CN106674815B - A kind of wood plastic composite and its manufacturing method of phase-change energy-storing heat preservation - Google Patents

A kind of wood plastic composite and its manufacturing method of phase-change energy-storing heat preservation Download PDF

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CN106674815B
CN106674815B CN201611233660.XA CN201611233660A CN106674815B CN 106674815 B CN106674815 B CN 106674815B CN 201611233660 A CN201611233660 A CN 201611233660A CN 106674815 B CN106674815 B CN 106674815B
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polyethylene glycol
energy storage
storage material
parts
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CN106674815A (en
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袁利萍
胡云楚
王文磊
黄自知
文瑞芝
冯斯宇
邓明向
李慧
吴袁泊
胡进波
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Central South University of Forestry and Technology
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/92Measuring, controlling or regulating
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02Materials undergoing a change of physical state when used
    • C09K5/06Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
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    • B29C2948/92704Temperature
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    • C08J2203/00Foams characterized by the expanding agent
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    • C08J2327/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08L2205/00Polymer mixtures characterised by other features
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    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/14Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16Fibres; Fibrils

Abstract

The invention discloses a kind of wood plastic composites of phase-change energy-storing heat preservation, there are resin cladding wood powder, matrix plastic and the auxiliary agent of phase-changing energy storage material including loading, it is described to load polyethylene glycol-isocyanates copolymer resins that the resin cladding wood powder for having phase-changing energy storage material includes compound wood powder, the polyethylene glycol composite phase-change energy storage material being supported on the compound wood powder and the cladding compound wood powder and the polyethylene glycol composite phase-change energy storage material.The wood plastic composite energy-storage thermal-insulating performance of the phase-change energy-storing heat preservation is good, phase-change material will not be revealed, mechanical strength is big.Another aspect of the present invention provides a kind of manufacturing method of the wood plastic composite of phase-change energy-storing heat preservation, there is the resin cladding wood powder of phase-changing energy storage material to be kneaded with PVC plastic powder and auxiliary agent by above-mentioned load, then carries out kneading extrusion, mill tabletting and cutting deburring and obtain.

Description

A kind of wood plastic composite and its manufacturing method of phase-change energy-storing heat preservation
Technical field
The present invention relates to technical field of composite materials, and in particular to a kind of wood plastic composite of phase-change energy-storing heat preservation and its Manufacturing method.
Background technique
Aircraft, steamer, the running environment of automobile are sometimes cold and sometimes hot, and range of temperature is very big.Sentry post, the field station, beacon, Wind-driven generator, bad environments, day and night temperature are big.For support personnel and the safety of equipment, need through air conditioner refrigeration or system Heat carrys out regulation and control temperature.
China's existing building area is 40,000,000,000 m2, the overwhelming majority is built for high energy consumption, and nearly 2,000,000,000 m of annual new building2, Wherein 95% or more is still high energy consumption building.With the high speed development of urban construction, the building energy consumption in China year by year significantly on It rises, has reached the 32% of whole society's energy-output ratio, in addition annual building construction material production energy consumption about 13%, building total energy consumption is Up to the 45% of national energy total flow.Mega structure energy consumption has become the great burden of national economy.Therefore, it builds Energy conservation is imperative comprehensively for industry.Comprehensive building energy conservation is conducive to fundamentally promote energy resources saving and rationally utilize, Alleviate the contradiction of China's energy resources supply and socio-economic development;Be conducive to accelerate development circular economy, realize economic society Sustainable development;Be conducive to ensure national energy security long-rangely, protection environment, improve people's quality of life.
Energy consumption form in building use is mainly reflected in energy consumption for cooling and heating energy consumption, to reach the mesh of building energy conservation , most direct approach is exactly while to extend the duration of indoor comfort degree on the basis of both reducing opening times.Base In this requirement, environmental temperature fluctuation can be offset using the energy storage characteristic of phase-changing energy storage material, improved building thermal inertia, extended Indoor comfortable temperature duration reduces building electricity consumption load, can meet the requirement of building energy conservation by this method.
Phase-change material has the ability for changing its physical state in certain temperature range.By taking solid-liquid phase change as an example, adding When heat arrives fusion temperature, the phase transformation from solid-state to liquid is just generated, during fusing, phase-change material is absorbed and stored a large amount of Latent heat;When phase-change material is cooling, the heat of storage will be dispersed into environment within the scope of certain temperature, be carried out from liquid To solid reverse transformation.In both phase transition process, stored or release energy is known as latent heat of phase change.Physical state occurs When variation, the temperature of material itself almost remains unchanged before phase transformation is completed, and a wide temperature platform is formed, although temperature is not Become, but the latent heat for absorbing or discharging is quite big.Phase change energy storage technology is not able to solve energy supply and demand over time and space not The contradiction matched is the effective means for improving energy utilization rate.Phase-changing energy storage material is applied to that environment can be reduced in building wall board Temperature change improves indoor comfort level to temperature fluctuation caused by interior, while can reduce building energy consumption and play energy conservation Effect.
Chinese invention patent 201510748000.4 discloses a kind of phase-changing energy storage material carrier and its encapsulation phase-change accumulation energy The method of material, the carrier using hollow metal material device as phase-changing energy storage material, peripheral seal are only set at top A circular hole feed inlet is set, it is only necessary to be sealed to it, packaging technology is easy, and during the metal material device is Sky, phase-change material compound quantity is high, and the thermal conductivity of metal material is good, can preferably carry out heat exchange, therefore be conducive to fill The energy-conserving action of phase-changing energy storage material is waved in distribution, obtains preferable energy-saving and temperature-regulating effect.
It is fine that Chinese invention patent 201410016578.6 discloses a kind of calcium alginate/macrogol ester dual network phase-change accumulation energy Dimension and preparation method thereof, calcium alginate/macrogol ester dual network phase-change energy-storage fibre is being handed over by sodium alginate and phase-change material It after being copolymerized under the conditions of joining existing for agent and initiator, solidifies, wherein the mass ratio of sodium alginate and phase-change material is 100: 15-100:30;The mass ratio of crosslinking agent and phase-change material is 0.5:100-2:100;The mass ratio of initiator and phase-change material is 0.1:100-0.8:100。
Chinese invention patent 201110399977.1 discloses a kind of compound polyethylene glycol phase change material, uses poly- second Glycol is as phase-changing energy storage material;Porosity absorption carrier is done with swelling perlite powder, zeolite powder, diatomite etc.;The friendship of use Joining agent is the second light industry bureau methyl the second light industry bureau base vinyl urea.
Chinese invention patent 201310548439.3 discloses a kind of phase-change accumulation energy microcapsules that organic-inorganic is compound And preparation method thereof, the water phase containing inorganic nanoparticles is handed over containing phase-change accumulation energy material, monoene hydrocarbon monomer, Polyene Hydrocarbons The oil of connection agent and initiator mixes, and is sufficiently stirred to obtain oil-in-water lotion;Then heating makes the lotion carry out lotion poly- It closes to form the phase-change accumulation energy microcapsules of core-shell structure.
Chinese invention patent 201510029074.2 discloses a kind of phase-change energy-storage temperature adjustment foam concrete and its preparation side Method, wherein phase-change energy-storage temperature adjustment foam concrete includes: the cement of 70-100 parts by weight;The flyash of 0-30 parts by weight;10- The phase transformation lightweight aggregate of 50 parts by weight;The fiber of 0-0.6 parts by weight;The water-reducing agent of 0.2-0.4 parts by weight;0.1-0.3 parts by weight Cell modifiers;The early strength agent of 0.1-0.3 parts by weight;The reinforcing agent of 0-1.5 parts by weight;The waterproofing agent of 0-3 parts by weight;2-9 weight Measure the chemical foaming agent of part;And the water of 25-40 parts by weight.Thus the phase-change energy-storage temperature adjustment foam concrete has stronger accumulation of heat Ability and temperature adjustment function.
Chinese invention patent 201510045505.4 discloses a kind of phase-change accumulation energy wall and its manufacturing method, by wall The different phase-changing energy storage material layer of phase transition temperature is arranged in the outer surface of body two sides, wherein the phase of wall outer side phase-changing energy storage material layer Temperature is higher than the phase transition temperature of phase-changing energy storage material layer on the inside of wall, in the outside of the wall as building envelope The relatively high phase-changing energy storage material layer of composite phase-change temperature prevents external heat from passing through wall by being isolated or absorbing heat Environment conveys heat into the building;The wall as building envelope inside composite phase-change temperature relatively Low phase-changing energy storage material layer maintains the stabilization of indoor environment temperature by being isolated or absorbing and releasing heat;It realizes to interior Effective regulation and control of environment temperature, it is long-term to maintain indoor environment temperature in OK range.
Chinese invention patent 201010603232.8 discloses a kind of phase change energy storage thermoplastic composite material and its preparation side Method, it is characterised in that be grouped as by group as follows count by weight percentage: polypropylene 5-30%, ethylene propylene diene rubber 10- 40%, paraffin 20-75%, crosslinking agent 0.5-10%, antioxidant 0.01-2%, auxiliary agent 0.01-10%, cross-linking aid 0-10%; The phase change energy storage thermoplastic composite material is prepared by dynamic vulcanization in the component.
Although the above research work achieves some gratifying achievements, existing plastics and wood materials heat-insulation and heat-preservation effect Fruit is undesirable, cannot build the space environment for maintaining human comfort's temperature range.Therefore, formulate a kind of energy-storage thermal-insulating performance it is good, Phase-change material will not be revealed, and the wood plastic composite using phase-change accumulation energy regulating and controlling temperature for having both preferable mechanical property is It is very necessary.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one The wood plastic composite for the phase-change energy-storing heat preservation that kind of energy-storage thermal-insulating performance is good, phase-change material will not be revealed, mechanical strength is big and its Manufacturing method.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of wood plastic composite of phase-change energy-storing heat preservation, including load have phase-changing energy storage material resin cladding wood powder, Matrix plastic and auxiliary agent, it is described load the resin cladding wood powder for having phase-changing energy storage material includes compound wood powder, be supported on it is described Polyethylene glycol composite phase-change energy storage material and the cladding compound wood powder and the polyethylene glycol compound phase on compound wood powder The polyethylene glycol of change energy-storage material-isocyanates copolymer resins.
The wood plastic composite of phase-change energy-storing heat preservation of the invention uses polyethylene glycol composite phase-change energy storage material, poly- second two The crystalline rate of alcohol is very high, and has biggish enthalpy of phase change, and non-corrosive, performance is more stable, is less prone to surfusion and phase Separation, and it is cheap, it is ideal for adjusting the polymeric phase change material of environment temperature.In addition, the present invention is using compound Wood powder absorption carriage polyethylene glycol composite phase-change energy storage material, and it is above-mentioned multiple with polyethylene glycol-isocyanates copolymer resins cladding It closes wood powder and polyethylene glycol composite phase-change energy storage material forms the resin cladding wood powder that load has phase-changing energy storage material, it is therein multiple It closes wood powder and is both the reinforced phase of wood plastic composite, while being the carrier of phase-change material again.It is independent to efficiently solve phase-change material When use the problem of liquid leakage.Furthermore the present invention is using polyethylene glycol-isocyanates copolymer resins to compound wood powder and poly- second Glycol composite phase-change energy storage material is coated, and polyethylene glycol-isocyanates copolymer resins are a kind of solid-solid phase-change heat absorption materials Material, can effectively improve the latent heat of phase change of composite material;Using polyethylene glycol-isocyanates copolymer resins covered composite yarn wood powder, Both the fluid leakage problems after polyethylene glycol melts can have been solved, can also eliminate between compound wood powder and matrix plastic incompatible asks Topic, can effectively improve the mechanical strength of the wood plastic composite.
As further improvement to above-mentioned technical proposal:
Preferably, the polyethylene glycol composite phase-change energy storage material includes following components by weight:
The enthalpy of phase change and phase transition temperature of polyethylene glycol change with the variation of the degree of polymerization, as the fusing point of PEG-400 is 5 ± 2 DEG C, the fusing point of PEG-600 is 20 ± 2 DEG C, and the fusing point of PEG-800 is 28 ± 2 DEG C, and the fusing point of PEG-1000 is 37 ± 2 DEG C, The fusing point of PEG-2000 is 51 ± 2 DEG C, and the fusing point of PEG-10000 is 61 ± 2 DEG C.The PEG of different polymerization degree is mixed in proportion, can To obtain required melting temperature and crystallization temperature.The present invention uses the Macrogol 600 and polyethylene glycol-800 of proper proportion As composite phase-change heat-absorbing material, and ferric sulfate and iron ammonium sulfate are added in polyethylene glycol composite phase-change energy storage material, The ferric sulfate and iron ammonium sulfate reaction in-situ in wood cell generate magnetic Fe3O4Nanoparticle.The magnetic Fe3O4Nanometer Particle can be with efficient absorption polyethylene glycol, and aligns polyethylene glycol, can increase substantially the phase transformation of polyethylene glycol Latent heat optimizes and revises phase transition temperature.Using phase-change energy-storing heat preservation prepared by above-mentioned polyethylene glycol composite phase-change energy storage material Environment temperature can be efficiently controlled and be adjusted within the scope of 20-30 DEG C of human comfort by wood plastic composite.
It is furthermore preferred that the compound wood powder includes following components by weight:
On the one hand the Poplar Powder of aspen fibers by using silicon and ultra-fine grain diameter that the present invention is distributed using certain length may be used as reinforced phase With the effective absorption carriage amount for making full use of the characteristic of the soft tracheid prosperity of poplar material to improve it to polyethylene glycol, while may be used also To guarantee the mechanical strength of wood plastic composite.
It is furthermore preferred that described matrix plastics are PVC plastic powder, the wood plastic composite of the phase-change energy-storing heat preservation is by weight Measuring part meter includes following components:
Wherein, the calcium zinc stabilizer, chlorinated paraffin, dioctyl phthalate, stearic acid, 2,6- di-t-butyl -4- Methylphenol antioxidant, ammonium polyphosphate flame retardant, AC-1600 foaming agent, silane coupling agent, ferric oxide red colorant and lightweight carbonic acid Calcium filler is auxiliary agent.
Filler is made using the foaming effect and precipitated calcium carbonate of AC-1600 foaming agent, the phase-change energy-storing heat preservation can be made Wood plastic composite has suitable density and weight.There is the resin packet of phase-changing energy storage material using the load of above-mentioned weight proportion The wood plastic composite for covering wood powder, PVC plastic powder and various auxiliary agents has good energy-storage thermal-insulating performance, can be by environment temperature It is efficiently controlled within the scope of 20-30 DEG C of human comfort, is provided simultaneously with good mechanical property.It is protected using above-mentioned phase-change accumulation energy The house that the wood plastic composite of temperature is built can resist room temperature in heat absorption on daytime and excessively rise, and discharge latent heat of phase change at night It is warming to go to a winter resort, the temperature range of human comfort is maintained, has the function of that cool in summer and warm in winter, cool night in daytime is warm, can be used to build comfortable Living space, for reduce energy consumption, realize low-carbon environment-friendly be of great significance.
As a general technical idea, another aspect of the present invention provides a kind of wood and plastic composite of phase-change energy-storing heat preservation The manufacturing method of material, comprising the following steps:
(1) taking polyethylene glycol 600, polyethylene glycol-800, organic silicon defoamer HT-508, six ferrous sulfate hydrate ammoniums and sulphur Sour iron carries out shearing dispersion in high speed disperser, obtains polyethylene glycol composite phase-change energy storage material;
(2) polyethylene glycol composite phase-change energy storage material obtained by step (1) is supported on compound wood powder, obtain load have it is poly- The compound wood powder of ethylene glycol composite phase-change energy storage material;
(3) load obtained by polyethylene glycol-isocyanates copolymer resins encapsulation steps (2) has the storage of polyethylene glycol composite phase-change The compound wood powder of energy material obtains the resin cladding wood powder that load has phase-changing energy storage material;
(4) load obtained by PVC plastic powder, auxiliary agent and step (3) is taken to have the resin cladding wood powder of phase-changing energy storage material, It is kneaded in high speed mixing smelting machine, obtains mixture;
(5) mixture obtained by step (4) is subjected to kneading extrusion, mill tabletting and cutting deburring successively to get phase transformation storage The wood plastic composite that can be kept the temperature.
The present invention by shearing dispersion, load and cladding and etc. obtain load have phase-changing energy storage material resin cladding wood Then powder obtains the wood plastic composite of phase-change energy-storing heat preservation by being kneaded, mediating extrusion, mill tabletting and cutting deburring, makes Make that method is simple and easy, obtained wood plastic composite energy-storage thermal-insulating effect is good, mechanical strength is big and phase-change material will not be let out Dew.
Above-mentioned manufacturing method, it is preferred that in step (1), the taking polyethylene glycol 600, polyethylene glycol-800, organosilicon Defoaming agent HT-508, six ferrous sulfate hydrate ammoniums and ferric sulfate carry out the specific steps of shearing dispersion in high speed disperser are as follows:
40-100 parts of Macrogol 600s, 40-100 parts of polyethylene glycol-800s, 0.2-0.6 parts of organosilicon defoamings are taken by weight Agent HT-508 is added sequentially in high speed disperser, the shearing dispersion 5-15min under 900-1100r/min revolving speed;Then exist Six ferrous sulfate hydrate ammonium of 0.1-0.3 part and 0.1-0.3 parts of ferric sulfate are sequentially added under 140-160r/min revolving speed, in 1800- Continue shearing dispersion 20-30min under 2200r/min revolving speed.
Above-mentioned manufacturing method, it is preferred that in step (2), the compound wood powder is prepared by the following method:
Take the poplar that aspen fibers by using silicon, 15-30 part length that 5-15 parts of length are 3-10mm are 0.5-3mm fine by weight The Poplar Powder of dimension, the Poplar Powder of 20-40 parts of 30-60 mesh and 25-50 parts of 100-325 mesh is stirred 10- in blender 30min。
Above-mentioned manufacturing method, more preferred, in step (2), polyethylene glycol composite phase-change energy storage material is supported on Specific steps on compound wood powder are as follows:
The compound wood powder is fitted into vacuum pressure immersion can, is vacuumized, makes pressure inside the tank 0.01-0.02MPa simultaneously Maintain this pressure 20-30min;
Liquid flowing valve is opened, polyethylene glycol composite phase-change energy storage material is pumped into vacuum pressure immersion can, poly- second two is made Compound wood powder is completely covered in the liquid level of alcohol composite phase-change energy storage material, then impregnates 1.0-4.0h under 0.5-1.8MPa pressure;
Draining valve is opened, polyethylene glycol composite phase-change energy storage material is transmitted back to reservoir with pressure;Open breather valve Then wood powder is taken out the dry compound wood powder for having polyethylene glycol composite phase-change energy storage material to get load by door pressure release.
Above-mentioned manufacturing method, it is preferred that in step (3), the polyethylene glycol-isocyanates copolymer resins by walking as follows Suddenly it is prepared:
Take 100 parts of acetone to be put into reaction kettle by weight, be added 100-300 parts of Macrogol 6000s, under stirring in 100-120 DEG C vacuumizes dehydration 3-4h;Then be slowly stirred under nitrogen protection, be slowly added dropwise at 55-65 DEG C 40-50 parts it is different Isophorone diisocyanate is stirred to react 1.5-2.5h;5-8 parts of 1,4-butanediol are added, and two laurel of 0.3-0.6 part is added dropwise Sour dibutyl tin, the reaction was continued 3-5h is to get polyethylene glycol-isocyanates copolymer resins;
The cladding operation is specific as follows:
In the case where high low speed mixing blender is stirred continuously, silane coupling agent is atomized with air atomization machine and sprays into step (2) Gained load has in the compound wood powder of polyethylene glycol composite phase-change energy storage material, stirs 4-6min, is then being stirred continuously process Middle polyethylene glycol-isocyanates copolymer resins that atomization is sprayed into glue sprayer stir lower cladding 12-18min.
Above-mentioned manufacturing method, it is preferred that in step (4), PVC plastic powder, auxiliary agent and load is taken to have phase-change accumulation energy The resin of material coats wood powder, the specific steps being kneaded in high speed mixing smelting machine are as follows:
Load obtained by 50 parts of steps (3) is taken to have resin the cladding wood powder, 30-60 parts of PVC of phase-changing energy storage material by weight Plastic powders, 1-5 part calcium zinc stabilizer, 4-12 parts of chlorinated paraffins, 5-15 parts of dioctyl phthalates, 1-10 parts of stearic acid, 0.1-0.5 parts of 2,6 di tert butyl 4 methyl phenol antioxidant, 5-25 parts of ammonium polyphosphate flame retardants, 0-5 parts of AC-1600 foaming Agent, 0-10 parts of silane coupling agents, 0-3 parts of ferric oxide red colorants and 0-20 parts of precipitated calcium carbonate fillers mix in high speed mixing smelting machine Refine 10-20min;
It is described to mediate extrusion, mill tabletting and the detailed process for cutting deburring in step (5) are as follows:
Add mixture into twin-screw kneading extruder, 120-130 DEG C of area's temperature, two 150-160 DEG C of area's temperature, Three 140-150 DEG C of area's temperature, four 155-165 DEG C of area's temperature, five 170-175 DEG C of area's temperature, 175-185 DEG C of machine neck die temperature, Under the conditions of screw speed 10-25r/min, mediates and squeeze out 8-12min;Then in two roll tablet open mills, in 150-180 DEG C of item Mill tabletting under part;Most deburring is cut through cutting machine afterwards.
Compared with the prior art, the advantages of the present invention are as follows:
(1) present invention utilizes polyethylene glycol-isocyanates copolymer resins covered composite yarn wood powder, not only effectively increases compound The latent heat of phase change of material, the fluid leakage problems after solving polyethylene glycol thawing, and be conducive to eliminate wood powder and PVC plastic Between inconsistent problem, effectively increase the mechanical strength of wood plastic composite.
(2) present invention using the Macrogol 600 and polyethylene glycol-800 of proper proportion as composite phase-change energy storage material, And ferric sulfate and iron ammonium sulfate are added in polyethylene glycol composite phase-change energy storage material, polyethylene glycol is greatly improved Latent heat of phase change has optimized and revised phase transition temperature.Obtained phase-change energy-storing heat preservation wood plastic composite can have environment temperature Effect control and adjusting are in 20-30 DEG C of comfort standard.
(3) the poplar material of the invention for using the soft tracheid prosperity of matter, and using the aspen fibers by using silicon of certain length distribution and surpass The Poplar Powder of fine grain is as the substrate of absorption carriage polyethylene glycol composite phase-change energy storage material and the enhancing of wood plastic composite Phase not only increases substrate to effective absorption carriage amount of polyethylene glycol, and ensure that the mechanical strength of wood plastic composite.
(4) present invention uses AC-1600 foaming agent and precipitated calcium carbonate filler, so that the wood moulding of the phase-change energy-storing heat preservation is multiple Condensation material has suitable density and weight.There is the resin cladding wood of phase-changing energy storage material using the load of appropriate weight proportion Powder, PVC plastic powder and various auxiliary agents are provided simultaneously with good so that wood plastic composite has good energy-storage thermal-insulating performance Mechanical property.
Specific embodiment
To facilitate the understanding of the present invention, present invention work more comprehensively, is meticulously described below in conjunction with preferred embodiment, But the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of wood plastic composite of phase-change energy-storing heat preservation of the present embodiment, the composite material are to utilize wood powder and wood-fibred Absorption carriage polyethylene glycol composite phase-change energy storage material, and after polyethylene glycol-isocyanates copolymer resins cladding, it is moulded with matrix Material and auxiliary agent are kneaded, and are then mediated extrusion, mill tabletting and cutting deburring and are prepared.The wood moulding of the phase-change energy-storing heat preservation is multiple The specific manufacturing method of condensation material the following steps are included:
(1) 100kg Macrogol 600,100kg polyethylene glycol-800,0.5kg organic silicon defoamer HT-508 are successively added Enter in high speed disperser, high speed shear disperses 10min under 1000r/min revolving speed;Then successively add under 150r/min revolving speed Enter 0.2kg iron ammonium sulfate and 0.2kg ferric sulfate, continues the shearing dispersion 25min under 1000r/min revolving speed.
(2) by compound wood powder, (aspen fibers by using silicon for being 3-10mm by 10kg length, the poplar that 20kg length is 0.5-3mm are fine Dimension, 30kg fineness be 30-60 mesh Poplar Powder and 40kg fineness be 100-325 mesh Poplar Powder, stirred in blender mixed 20min is closed to form) it is fitted into high pressure vacuum pressure immersion can, it opens vacuum pump and vacuumizes, pressure inside the tank is 0.02MPa maintenance 25min;It opens the polyethylene glycol composite phase-change energy storage material that liquid flowing valve prepares step (1) to be pumped into immersion can, makes poly- second Compound wood powder is completely covered in the liquid level of glycol composite phase-change energy storage material solution, adds 1.0MPa pressure impregnation 1.5h;Open drain Polyethylene glycol composite phase-change energy storage material is transmitted back to reservoir (giving over to next use after adjustment proportion) with pressure by valve;It opens Then wood powder is taken out drying by the complete pressure release of unblank air valve, obtaining absorption carriage has polyethylene glycol composite phase-change energy storage material Compound wood powder.
(3) in the case where high low speed mixing blender is stirred continuously, 8kg silane coupling agent is atomized with air atomization machine and is sprayed into Load obtained by 100kg step (2) has in the compound wood powder of polyethylene glycol composite phase-change energy storage material, 5min is stirred, then not 16kg polyethylene glycol-isocyanates copolymer resins (polyethylene glycol-isocyanates of atomization is sprayed into disconnected whipping process with glue sprayer The preparation method of copolymer resins is: in a kettle, 10kg acetone is added, adds 25kg Macrogol 6000, is constantly stirring It mixes down and vacuumizes dehydration 3h in 110 DEG C;It is slowly stirred under nitrogen protection, the different Fo Er of 4.5kg is slowly added dropwise at a temperature of 60 DEG C Ketone diisocyanate, is stirred to react 2h;0.6kg 1,4-butanediol is added, and it is dibutyltindilaurate catalyzed that 0.04kg is added dropwise Agent, the reaction was continued 4h), continue to stir lower cladding 15min, obtains the resin cladding wood powder that load has phase-changing energy storage material.
(4) resin of phase-changing energy storage material coats wood powder, 60kg PVC plastic feed powder load prepared by 50kg step (3) End, 4kg AC-1600 foaming agent, 5kg calcium zinc stabilizer, 10kg chlorinated paraffin, 10kg dioctyl phthalate, 8kg are stearic Acid, 6kg silane coupling agent, 0.2kg2,6- di-tert-butyl-4-methy phenol antioxidant, 20kg ammonium polyphosphate flame retardant, 1kg oxygen Change in iron oxide red pigment and 20kg precipitated calcium carbonate filler input high speed mixing smelting machine and be kneaded 20min, obtains mixture.
(5) by step (4) be kneaded obtain mixture in twin-screw kneading extruder, 120-130 DEG C of area's temperature, Two 150-160 DEG C of area's temperature, three 140-150 DEG C of area's temperature, four 155-165 DEG C of area's temperature, five 170-175 DEG C of area's temperature, machine neck Under the conditions of 175-185 DEG C of die temperature, screw speed 20r/min, mediates and squeeze out 8min;Then in two roll tablet open mills, Mill tabletting under the conditions of 160 DEG C;Most cut deburring through cutting machine afterwards, obtain the wood plastic composite of phase-change energy-storing heat preservation at Product.
Thermal insulation property and mechanical property to the wood plastic composite of the phase-change energy-storing heat preservation etc. are tested.Wherein, it protects The test method of 18 DEG C of temperature are as follows:, will be wooden using 400mm × 400mm × 400mm square wooden case is made into a thickness of the plate of 20mm Case is placed in 30 DEG C of oven heats to wooden the temperature inside the box and reaches 30 DEG C, then with the temperature of the cooling rate control insulating box of 3 DEG C/h Degree measures the time required for wooden the temperature inside the box is reduced to 18 DEG C as 30 DEG C;The test method of 30 DEG C of heat preservation are as follows: be placed in wooden case 20 DEG C of insulating boxs make wooden the temperature inside the box reach 20 DEG C, then with the temperature of the heating rate control insulating box of 3 DEG C/h, measure wooden case Time required for interior temperature rises to 30 DEG C as 20 DEG C.Specific test result is shown in Table 1.
Embodiment 2:
A kind of wood plastic composite of phase-change energy-storing heat preservation of the present embodiment, the composite material are to utilize wood powder and wood-fibred Absorption carriage polyethylene glycol composite phase-change energy storage material, and after polyethylene glycol-isocyanates copolymer resins cladding, it is moulded with matrix Material and auxiliary agent are kneaded, and are then mediated extrusion, mill tabletting and cutting deburring and are prepared.The wood moulding of the phase-change energy-storing heat preservation is multiple The specific manufacturing method of condensation material the following steps are included:
(1) 110kg Macrogol 600,90kg polyethylene glycol-800,0.5kg organic silicon defoamer HT-508 are sequentially added In high speed disperser, high speed shear disperses 10min under 1000r/min revolving speed;Then it is sequentially added under 150r/min revolving speed 0.2kg iron ammonium sulfate and 0.2kg ferric sulfate continue the shearing dispersion 25min under 1000r/min revolving speed.
(2) by compound wood powder, (aspen fibers by using silicon for being 3-10mm by 10kg length, the poplar that 20kg length is 0.5-3mm are fine Dimension, 20kg fineness be 30-60 mesh Poplar Powder and 50kg fineness be 100-325 mesh Poplar Powder, stirred in blender mixed 20min is closed to form) it is fitted into high pressure vacuum pressure immersion can, it opens vacuum pump and vacuumizes, pressure inside the tank is 0.02MPa maintenance 25min;It opens the polyethylene glycol composite phase-change energy storage material that liquid flowing valve prepares step (1) to be pumped into immersion can, makes poly- second Compound wood powder is completely covered in the liquid level of glycol composite phase-change energy storage material solution, adds 1.0MPa pressure impregnation 1.5h;Open drain Polyethylene glycol composite phase-change energy storage material is transmitted back to reservoir (giving over to next use after adjustment proportion) with pressure by valve;It opens Then wood powder is taken out drying by the complete pressure release of unblank air valve, obtain absorption carriage polyethylene glycol composite phase-change energy storage material Compound wood powder.
(3) in the case where high low speed mixing blender is stirred continuously, 8kg silane coupling agent is atomized with air atomization machine and is sprayed into The load of 100kg step (2) preparation has in the compound wood powder of polyethylene glycol composite phase-change energy storage material, stirs 5min, then exists 16kg polyethylene glycol-isocyanates copolymer resins (polyethylene glycol-isocyanic acid of atomization is sprayed into during being stirred continuously with glue sprayer The preparation method of ester copolymer resins is: in a kettle, 10kg acetone is added, 25kg Macrogol 6000 is added, continuous Dehydration 3h is vacuumized under stirring in 110 DEG C;It is slowly stirred under nitrogen protection, the different Buddhist of 4.5kg is slowly added dropwise at a temperature of 60 DEG C That ketone diisocyanate, is stirred to react 2h;0.6kg 1,4-butanediol is added, and 0.04kg dibutyl tin dilaurate is added dropwise and urges Agent, the reaction was continued 4h), continue to stir lower cladding 15min, obtains the resin cladding wood powder that load has phase-changing energy storage material.
(4) resin of phase-changing energy storage material coats wood powder, 60kg PVC plastic feed powder load prepared by 50kg step (3) End, 4kg AC-1600 foaming agent, 5kg calcium zinc stabilizer, 10kg chlorinated paraffin, 10kg dioctyl phthalate, 8kg are stearic Acid, 6kg silane coupling agent, 0.2kg2,6- di-tert-butyl-4-methy phenol antioxidant, 20kg ammonium polyphosphate flame retardant, 1kg oxygen Change in iron oxide red pigment and 20kg precipitated calcium carbonate filler input high speed mixing smelting machine and be kneaded 20min, obtains mixture.
(5) by step (4) be kneaded obtain mixture in twin-screw kneading extruder, 120-130 DEG C of area's temperature, Two 150-160 DEG C of area's temperature, three 140-150 DEG C of area's temperature, four 155-165 DEG C of area's temperature, five 170-175 DEG C of area's temperature, machine neck Under the conditions of 175-185 DEG C of die temperature, screw speed 20r/min, mediates and squeeze out 8min;Then in two roll tablet open mills, Mill tabletting under the conditions of 160 DEG C;Most cut deburring through cutting machine afterwards, obtain the wood plastic composite of phase-change energy-storing heat preservation at Product.
The thermal insulation property and mechanical property of the wood plastic composite of the phase-change energy-storing heat preservation are tested.Test method with Embodiment 1 is identical.Specific test result is shown in Table 1.
Comparative example 1:
This comparative example is a kind of fretting map flame-proof PVC wood plastic composite without adding phase-change energy-storing thermal insulation material, should The manufacturing method of fretting map flame-proof PVC wood plastic composite the following steps are included:
(1) aspen fibers by using silicon for being 3-10mm by 10kg length, 20kg length are the aspen fibers by using silicon of 0.5-3mm, 20kg fineness For the Poplar Powder of 30-60 mesh, 50kg fineness is the Poplar Powder of 100-325 mesh, is stirred 20min in blender and forms, obtains Obtain compound wood powder.
(2) by the compound wood powder of 50kg step (1) preparation, 60kg PVC plastic powder, 4kg AC-1600 foaming agent, 5kg Calcium zinc stabilizer, 10kg chlorinated paraffin, 10kg dioctyl phthalate DOP, 8kg stearic acid, 6kg silane coupling agent, 0.2kg2,6- di-tert-butyl-4-methy phenol antioxidant, 20kg ammonium polyphosphate flame retardant, 1kg ferric oxide red colorant and 20kg are light It is kneaded 20min in matter pearl filler input high speed mixing smelting machine, obtains mixture.
(3) by step (2) be kneaded obtain mixture in twin-screw kneading extruder, 120-130 DEG C of area's temperature, Two 150-160 DEG C of area's temperature, three 140-150 DEG C of area's temperature, four 155-165 DEG C of area's temperature, five 170-175 DEG C of area's temperature, machine neck Under the conditions of 175-185 DEG C of die temperature, screw speed 20r/min, mediates and squeeze out 8min;Then in two roll tablet open mills, Mill tabletting under the conditions of 160 DEG C;Deburring most is cut through cutting machine afterwards, obtains fretting map flame-proof PVC wood plastic composite finished product.
The thermal insulation property and mechanical property of the fretting map flame-proof PVC wood plastic composite are tested.Test method with Embodiment 1 is identical.Specific test result is shown in Table 1.
The performance parameter of 1 wood plastic composite of table compares
Seen from table 1, the wood plastic composite of the phase-change energy-storing heat preservation of embodiment 1 and embodiment 2 is compared in comparative example 1 Fretting map flame-proof PVC wood plastic composite specific heat capacity significantly increase, the enthalpy of phase change of unit mass increases, lower than 18 DEG C or high Increase in 30 DEG C of lag times, therefore, the comfort level of living space increases;Simultaneously as using polyethylene glycol-isocyanates Copolymer resins cladding load has the compound wood powder of polyethylene glycol composite phase-change energy storage material, the wood of prepared phase-change energy-storing heat preservation The mechanical strength of plastic composite materials is also increased compared to the fretting map flame-proof PVC wood plastic composite in comparative example 1.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of wood plastic composite of phase-change energy-storing heat preservation, which is characterized in that there is the resin of phase-changing energy storage material including loading Wood powder, matrix plastic and auxiliary agent are coated, described load has the resin cladding wood powder of phase-changing energy storage material to include compound wood powder, bear The polyethylene glycol composite phase-change energy storage material and the cladding compound wood powder that are loaded on the compound wood powder and the poly- second two The polyethylene glycol of alcohol composite phase-change energy storage material-isocyanates copolymer resins;The polyethylene glycol composite phase-change energy storage material is pressed Parts by weight meter includes following components:
2. the wood plastic composite of phase-change energy-storing heat preservation according to claim 1, which is characterized in that the compound wood powder is pressed Parts by weight meter includes following components:
3. the wood plastic composite of phase-change energy-storing heat preservation according to claim 2, which is characterized in that described matrix plastics are The wood plastic composite of PVC plastic powder, the phase-change energy-storing heat preservation includes following components by weight:
Wherein, the calcium zinc stabilizer, chlorinated paraffin, dioctyl phthalate, stearic acid, 2,6- di-t-butyl -4- methyl Phenolic antioxidants, ammonium polyphosphate flame retardant, AC-1600 foaming agent, silane coupling agent, ferric oxide red colorant and precipitated calcium carbonate are filled out Material is auxiliary agent.
4. a kind of manufacturing method of the wood plastic composite of phase-change energy-storing heat preservation as claimed in claim 3, comprising the following steps:
(1) taking polyethylene glycol 600, polyethylene glycol-800, organic silicon defoamer HT-508, six ferrous sulfate hydrate ammoniums and ferric sulfate Shearing dispersion is carried out in high speed disperser, obtains polyethylene glycol composite phase-change energy storage material;
(2) polyethylene glycol composite phase-change energy storage material obtained by step (1) is supported on compound wood powder, obtaining load has poly- second two The compound wood powder of alcohol composite phase-change energy storage material;
(3) load obtained by polyethylene glycol-isocyanates copolymer resins encapsulation steps (2) has polyethylene glycol composite phase change energy-storing material The compound wood powder of material obtains the resin cladding wood powder that load has phase-changing energy storage material;
(4) load obtained by PVC plastic powder, auxiliary agent and step (3) is taken to have the resin cladding wood powder of phase-changing energy storage material, in height It is kneaded in fast kneading machine, obtains mixture;
(5) mixture obtained by step (4) is subjected to kneading extrusion, mill tabletting and cutting deburring successively to get phase-change accumulation energy guarantor The wood plastic composite of temperature.
5. manufacturing method according to claim 4, which is characterized in that in step (1), the taking polyethylene glycol 600, poly- second Glycol 800, organic silicon defoamer HT-508, six ferrous sulfate hydrate ammoniums and ferric sulfate carry out shearing dispersion in high speed disperser Specific steps are as follows:
40-100 parts of Macrogol 600s, 40-100 parts of polyethylene glycol-800s, 0.2-0.6 parts of organic silicon defoamers are taken by weight HT-508 is added sequentially in high speed disperser, the shearing dispersion 5-15min under 900-1100r/min revolving speed;Then in 140- Six ferrous sulfate hydrate ammonium of 0.1-0.3 part and 0.1-0.3 parts of ferric sulfate are sequentially added under 160r/min revolving speed, in 1800- Continue shearing dispersion 20-30min under 2200r/min revolving speed.
6. manufacturing method according to claim 4, which is characterized in that in step (2), the compound wood powder is by the following method It is prepared:
The aspen fibers by using silicon, 20- that aspen fibers by using silicon, 15-30 part length that 5-15 parts of length are 3-10mm are 0.5-3mm are taken by weight The Poplar Powder of 40 parts of 30-60 mesh and the Poplar Powder of 25-50 parts of 100-325 mesh are stirred 10-30min in blender.
7. manufacturing method according to claim 6, which is characterized in that in step (2), by polyethylene glycol composite phase change energy-storing Specific steps of the material load on compound wood powder are as follows:
The compound wood powder is fitted into vacuum pressure immersion can, is vacuumized, pressure inside the tank 0.01-0.02MPa is made and is maintained This pressure 20-30min;
Liquid flowing valve is opened, polyethylene glycol composite phase-change energy storage material is pumped into vacuum pressure immersion can, polyethylene glycol is answered Compound wood powder is completely covered in the liquid level for closing phase-changing energy storage material, then impregnates 1.0-4.0h under 0.5-1.8MPa pressure;
Draining valve is opened, polyethylene glycol composite phase-change energy storage material is transmitted back to reservoir with pressure;Gas valve is opened to let out Then wood powder is taken out the dry compound wood powder for having polyethylene glycol composite phase-change energy storage material to get load by pressure.
8. manufacturing method according to claim 4, it is characterised in that:
In step (3), the polyethylene glycol-isocyanates copolymer resins are prepared by following steps:
It takes 100 parts of acetone to be put into reaction kettle by weight, 100-300 parts of Macrogol 6000s is added, in 100-120 under stirring DEG C vacuumize dehydration 3-4h;Then it is slowly stirred under nitrogen protection, 40-50 parts of isophorones is slowly added dropwise at 55-65 DEG C Diisocyanate is stirred to react 1.5-2.5h;5-8 parts of 1,4-butanediol are added, and 0.3-0.6 parts of two fourths of tin dilaurate are added dropwise Ji Xi, the reaction was continued 3-5h are to get polyethylene glycol-isocyanates copolymer resins;
The cladding operation is specific as follows:
In the case where high low speed mixing blender is stirred continuously, silane coupling agent is atomized with air atomization machine and is sprayed into obtained by step (2) Load has in the compound wood powder of polyethylene glycol composite phase-change energy storage material, stirs 4-6min, then uses during being stirred continuously Glue sprayer sprays into polyethylene glycol-isocyanates copolymer resins of atomization, stirs lower cladding 12-18min.
9. the manufacturing method according to any one of claim 4-8, it is characterised in that:
In step (4), PVC plastic powder, auxiliary agent and load is taken to have the resin cladding wood powder of phase-changing energy storage material, it is mixed in high speed The specific steps being kneaded in mill are as follows:
Load obtained by 50 parts of steps (3) is taken to have resin the cladding wood powder, 30-60 parts of PVC plastics of phase-changing energy storage material by weight Powder, 1-5 part calcium zinc stabilizer, 4-12 parts of chlorinated paraffins, 5-15 parts of dioctyl phthalates, 1-10 parts of stearic acid, 0.1- 0.5 part of 2,6 di tert butyl 4 methyl phenol antioxidant, 5-25 parts of ammonium polyphosphate flame retardants, 0-5 parts of AC-1600 foaming agents, 0- 10 parts of silane coupling agents, 0-3 parts of ferric oxide red colorants and 0-20 parts of precipitated calcium carbonate fillers, are kneaded 10- in high speed mixing smelting machine 20min;
It is described to mediate extrusion, mill tabletting and the detailed process for cutting deburring in step (5) are as follows:
It adds mixture into twin-screw kneading extruder, in 120-130 DEG C of area's temperature, two 150-160 DEG C of area's temperature, 3rd area 140-150 DEG C of temperature, four 155-165 DEG C of area's temperature, five 170-175 DEG C of area's temperature, 175-185 DEG C of machine neck die temperature, screw rod Under the conditions of revolving speed 10-25r/min, mediates and squeeze out 8-12min;Then in two roll tablet open mills, under the conditions of 150-180 DEG C Mill tabletting;Most deburring is cut through cutting machine afterwards.
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