG C of mills, obtain mixing uniform polymeric matrix, then add vegetable fibre mixing 10 minutes, continue to add fire retardant mixing 10 minutes, obtain mixing uniform matrix material;
(3) the hot batch mixing that step (2) obtains is put into the vulcanizing press hot pressing 8 minutes of 190 DEG C, then transfer in the vulcanizing press under normal temperature and cold pressing 4 minutes, be i.e. obtained microporous foam flame-retardant wood-plastic composite.After tested, the wood plastic composite evenly heat rate of release prepared is 107kW/m
2, burning time is 66s, and oxygen index is 31.4, tensile strength 29.8MPa, shock strength 10.1kJ/m
2.
embodiment 4
A kind of wood plastic composite of microporous foam flame retardant effect, be made up of vegetable fibre, plastics, fire retardant, compatilizer, lubricant, its proportioning is as follows: 100 parts of polyethylene, 67 portions of bagasse, fire retardant is made up of 5 parts of red phosphorus, 20 parts of ammonium polyphosphates, 7 parts of trimeric cyanamides, 5 parts of zinc borates, 20 parts of inorganic hydroxides, 5 parts of iron rust, add the graft copolymer of 7 parts of polyethylene and maleic anhydride and the graft copolymer of 2 parts of polyethylene waxs and maleic anhydride, lubricant is made up of 5 parts of flame retardant type softening agent, 1 part of stearic acid and 1 part of washing powder;
Preparation method comprises the steps:
(1) vegetable fibre taken, fire retardant and compatilizer are put into high-speed mixer, mixed 5 minutes of heat at 100 DEG C, under treating that temperature is down to normal temperature, the plastics taken, lubricant to be put in high-speed mixer remix 10 minutes, the material that must mix;
(2) material mixed that step (1) obtains is put into barrel zone temperature is 200 DEG C, die temperature is 160 DEG C, screw speed is carry out in the twin screw extruder of 120r/min melt extruding granulation, then injection molding is adopted, i.e. obtained microporous foam flame-retardant wood-plastic composite.After tested, the wood plastic composite evenly heat rate of release prepared is 154kW/m
2, burning time is 44s, and oxygen index is 28.6, tensile strength 24.5MPa, shock strength 8.5kJ/m
2.
embodiment 5
A kind of wood plastic composite of microporous foam flame retardant effect, by vegetable fibre, plastics, fire retardant, compatilizer, lubricant forms, its proportioning is as follows: 100 parts of vinyons, 150 parts of bamboo powder, fire retardant is by 5 parts of red phosphorus, 20 parts of ammonium polyphosphates, 7 parts of trimeric cyanamides, 5 parts of zinc borates, 20 parts of inorganic hydroxides, 5 parts of iron rust compositions, add 7 parts of polyethylene and maleic anhydride, the graft copolymer of methyl methacrylate and butyl acrylate and 2 parts of polyethylene waxs and maleic anhydride, the graft copolymer of methyl methacrylate and butyl acrylate, lubricant is made up of 1 part of stearic acid and 1 part of washing powder,
Preparation method comprises the steps:
(1) plastics taken, compatilizer are put into mixing 10 minutes of 180 DEG C of mills, obtain mixing uniform polymeric matrix, then add vegetable fibre mixing 5 minutes, continue to add fire retardant and mixing 15 minutes of lubricant, obtain mixing uniform matrix material;
(2) the hot batch mixing that step (2) obtains is put into the vulcanizing press hot pressing 5 minutes of 190 DEG C, then transfer in the vulcanizing press under normal temperature and cold pressing 5 minutes, be i.e. obtained microporous foam flame-retardant wood-plastic composite.After tested, the wood plastic composite evenly heat rate of release prepared is 132kW/m
2, burning time is 63s, and oxygen index is 29.9, tensile strength 29.7MPa, shock strength 8.4kJ/m
2.
embodiment 6
Comparative example: a kind of wood plastic composite of microporous foam flame retardant effect, be made up of vegetable fibre, plastics, compatilizer, lubricant, its proportioning is as follows: 100 parts of polyethylene, 100 parts of wood powders, and lubricant is made up of 5 parts of flame retardant type softening agent, 1 part of stearic acid and 1 part of washing powder;
A preparation method for the wood plastic composite of microporous foam flame retardant effect, comprises the steps:
(1) plastics taken, compatilizer are put into mixing 10 minutes of 180 DEG C of mills, obtain mixing uniform polymeric matrix, then add vegetable fibre mixing 5 minutes, continue to add lubricant 15 minutes, obtain mixing uniform matrix material;
(2) the hot batch mixing that step (1) obtains is put into the vulcanizing press hot pressing 5 minutes of 190 DEG C, then transfer in the vulcanizing press under normal temperature and cold pressing 5 minutes, be i.e. obtained not flame-retardant modified wood plastic composite.After tested, the wood plastic composite prepared is easy to burning, and evenly heat rate of release is 220kW/m
2, burning time is 27s, and oxygen index is 21.8, tensile strength 11.9MPa, shock strength 4.3kJ/m
2.
Claims (10)
1. a microporous foam flame-retardant wood-plastic composite, is characterized in that: be made up of the component of following weight part: 40 ~ 250 parts, vegetable fibre, polyolefin plastics 80 ~ 120 parts, fire retardant 26 ~ 100 parts, compatilizer 1 ~ 10 part, lubricant 1 ~ 5 part.
2. a kind of microporous foam fire-retardant polyolefin based wood plastic composite material according to claim 1, is characterized in that: described vegetable fibre is any ratio mixing of one or more in wood powder, bagasse, rice chaff, bamboo powder, sawdust, sisal hemp; The particle of sponge is 40 ~ 200 orders; Vegetable fibre is through tributyl phosphate modification or the vegetable fibre without tributyl phosphate modification.
3. a kind of microporous foam fire-retardant polyolefin based wood plastic composite material according to claim 2, it is characterized in that: described tributyl phosphate modified plant fibers, its method of modifying be 5 parts of tributyl phosphates are mixed with 10% aqueous dispersions, spray the plant fibre surface in stirring, dry at 60 DEG C, obtain tributyl phosphate modified plant fibers.
4. a kind of microporous foam fire-retardant polyolefin based wood plastic composite material according to claim 1, is characterized in that: described polyolefin plastics be in high density polyethylene(HDPE), Low Density Polyethylene one or both arbitrarily than mixture.
5. a kind of microporous foam fire-retardant polyolefin based wood plastic composite material according to claim 1, is characterized in that: described fire retardant is made up of 2.5 ~ 10 parts of red phosphorus, 10 ~ 30 parts of ammonium polyphosphates, 3.5 ~ 10.5 parts of trimeric cyanamides, 2.5 ~ 10 parts of zinc borates, 5 ~ 30 parts of inorganic hydroxides, 2.5 ~ 10 parts of iron rust; Described inorganic hydroxide be in aluminium hydroxide, magnesium hydroxide one or both arbitrarily than mixture.
6. a kind of microporous foam fire-retardant polyolefin based wood plastic composite material according to claim 1, is characterized in that: described compatilizer by a kind of molecular weight be 40000 ~ 500000 polyolefin graft copolymer and a kind of molecular weight be 1000 ~ 5000 polyolefin-wax graft copolymer form by the mass ratio of 7:0 ~ 0:7; Described polyolefine is one or both any ratio mixing in high density polyethylene(HDPE), Low Density Polyethylene; Polyolefin-wax be in polyethylene wax, EVA wax one or both arbitrarily than mixture.
7. a kind of microporous foam fire-retardant polyolefin based wood plastic composite material according to claim 7, is characterized in that: the monomer that described polyolefin graft copolymer and polyolefin-wax graft copolymer adopt is one or more graft copolymers in maleic anhydride, glycidyl methacrylate, vinylbenzene, methyl methacrylate, butyl acrylate.
8. a kind of microporous foam fire-retardant polyolefin based wood plastic composite material according to claim 1, is characterized in that: described lubricant be in stearic acid, washing powder, tributyl phosphate one or more arbitrarily than mixture.
9. a preparation method for microporous foam fire-retardant polyolefin based wood plastic composite material, is characterized in that, comprises the steps:
(1) vegetable fibre taken, fire retardant and compatilizer are put into high-speed mixer, mixed 5 minutes of heat at 100 DEG C, under treating that temperature is down to normal temperature, the plastics taken, lubricant to be put in high-speed mixer remix 10 minutes, the material that must mix;
(2) material mixed that step (1) obtains is put into barrel zone temperature is 150 ~ 200 DEG C, die temperature is 150 ~ 180 DEG C, screw speed is carry out in the twin screw extruder of 60 ~ 200r/min melt extruding granulation, then injection molding is adopted, i.e. obtained microporous foam flame-retardant wood-plastic composite.
10. the preparation method of a microporous foam fire-retardant polyolefin based wood plastic composite material, it is characterized in that, plastics and compatilizer are comprised the steps: to be pre-mixed evenly in two roller mill or Banbury mixer, add vegetable fibre subsequently successively, fire retardant, lubricant are further evenly mixing, be put in mould hot-forming, i.e. obtained microporous foam flame-retardant wood-plastic composite.
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| CN110922642A (en) * | 2019-12-05 | 2020-03-27 | 南京旭华圣洛迪新型建材有限公司 | Indoor antibiotic wood-plastic composite wallboard of fibrilia base |
| CN112480590A (en) * | 2020-10-29 | 2021-03-12 | 芜湖亚太通用托盘包装有限公司 | High-performance wood-plastic tray and manufacturing method thereof |
| CN113527807A (en) * | 2021-07-02 | 2021-10-22 | 武汉理工大学 | Microporous plant fiber composite material and preparation method thereof |
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| CN110922642A (en) * | 2019-12-05 | 2020-03-27 | 南京旭华圣洛迪新型建材有限公司 | Indoor antibiotic wood-plastic composite wallboard of fibrilia base |
| CN112480590A (en) * | 2020-10-29 | 2021-03-12 | 芜湖亚太通用托盘包装有限公司 | High-performance wood-plastic tray and manufacturing method thereof |
| CN113527807A (en) * | 2021-07-02 | 2021-10-22 | 武汉理工大学 | Microporous plant fiber composite material and preparation method thereof |
| CN113527807B (en) * | 2021-07-02 | 2022-04-01 | 武汉理工大学 | Microporous plant fiber composite material and preparation method thereof |
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