CN101768334A - Wood-plastic composite material and forming plate made of wood-plastic composite material - Google Patents
Wood-plastic composite material and forming plate made of wood-plastic composite material Download PDFInfo
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- CN101768334A CN101768334A CN200810246687A CN200810246687A CN101768334A CN 101768334 A CN101768334 A CN 101768334A CN 200810246687 A CN200810246687 A CN 200810246687A CN 200810246687 A CN200810246687 A CN 200810246687A CN 101768334 A CN101768334 A CN 101768334A
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Abstract
The invention provides a wood-plastic composite material which contains wood powder and resin. The wood-plastic composite material also contains a foaming agent; the resin is biodegradable and thermoplastic; with the total weight of the wood-plastic composite material as an reference, the weight percent of the wood powder is within 20 to 49%, the weight percent of the biodegradable and thermoplastic resin is within 50 to 79%, and the weight percent of the foaming agent is within 0.1 to 10%. The invention further provides a forming plate made of the wood-plastic composite material. The wood-plastic composite material has excellent biodegradability owing to the contained biodegradable and thermoplastic resin, and has low density owing to the contained foaming agent.
Description
Technical field
The profiled sheeting that the present invention relates to a kind of wood plastic composite and make by this wood plastic composite.
Background technology
In recent years; owing to global environmental protection requires to guarantee the surging of the forest reserves and timber cost; and timber-work is felt inveteracy potential demand in order to tackle; set about developing the Homogenholz that the energy replacing wood is applied in the matrix material on furniture and the daily necessities and uses matrix material to make, so that obtain the surface properties close with natural timber.For example, a kind of synthetic method of reactive wood powder polyurethane foamed material is disclosed among the CN 1032694C, this method is included in catalyzer and exists down, under 90-125 ℃, make wood powder and polyether reactant, make wood powder polyether, then wood powder polyether and polyisocyanic acid ester foaming are obtained reactive wood powder polyurethane foamed material, wherein, described polyethers can be that Sorbitol Powder is a polyethers, used wood powder is that particle diameter is kahikatea, Korean pine, poplar, linden, the sawdust of paulownia wood, wood shavings, the wood chip of 74-175 micron, and the weight ratio of wood powder and polyethers is 1: 2-9.
CN 1128053C discloses a kind of plastic-wood section moulding process and equipment, it is characterized in that, the composition of raw materials of this section bar comprises the 30-80 weight account polyethylene, 20-70 weight part vegetable fibre powder, 0.1-0.5 weight part hardened resin, 0.1-2.0 weight account polyethylene wax, 0.1-0.5 weight part oxidation inhibitor and 1-5 weight part reinforced modifier, its technical process comprise with above-mentioned prescription by the metering of all raw materials after, at first the vegetable fibre powder is put into high-speed mixer and stir intensification, with dynamic drying process with the moisture removal in the vegetable fibre powder, the terminal temperature scope is 90-100 ℃, add polyvinyl resin and other component then, continue to stir, carry out secondary temperature elevation to 100-120 ℃, then material is entered in the low speed mixer, be cooled to below 40 ℃, be stirred in the barrel helical-ribbon type then that the continual material that stirs up and down makes material not stratified in the whole process of production, make the material after drying then, dry good material enters the conical double screw extruder plasticizing, from the mould extrusion moulding, cooling and shaping then, after section bar reaches predetermined length, cutting automatically.
Above-mentioned wood plastic composite is that this material property mainly is subjected to the restriction of plastics performance by wood powder and the compound material that obtains of plastics (being synthetic resins).When wood powder content was high, because wood powder friction resistance when mobile is big, feasible to add the material fluidity in man-hour low, causes production efficiency low etc.Simultaneously because timber at high temperature can decompose charing, so can not solve by the method that improves processing temperature by taking.In order to reach the production purpose, what adopt usually in the processing of wood plastic composite at present is the lower plastics of melting temperature such as polyethylene and polymethyl acrylate.But often intensity is lower for the wood plastic composite made with these plastics, can not use as structured material.In order to make wood plastic composite have range of application widely, just must employing itself have the plastics of higher physical and mechanical property as flowing carrier.But there are problems such as processing temperature height in the plastics of these kinds.And the consistency of wood powder and resin material is poor, makes the uneven components of the wood powder in the Homogenholz be included in moulding, and the result causes density unevenness even, makes the processing characteristics of matrix material and mechanics of materials intensity all be subjected to very big influence.
For this reason, CN 1116154C discloses a kind of synthetic wood and method and apparatus and Homogenholz and forming method and device, described synthetic wood comprises that water ratio 0.1-0.3 weight %, the median size of 45-70 weight % are the thermoplastic resin material mixing of following cellulosic materials particle of 20 orders and 30-55 weight %, and the formation particle diameter is the gelatinous mixture below 10 millimeters.The manufacture method of described synthetic wood comprises being reinstated to stir and impact blade by the thermoplastic resin material one that 45-70 weight % impacts the heat of friction that produces when blade mixes to be dried to water ratio be 0.1-0.3 weight %, adds after the cellulosic materials particle drying below median size 20 orders 30-55 weight % through paddle and is mixed and made into mixture, by heat of friction mixingly described dried fibres quality particle is sneaked in the described resin form gelatinous mixture, cool off then, to make the particle diameter of compound particles be below 10 millimeters for pulverizing and whole this mixture of grain.This patent is the porphyrization by the spheroid frictional force in the pulverizer, with the Roughen Edges of wood powder, protrude the position and must the shape fiber change over the particle of soccer star or almost spherical, to improve the mobile and dispersed of shaping wood powder.That is to say, this patent is to improve flowability, dispersiveness and the wood powder of wood powder and the consistency of resin by the improvement to processing units, for example, by lead-in portion heating extruded material, so that extruded material keeps mobile and suitable mixing state at device; Inner wall surface in the working chamber is comprising the internal layer that is formed by the little fluoro-resin of resistance coefficient, cellulosic materials particle in the extruded material can be flowed glossily and can not be subjected to big resistance.The mechanical property of the Homogenholz that makes with this method is very good.Yet the biodegradability of the Homogenholz that this method makes is relatively poor, and density is higher.
Summary of the invention
The objective of the invention is in order to overcome the relatively poor and higher shortcoming of density of wood plastic composite biodegradability of the prior art, the profiled sheeting that a kind of biodegradability excellence and low density wood plastic composite is provided and makes by this wood plastic composite.
The invention provides a kind of wood plastic composite, this wood plastic composite contains wood powder and resin, wherein, described wood plastic composite also contains whipping agent, described resin is biodegradable thermoplastic resin, and is benchmark with the gross weight of described wood plastic composite, and the content of described wood powder is 20-49 weight %, the content of described biodegradable thermoplastic resin is 50-79 weight %, and the content of described whipping agent is 0.1-10 weight %.
The present invention also provides the profiled sheeting that is made by described wood plastic composite.
Wood plastic composite provided by the invention is owing to contain biodegradable thermoplastic resin, so its biodegradability significantly improved, and because the existence of whipping agent, thereby reduced the density of the wood plastic composite that is obtained significantly.Carry out performance test by the profiled sheeting to the wood plastic composite that makes among the embodiment and draw, the density of the profiled sheeting that is made by wood plastic composite provided by the invention is low to moderate 0.75 gram/cubic centimetre, and the degraded rate of weight loss is up to 73.0 weight %.Particularly, from test result as can be seen, a preferred embodiment of the invention, when using Cellmic C 121, N, N-dinitroso five methyne tetramines and 4, the mixture of 4-disulfonyl hydrazide diphenyl ether are as whipping agent and Cellmic C 121: N, N-dinitroso five methyne tetramines: 4, the mol ratio of 4-disulfonyl hydrazide diphenyl ether is 1: (0.1-2): in the time of (0.1-3), not only density is lower but also mechanical property is also very excellent for the wood plastic composite that is obtained.
Embodiment
The invention provides a kind of wood plastic composite, this wood plastic composite contains wood powder and resin, wherein, described wood plastic composite also contains whipping agent, described resin is biodegradable thermoplastic resin, and is benchmark with the gross weight of described wood plastic composite, and the content of described wood powder is 20-49 weight %, the content of described biodegradable thermoplastic resin is 50-79 weight %, and the content of described whipping agent is 0.1-10 weight %.For the wood plastic composite that makes acquisition has better biodegradability and mechanical property, gross weight with described wood plastic composite is a benchmark, the content of described wood powder is preferably 30-40 weight %, and the content of described biodegradable thermoplastic resin is preferably 55-69 weight %.
There is no particular limitation for the biodegradable thermoplastic resin that adopts in the present invention, can be for well known to a person skilled in the art various biodegradable thermoplastic resins, for example can be among poly butylene succinate (PBS), polyethylene glycol adipate, polypropylene adipate (PPA), poly adipate succinic acid ester, poly-hexanodioic acid hexylene glycol ester, polydiethylene glycol succinate, poly-succsinic acid propylene glycol ester, poly-succsinic acid tetramethylene adipate, poly terephthalic acid succsinic acid glycol ester and the poly-hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester one or more.Because when using poly butylene succinate as biodegradable thermoplastic resin, the wood plastic composite that is obtained not only has better biodegradability, and mechanical property is also excellent more, so described biodegradable thermoplastic resin is preferably the mixture of poly butylene succinate or poly butylene succinate and above-mentioned other biodegradable thermoplastic resin.Further under the preferable case, in the described biodegradable thermoplastic resin, the content of poly butylene succinate is 50-100 weight %.
Under the preferable case, the weight-average molecular weight of described biodegradable thermoplastic resin is 5 * 10
4-1 * 10
6
Among the present invention, described wood powder can be various cellulosic materials particles, and commonly used is in the sawdust of kahikatea, Korean pine, poplar, linden, paulownia wood of 20-300 micron or chip, cotton shell, nut duricrust, the coconut husk one or more as particle diameter.Described wood powder can in all sorts of ways and obtain, and obtains after for example pulverizing with various waste wood.The water ratio of preferred wood powder is lower than 5 weight %.The water ratio that can in all sorts of ways wood powder is reduced to below the 5 weight %.
The content of whipping agent is also restricted in wood plastic composite of the present invention, and when the content of whipping agent was higher than 10 weight %, though the wood plastic composite density that is obtained is very low, mechanical property was very poor; When the content of whipping agent during less than 0.1 weight %, then because the too low density that makes the wood plastic composite that obtained of content reduces not obviously, and when content during less than 0.05 weight %, the density of the wood plastic composite that is obtained can reduce hardly.The density of the wood plastic composite that obtains in order to make suitably reduces and has a mechanical property preferably, is benchmark with the gross weight of described wood plastic composite, and the content of described wood powder is preferably 0.4-6 weight %.The present invention does not limit especially for described whipping agent, well known to a person skilled in the art that various whipping agents can be used among the present invention and realize purpose of the present invention, described whipping agent can be chemical foaming agent, pneumatogen or surfactant-based whipping agent.Described chemical foaming agent can be N, N-dinitroso five methyne tetramines, Cellmic C 121, Diisopropyl azodicarboxylate, diisopropyl azodiformate, diethyl azodiformate, azoformic acid barium, 4,4-disulfonyl hydrazide diphenyl ether, p-toluene sulfonyl hydrazide, 1,3-benzene disulfohydrazide, 1, one or more in the 4-benzene disulfohydrazide; Described pneumatogen can be in normal butane, Skellysolve A, normal hexane, normal heptane, sherwood oil, trichlorofluoromethane, dichlorofluoromethane, Refrigerant 12, the dichloro tetrafluoro ethane one or more; Described surfactant-based whipping agent can be in sodium lauryl sulphate, polyoxyethylenated alcohol sodium sulfate, rosined soap class whipping agent, the plant animal protein class whipping agent one or more.Further under the preferable case, in order further to reduce the density of described wood plastic composite and to guarantee mechanical property preferably, described whipping agent is a chemical foaming agent, and described chemical foaming agent is as above-mentioned chemical foaming agent.Under the most preferred case, described whipping agent is Cellmic C 121, N, N-dinitroso five methyne tetramines and 4, the mixture of 4-disulfonyl hydrazide diphenyl ether, and Cellmic C 121: N, N-dinitroso five methyne tetramines: 4, the mol ratio of 4-disulfonyl hydrazide diphenyl ether is 1: (0.1-2): (0.1-3).
For the hardness and the toughness of the wood plastic composite that makes acquisition significantly improves, described wood plastic composite can also contain nanoparticle, the preferred inorganic nano-particle of particle dia as the 10-100 nanometer that use is as in lime carbonate, diatomite mica, talcum powder, process white, kaolin, the hollow glass micropearl one or more.Because described nanoparticle particle diameter is little, have high workability and can with macromole generation bonding action, therefore the existence of described nanoparticle can improve the flowability of wood powder and the consistency between wood powder and the resin, thereby improves the mechanical property of wood plastic composite.
Under the preferable case, in wood plastic composite provided by the invention, can also contain coupling agent in the described wood plastic composite, described coupling agent is for increasing the material of avidity between wood powder, nano particle, the resin (consistency).Among the present invention, described coupling agent can be various materials with both sexes structure, as in silicane, aluminic acid ester, titanic acid ester, the aluminium titanic acid ester one or more.Preferred described coupling agent is silane coupling agent, titante coupling agent, aluminate coupling agent, aluminium titante coupling agent or their mixture in the specific embodiment of the invention, described coupling agent can reduce the autohemagglutination of wood powder, improve the dispersiveness of wood powder, like this in the course of processing, can combine more closely between wood powder and the biodegradable thermoplastic resin.Under the preferable case, described coupling agent is a titanate coupling agent, because titanic acid ester not only can prevent the reunion of described nano particle particle, make described nano particle reach the optimum dispersion effect, but also can carry out crooked better the entanglement with biodegradable thermoplastic resin, thereby improve the consistency of biodegradable thermoplastic resin and wood powder and other composition, and obviously improve the mechanical property of the wood plastic composite that is obtained thus.Further under the preferable case, described coupling agent is one or more in hydramine titan-alkoxide acid esters, hydramine two phosphorus acyloxy oxyacetate titanates, hydramine second two support titanic acid ester, the hydramine two pyrophosphoryl oxygen base oxyacetate titanates, meets the mechanical property that this preferable case can make the wood plastic composite of acquisition and improves more significantly.
In the present invention, the content of described nano particle and the coupling agent amount that is respectively nano particle and coupling agent routine just can realize purpose of the present invention.Yet, under the preferable case, gross weight with described wood plastic composite is a benchmark, the content of described wood powder is 20-49 weight %, the content of described biodegradable thermoplastic resin is 50-79 weight %, the total content of described nano particle and coupling agent is 0.5-25 weight %, and the content of described nano particle is 0.1-15 weight %, and the content of described coupling agent is 0.5-10 weight %.
In addition, in wood plastic composite provided by the invention, can also contain other various additives in the described wood plastic composite, as in softening agent, neutralizing agent, oxidation inhibitor, light/thermo-stabilizer, photooxidant, antifogging agent, fire retardant, static inhibitor, lubricant, the pigment one or more.Described softening agent can be the various materials that can increase wood plastic composite plasticity, as in epoxy soybean oil, Sorbitol Powder, glycerine, the tetramethylolmethane one or more.Described neutralizing agent can be various can in and the material of wood vinegar gas, as urea or aqueous solution of urea, described aqueous solution of urea is preferably the aqueous solution of urea that contains ammonia, phenol, trimeric cyanamide, the concentration of solution can be 5-50 weight %.The amount of described neutralizing agent is preferably the 0.5-2 weight % of wood powder weight.Described oxidation inhibitor can be selected from four (3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) in the propionic acid pentaerythritol ester (abbreviation antioxidant 1010), thio-2 acid SUNSOFT Q-182S (being called for short oxidation inhibitor DSTP), phosphorous acid esters, composite antioxidant PKY, dihydroxyphenyl propane one or more.Light/thermo-stabilizer can be selected from one or more in UV-series light/thermo-stabilizer, carbon black, organic tin light/thermo-stabilizer, trisnonyl phenyl phosphite (TNPP), the epoxy soybean oil.Wherein, UV-series light/thermo-stabilizer can be Alpha-hydroxy-4-oxy-octyl benzophenone (being called for short UV-531).Described organic tin light/thermo-stabilizer can be selected from one or more in dibutyl tin laurate, the different monooctyl ester diformazan of dithioglycol ester group ethylidene tin (being called for short ester group tin), ester group tin RWS-784, two (the different monooctyl ester of sulfo-glycolic acid) dioctyltin (being called for short capital tin 8831), two toxilic acid dibutyl tins, the different monooctyl ester dibutyl tin of sulfo-glycol.Described lubricating oil can be selected from one or more in whiteruss, the sherwood oil.Lubricating oil is used to reduce the friction between material and the equipment, helps the demoulding.Described pigment can be one or more in titanium dioxide, red iron oxide, Victoria Green WPB, the cobalt blue.The kind of above-mentioned various additives and the selection of consumption have been conventionally known to one of skill in the art.Under the preferable case, be benchmark with the gross weight of described wood plastic composite, the consumption of described wood powder is 20-49 weight %, and the consumption of described biodegradable thermoplastic resin is 50-79 weight %, and the consumption of described additive is 0.1-19 weight %.
The production method of described wood plastic composite provided by the invention is fairly simple, adopts the production method of conventional wood plastic composite to get final product, and different is the composition of wood plastic composite to be changed into the composition of wood plastic composite of the present invention.Particularly, the production method of described wood plastic composite comprises and will form the various components such as the wood powder of described wood plastic composite, biodegradable thermoplastic resin and whipping agent are mixed with each other evenly, obtain containing wood powder, the mixture of biodegradable thermoplastic resin and whipping agent, then this is contained wood powder, the mixture plasticizing granulation of biodegradable thermoplastic resin and whipping agent, described plasticizing granulation is carried out in twin screw extruder, the length-to-diameter ratio of forcing machine can be 20-64, screw speed can be 5-50 rev/min, the temperature of plasticizing granulation can be 140-200 ℃, and vacuum tightness is below 300 handkerchiefs.Described vacuum tightness refers to the absolute pressure in the twin screw extruder.The numerical value of vacuum tightness is more little, represents the air in this vacuum chamber few more.
In described production method, the described mixture that contains wood powder, biodegradable thermoplastic resin and whipping agent mixes to adopt and well known to a person skilled in the art that any method carries out, under the preferable case, raw materials such as wood powder, biodegradable thermoplastic resin and whipping agent are added in the homogenizer, and low whipping speed is under 500-1000 rev/min, mixed 3-100 minute down at 80-135 ℃.Further under the preferable case, low whipping speed is with wood powder and coupling agent uniform mixing 1-15 minute under 500-1000 rev/min, under 80-135 ℃, all the other raw materials that add then except that whipping agent continue to mix 2-85 minute, again products therefrom is mixed with whipping agent after mixing, can be by pulverous whipping agent be mixed the uniform mixing that the mode that is fitted in the material of main part and mixes realizes whipping agent.For whipping agent is mixed more equably with material of main part, under the preferable case, whipping agent is dissolved in forms solution in the solvent, with the above-mentioned products therefrom of this solution impregnation.Described solvent be selected from any not with other composition reaction of whipping agent and wood plastic composite and the solvent removed easily, commonly used have dimethyl sulfoxide (DMSO) (DMSO), N, a dinethylformamide (DMF).The concentration of described solution is minimum to be 0.5 weight %, and maximum concentration can be the concentration of whipping agent when reaching capacity in solvent.The condition optimization of dipping in temperature be 20-105 ℃, pressure be under the condition of 0.15-15 MPa in autoclave dipping 3-360 minute.Mix the back except that desolvating, remove the method for desolvating and be preferably removal of solvent under reduced pressure.
The present invention also provides the profiled sheeting that is made by described wood plastic composite.The production method of described profiled sheeting can adopt the production method of the profiled sheeting of various routines, as can to as described in wood plastic composite directly be shaped to profiled sheeting, the concrete operations of described moulding have been conventionally known to one of skill in the art, do not repeat them here.Simultaneously, one skilled in the art will appreciate that and after containing the composition plasticizing of composition of wood plastic composite provided by the invention, directly to make profiled sheeting, thereby save the step of granulation.Wood plastic composite provided by the invention can also be made the Wood model compound products of the various conventional shapes except that tabular profiled sheeting.
Following examples will the present invention is described further, employed Cellmic C 121 is all available from Shanghai Zhuo Rui chemical industry company limited in following each embodiment and Comparative Examples, N, N-dinitroso five methyne tetramines are all available from the outstanding surplus industry and trade in Shanghai company limited, 4, the 4-disulfonyl hydrazide diphenyl ether is all available from Hangzhou Hi-Tech Fine Chemical Co., Ltd.
Embodiment 1
Present embodiment is used to illustrate that wood plastic composite provided by the invention reaches by its profiled sheeting that makes.
With 35 weight part wood powders (particle dia is the paulownia wood saw end of 100-200 micron) under 120 ℃ of temperature, dry back and 3 weight part hydramine titan-alkoxide acid esters (the sharp evolution worker in Changzhou company limited, TNS type) in homogenizer, under 115 ℃ with 1000 rev/mins of high-speed mixing 10 minutes, add 3 weight part nano-calcium carbonates (particle dia is the 50-100 nanometer) then, (weight-average molecular weight is 2.5 * 10 to 55 weight part poly butylene succinates
5), and under 115 ℃, continue high-speed mixing after 30 minutes, under 50 ℃, be in the solution of 1 weight % with the impregnation mixture that mixes in the concentration of whipping agent that contains 4 weight parts and whipping agent under the pressure of 10 MPas, the whipping agent that uses in described solution is Cellmic C 121: N, N-dinitroso five methyne tetramines: 4, the mol ratio of 4-disulfonyl hydrazide diphenyl ether is 1: 1: 1.5 a mixed foaming agent, and the solvent that uses is N, dinethylformamide, flood and adopt Rotary Evaporators under 70 ℃, to remove solvent fully after 50 minutes, thereby obtain mixed uniformly mixture and it is changed over to
Plastify in the tapered twin screw extruder, to be respectively 155 ℃, 165 ℃, 175 ℃, 180 ℃, 175 ℃, screw speed be that 1000 rev/mins, vacuum tightness are 300 handkerchiefs to the Heating temperature of each section in the twin screw extruder; Material through after the fusion, shearing, dispersion, reaction, compression, exhaust, plasticizing, again after mould molding, cutting, thereby makes the profiled sheeting sample A1 of wood plastic composite in the screw rod and cylindrical shell of above-mentioned forcing machine.
Embodiment 2
Present embodiment is used to illustrate that wood plastic composite provided by the invention reaches by its profiled sheeting that makes.
With 20 weight part wood powders (particle dia is the cotton shell powder of 100-200 micron) under 120 ℃ of temperature, dry back and 0.5 weight part hydramine, two phosphorus acyloxy oxyacetate titanates (the sharp evolution worker in Changzhou company limited, CT-117 type) in homogenizer, under 80 ℃ with 1000 rev/mins of high-speed mixing 15 minutes, add 0.1 weight part nanometer process white (particle dia is the 30-80 nanometer) then, (weight-average molecular weight is 5 * 10 to 45 weight part poly butylene succinates
4), (weight-average molecular weight is 5 * 10 to the poly-succsinic acid tetramethylene adipate of 34 weight parts
4), and under 80 ℃, continue high-speed mixing after 85 minutes, under 50 ℃, be in the solution of 0.5 weight % with the impregnation mixture that mixes in the concentration of whipping agent that contains 0.4 weight part and whipping agent under the pressure of 10 MPas, the whipping agent that uses in described solution is Cellmic C 121: N, N-dinitroso five methyne tetramines: 4, the mol ratio of 4-disulfonyl hydrazide diphenyl ether is 1: 0.1: 3 a mixed foaming agent, and the solvent that uses is N, dinethylformamide, flood and adopt Rotary Evaporators under 70 ℃, to remove solvent fully after 50 minutes, thereby obtain mixed uniformly mixture and it is changed over to
Plastify in the tapered twin screw extruder, to be respectively 155 ℃, 165 ℃, 175 ℃, 180 ℃, 175 ℃, screw speed be that 1000 rev/mins, vacuum tightness are 300 handkerchiefs to the Heating temperature of each section in the twin screw extruder; Material through after the fusion, shearing, dispersion, reaction, compression, exhaust, plasticizing, again after mould molding, cutting, thereby makes the profiled sheeting sample A2 of wood plastic composite in the screw rod and cylindrical shell of above-mentioned forcing machine.
Embodiment 3
Present embodiment is used to illustrate that wood plastic composite provided by the invention reaches by its profiled sheeting that makes.
With 49 weight part wood powders (particle dia is the poplar sawdust of 100-200 micron) under 120 ℃ of temperature, dry back and 0.5 weight part hydramine, two phosphorus acyloxy oxyacetate titanates (the sharp evolution worker in Changzhou company limited, CT-117 type) in homogenizer, under 80 ℃ with 1000 rev/mins of high-speed mixing 15 minutes, add 0.1 weight part nanometer process white (particle dia is the 30-80 nanometer) then, (weight-average molecular weight is 5 * 10 to 30 weight part poly butylene succinates
4), (weight-average molecular weight is 5 * 10 to the poly-succsinic acid tetramethylene adipate of 20 weight parts
4), and under 80 ℃, continue high-speed mixing after 85 minutes, under 50 ℃, be in the solution of 0.5 weight % with the impregnation mixture that mixes in the concentration of whipping agent that contains 0.4 weight part and whipping agent under the pressure of 10 MPas, the whipping agent that uses in described solution is Cellmic C 121: N, N-dinitroso five methyne tetramines: 4, the mol ratio of 4-disulfonyl hydrazide diphenyl ether is 1: 0.1: 3 a mixed foaming agent, and the solvent that uses is N, dinethylformamide, flood and adopt Rotary Evaporators under 70 ℃, to remove solvent fully after 50 minutes, thereby obtain mixed uniformly mixture and it is changed over to
Plastify in the tapered twin screw extruder, to be respectively 155 ℃, 165 ℃, 175 ℃, 180 ℃, 175 ℃, screw speed be that 1000 rev/mins, vacuum tightness are 300 handkerchiefs to the Heating temperature of each section in the twin screw extruder; Material through after the fusion, shearing, dispersion, reaction, compression, exhaust, plasticizing, again after mould molding, cutting, thereby makes the profiled sheeting sample A3 of wood plastic composite in the screw rod and cylindrical shell of above-mentioned forcing machine.
Embodiment 4
Present embodiment is used to illustrate that wood plastic composite provided by the invention reaches by its profiled sheeting that makes.
With 30 weight part wood powders (particle dia is the coconut shell flour of 100-200 micron) under 120 ℃ of temperature, dry back and 5 weight part hydramine second two support titanic acid ester (the sharp evolution worker in Changzhou company limited, CT-AT type) and 5 weight part hydramine, two pyrophosphoryl oxygen base oxyacetate titanates (Changzhou profit evolution worker company limited, CT-115A type) in homogenizer, under 135 ℃ with 1000 rev/mins of high-speed mixing 1 minute, add 3.5 weight part nano diatomite micas (particle dia is the 50-100 nanometer) then, (weight-average molecular weight is 1 * 10 to 25 weight part poly butylene succinates
6), (weight-average molecular weight is 1 * 10 to the poly-hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester of 25 weight parts
6) and 0.5 weight part antioxidant 1010 (the rich foreign trade in Xinda, Tianjin company limited), and under 135 ℃, continue high-speed mixing after 2 minutes, under 50 ℃, be in the solution of 2 weight % with the impregnation mixture that mixes in the concentration of whipping agent that contains 6 weight parts and whipping agent under the pressure of 10 MPas, the whipping agent that uses in described solution is Cellmic C 121: N, N-dinitroso five methyne tetramines: 4, the mol ratio of 4-disulfonyl hydrazide diphenyl ether is 1: 2: 0.1 a mixed foaming agent, and the solvent that uses is N, dinethylformamide, flood and adopt Rotary Evaporators under 70 ℃, to remove solvent fully after 50 minutes, thereby obtain mixed uniformly mixture and it is changed over to
Plastify in the tapered twin screw extruder, to be respectively 155 ℃, 165 ℃, 175 ℃, 180 ℃, 175 ℃, screw speed be that 1000 rev/mins, vacuum tightness are 300 handkerchiefs to the Heating temperature of each section in the twin screw extruder; Material through after the fusion, shearing, dispersion, reaction, compression, exhaust, plasticizing, again after mould molding, cutting, thereby makes the profiled sheeting sample A4 of wood plastic composite in the screw rod and cylindrical shell of above-mentioned forcing machine.
Embodiment 5
Present embodiment is used to illustrate that wood plastic composite provided by the invention reaches by its profiled sheeting that makes.
Method according to embodiment 1 is produced wood plastic composite and profiled sheeting, and (weight-average molecular weight is 2.5 * 10 to the different poly-succsinic acid propylene glycol esters that is to use 30 weight parts
5) and the poly terephthalic acid succsinic acid glycol ester of 25 weight parts (weight-average molecular weight is 2.5 * 10
5) (weight-average molecular weight is 2.5 * 10 to replace the poly butylene succinate of 55 weight parts
5), thereby make the profiled sheeting sample A5 of wood plastic composite.
Embodiment 6
Present embodiment is used to illustrate that wood plastic composite provided by the invention reaches by its profiled sheeting that makes.
Method according to embodiment 1 is produced wood plastic composite and profiled sheeting, and (weight-average molecular weight is 2.5 * 10 to the different poly terephthalic acid succsinic acid glycol esters that is to use 55 weight parts
5) (weight-average molecular weight is 2.5 * 10 to replace the poly butylene succinate of 55 weight parts
5), thereby make the profiled sheeting sample A6 of wood plastic composite.
Embodiment 7
Present embodiment is used to illustrate that wood plastic composite provided by the invention reaches by its profiled sheeting that makes.
Method according to embodiment 1 is produced wood plastic composite, and the different vinyl trichloro silanes (Qufu Wanda's chemical industry company limited, NQ-50 type) that are to use replace hydramine titan-alkoxide acid esters as coupling agent, thereby make the profiled sheeting sample A7 of wood plastic composite.
Embodiment 8
Present embodiment is used to illustrate that wood plastic composite provided by the invention reaches by its profiled sheeting that makes.
Method according to embodiment 1 is produced wood plastic composite and profiled sheeting, the different dichlorofluoromethane (available from Shanghai Qi An chemical industry company limited) that are to use replace Cellmic C 121, N, N-dinitroso five methyne tetramines and 4, the mixture of 4-disulfonyl hydrazide diphenyl ether is as whipping agent, thereby makes the profiled sheeting sample A8 of wood plastic composite.
Embodiment 9
Present embodiment is used to illustrate that wood plastic composite provided by the invention reaches by its profiled sheeting that makes.
Method according to embodiment 1 prepares wood plastic composite and profiled sheeting, different is with 41 weight part wood powders (particle dia is the paulownia wood saw end of 100-200 micron) and 55 weight part poly butylene succinate uniform mixing, and impregnated in afterwards in the solution of the described whipping agent that contains 4 weight parts, thereby make the profiled sheeting sample A9 of wood plastic composite.
Comparative Examples 1
Produce wood plastic composite and profiled sheeting according to the method for embodiment 1, the consumption of different is wood powder is 5 weight parts, and the consumption of poly butylene succinate is 85 weight parts, thereby makes the profiled sheeting sample D1 of wood plastic composite.
Comparative Examples 2
Produce wood plastic composite and profiled sheeting according to the method for embodiment 1, the consumption of different is wood powder is 65 weight parts, and the consumption of poly butylene succinate is 25 weight parts, thereby makes the profiled sheeting sample D2 of wood plastic composite.
Comparative Examples 3
Method according to embodiment 1 is produced wood plastic composite and profiled sheeting, different is that whipping agent (is Cellmic C 121, N, N-dinitroso five methyne tetramines and 4, the mixture of 4-disulfonyl hydrazide diphenyl ether) consumption is 11 weight parts, the consumption of biodegradable thermoplastic resin (being poly butylene succinate) is 48 weight parts, thereby makes the profiled sheeting sample D3 of wood plastic composite.
Comparative Examples 4
Method according to embodiment 1 is produced wood plastic composite and profiled sheeting, different is not use whipping agent, and use 2.0 weight part epoxy soybean oils and 2.0 weight part antioxidant 1010s (the rich foreign trade in Xinda, Tianjin company limited) to replace the whipping agent of 4 weight parts, and epoxy soybean oil and antioxidant 1010 directly mix adding, thereby make the profiled sheeting sample D4 of wood plastic composite.
Performance test
＜density measurement 〉
According to the test determines profiled sheeting sample A1-A9 of GB/T 6343-1995 density of material and the density of D1-D4, test result is as shown in table 1 below.
＜Mechanics Performance Testing 〉
Adopt following method to carry out Mechanics Performance Testing respectively above-mentioned profiled sheeting sample A1-A9 and D1-D4, test result is as shown in table 1 below.
(1) tensile strength of the test determines wood plastic composite of usefulness GB/T1040-92 material extending performance;
(2) flexural strength of the test determines wood plastic composite of usefulness GB/T9341-2000 material bending performance;
(3) simple beam impact strength of the ballistic test determines wood plastic composite of usefulness GB/T1043-93 material simply supported beam.
＜biodegradability test 〉
Above-mentioned profiled sheeting sample A1-A9 and D1-D4 be cut into respectively be of a size of millimeter (wide) * 1.0,100 millimeters (length) * 10 millimeter (thick) standard batten, be used for following performance test.
The weight of weighing and record each standard batten this moment; Respectively 13 standard battens are wrapped between gauze then, are embedded in the liftoff surperficial 20 centimetres flower nursery soil; Take out after 30 days and clean back oven dry weighing and write down weight.
Rate of weight loss with following method base of calculation batten:
Weight * 100% before rate of weight loss (%)=(weight-be embedded in before the test in the soil after 30 days weight)/test
Its calculation result is shown in the following table 1.
Table 1
| ??A1 | ??A2 | ??A3 | ??A4 | ??A5 | ??A6 | ??A7 | ??A8 | ??A9 | ??D1 | ??D2 | ??D3 | ??D4 | |
| Density (gram/cubic centimetre) | ??0.75 | ??0.89 | ??0.87 | ??0.79 | ??0.84 | ??0.85 | ??0.82 | ??0.95 | ??0.85 | ??0.84 | ??0.85 | ??0.69 | ??1.24 |
| Draw and stretch intensity (MPa) | ??47 | ??44 | ??43 | ??46 | ??38 | ??37 | ??33 | ??34 | ??30 | ??27 | ??24 | ??18 | ??45 |
| Flexural strength (MPa) | ??83 | ??80 | ??79 | ??82 | ??75 | ??75 | ??69 | ??71 | ??63 | ??59 | ??55 | ??41 | ??81 |
| Shock strength (MPa) | ??40 | ??37 | ??35 | ??39 | ??31 | ??32 | ??22 | ??33 | ??20 | ??14 | ??15 | ??16 | ??30 |
| ??A1 | ??A2 | ??A3 | ??A4 | ??A5 | ??A6 | ??A7 | ??A8 | ??A9 | ??D1 | ??D2 | ??D3 | ??D4 | |
| Rate of weight loss (weight %) | ??73.0 | ??72.5 | ??71.7 | ??71.1 | ??65.3 | ??65.1 | ??70.2 | ??70.5 | ??69.8 | ??68.1 | ??57.6 | ??65.1 | ??72.9 |
Data by table 1 as can be seen, compare with the wood plastic composite that does not adopt biodegradable thermoplastic resin in the prior art, wood plastic composite provided by the invention has been owing to adopted biodegradable thermoplastic resin, thereby has excellent biodegradability; When having excellent biodegradability, when use comprises the biodegradable thermoplastic resin of poly butylene succinate and uses titanate coupling agent, thereby the mechanical property of the wood plastic composite that makes improves highly significant; And, in wood plastic composite of the present invention, because the existence of whipping agent, thereby significantly reduced the density of wood plastic composite, particularly when using Cellmic C 121, N, N-dinitroso five methyne tetramines and 4, the mixture of 4-disulfonyl hydrazide diphenyl ether are during as whipping agent, thus the wood plastic composite that makes not only density reduce significantly and also mechanical property also very excellent.
Claims (11)
1. wood plastic composite, this wood plastic composite contains wood powder and resin, it is characterized in that, described wood plastic composite also contains whipping agent, described resin is biodegradable thermoplastic resin, and is benchmark with the gross weight of described wood plastic composite, and the content of described wood powder is 20-49 weight %, the content of described biodegradable thermoplastic resin is 50-79 weight %, and the content of described whipping agent is 0.1-10 weight %.
2. wood plastic composite according to claim 1, wherein, be benchmark with the gross weight of described wood plastic composite, the content of described wood powder is 30-40 weight %, the content of described biodegradable thermoplastic resin is 55-69 weight %, and the content of described whipping agent is 0.4-6 weight %.
3. wood plastic composite according to claim 2, wherein, described biodegradable thermoplastic resin is one or more among poly butylene succinate, polyethylene glycol adipate, polypropylene adipate (PPA), poly adipate succinic acid ester, poly-hexanodioic acid hexylene glycol ester, polydiethylene glycol succinate, poly-succsinic acid propylene glycol ester, poly-succsinic acid tetramethylene adipate, poly terephthalic acid succsinic acid glycol ester, the poly-hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester.
4. wood plastic composite according to claim 3, wherein, described biodegradable thermoplastic resin is one or more the mixture among poly butylene succinate or poly butylene succinate and polyethylene glycol adipate, polypropylene adipate (PPA), poly adipate succinic acid ester, poly-hexanodioic acid hexylene glycol ester, polydiethylene glycol succinate, poly-succsinic acid propylene glycol ester, poly-succsinic acid tetramethylene adipate, poly terephthalic acid succsinic acid glycol ester, the poly-hexanodioic acid mutual-phenenyl two acid bromide two alcohol ester.
5. wood plastic composite according to claim 4, wherein, in the described biodegradable thermoplastic resin, the content of poly butylene succinate is 50-100 weight %.
6. according to any described wood plastic composite among the claim 1-5, wherein, the weight-average molecular weight of described biodegradable thermoplastic resin is 5 * 10
4-1 * 10
6
7. wood plastic composite according to claim 1 and 2, wherein, described wood powder comprises one or more in wood shavings or chip, cotton shell, nut duricrust, the coconut husk; Described whipping agent is N, N-dinitroso five methyne tetramines, Cellmic C 121, Diisopropyl azodicarboxylate, diisopropyl azodiformate, diethyl azodiformate, azoformic acid barium, 4,4-disulfonyl hydrazide diphenyl ether, p-toluene sulfonyl hydrazide, 1,3-benzene disulfohydrazide, 1, one or more in 4-benzene disulfohydrazide, normal butane, Skellysolve A, normal hexane, normal heptane, sherwood oil, trichlorofluoromethane, dichlorofluoromethane, Refrigerant 12, the dichloro tetrafluoro ethane.
8. wood plastic composite according to claim 7, wherein, described whipping agent is Cellmic C 121, N, N-dinitroso five methyne tetramines and 4, the mixture of 4-disulfonyl hydrazide diphenyl ether, and Cellmic C 121: N, N-dinitroso five methyne tetramines: 4, the mol ratio of 4-disulfonyl hydrazide diphenyl ether is 1: (0.1-2): (0.1-3).
9. wood plastic composite according to claim 1 and 2, wherein, described wood plastic composite also contains nano particle and/or coupling agent, gross weight with described wood plastic composite is a benchmark, the content of described wood powder is 20-49 weight %, the content of described biodegradable thermoplastic resin is 50-79 weight %, the content of described whipping agent is 0.1-10 weight %, the total content of described nano particle and coupling agent is 0.5-25 weight %, and the particle dia of described nano particle is the 10-100 nanometer, and described nano particle is selected from lime carbonate, the diatomite mica, talcum powder, process white, kaolin, in the hollow glass micropearl one or more; Described coupling agent is selected from one or more in silane coupling agent, titanate coupling agent, aluminate coupling agent, the aluminium titanate coupling agent.
10. wood plastic composite according to claim 9, wherein, gross weight with described wood plastic composite is a benchmark, the content of described coupling agent is 0.5-10 weight %, described coupling agent is a titanate coupling agent, and described titanate coupling agent is one or more in hydramine titan-alkoxide acid esters, hydramine two phosphorus acyloxy oxyacetate titanates, hydramine second two support titanic acid ester, the hydramine two pyrophosphoryl oxygen base oxyacetate titanates.
11. one kind by any profiled sheeting that described wood plastic composite makes among the claim 1-10.
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| CN105209227A (en) * | 2013-06-21 | 2015-12-30 | 乐金华奥斯株式会社 | Board comprising biodegradable resin and wooden flour and method of manufacturing the same |
| CN105802143A (en) * | 2015-01-01 | 2016-07-27 | 晋江凯基高分子材料有限公司 | PBAT (poly(butylene adipate/terephthalate)) foam, preparation method therefor and application of PBAT foam |
| CN106280511A (en) * | 2015-05-21 | 2017-01-04 | 中国科学院理化技术研究所 | A kind of expanded material, preparation method and application |
| CN108976464A (en) * | 2018-06-29 | 2018-12-11 | 芜湖市新京桥包装科技有限公司 | A kind of foaming agent promoting polyurethane toughness |
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| CN1260279C (en) * | 2003-11-17 | 2006-06-21 | 中国科学院长春应用化学研究所 | Biodegradable poly-lactic acid foam plastic containing chain extender and method for preparing the same |
| CN101020780B (en) * | 2007-03-15 | 2010-05-19 | 上海交通大学 | Preparation process of polylactic acid-base thermoplastic wood-plastic composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105209227A (en) * | 2013-06-21 | 2015-12-30 | 乐金华奥斯株式会社 | Board comprising biodegradable resin and wooden flour and method of manufacturing the same |
| CN105802143A (en) * | 2015-01-01 | 2016-07-27 | 晋江凯基高分子材料有限公司 | PBAT (poly(butylene adipate/terephthalate)) foam, preparation method therefor and application of PBAT foam |
| CN106280511A (en) * | 2015-05-21 | 2017-01-04 | 中国科学院理化技术研究所 | A kind of expanded material, preparation method and application |
| CN108976464A (en) * | 2018-06-29 | 2018-12-11 | 芜湖市新京桥包装科技有限公司 | A kind of foaming agent promoting polyurethane toughness |
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