CN110283472A - Anti-aging impact-resistant modified wood plastic composite of one kind and preparation method thereof - Google Patents
Anti-aging impact-resistant modified wood plastic composite of one kind and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K2003/2241—Titanium dioxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The present invention provides a kind of anti-aging impact-resistant modified wood plastic composites and preparation method thereof, the wood plastic composite includes the raw material of following parts by weight: 20-50 parts of polyolefin, enzymatic hydrolysis (EH) lignin modified plant fiber 30-70 parts, 1-3.5 parts of newtrex, 0.1-10 parts of inorganic filler, 0.1-4 parts of antioxidant, 0.1-3 parts of anti ultraviolet agent, the enzymatic hydrolysis (EH) lignin modified plant fiber are to be obtained by enzymolysis xylogen and plant fiber by anhydride reaction.Affinity is high between the plant fiber and plastics of modified composite material of woods and plastics prepared by the present invention, and composite gauge stability is high, and rigidity and toughness are balanced, while ageing resistance also has promotion；During preparing enzymolysis xylogen, a certain amount of lignoenzyme is added, additionally it is possible to improve the impact resistance of wood plastic composite prepared by enzymatic hydrolysis (EH) lignin modified plant fiber.It is provided by the invention to utilize lignin modification plant fiber method, Liginon Resource is made full use of, is turned waste into wealth, the comprehensive utilization of Liginon Resource is realized.
Description
Technical field
The invention belongs to field of compound material, more particularly to a kind of anti-aging impact-resistant modified wood plastic composite and its
Preparation method.
Background technique
Wood plastic composite (Wood-Plastic Composites, WPC) is that domestic and international one kind being surging forward in recent years is new
Type composite material, refers to using polyethylene, polypropylene and polyvinyl chloride etc., instead of common resin adhesive, with more than 50% with
On the useless plant fiber such as wood powder, rice husk, stalk be mixed into new wood materials, then through plastics such as extruding, molding, injection mouldings
Processing technology, the plate or profile produced.It is mainly used for the industries such as building materials, furniture, logistics packaging.Wood plastic composite is
Focus is placed on plastic components, enhancing, toughening filler and weather resisting agent type by rise like a raging fire, most of prior art
On, for the rare report of research of modified plant fibers enhancing.
There are some documents in the prior art, lignin is added in wood plastic composite.Such as patent
CN201810148584.5 discloses a kind of PVC- lignin-sulfate wood plastic composite and preparation method thereof, the wood moulding material
The formula of material includes the component of following mass parts: PVC100 parts, 5-150 parts of plant fiber, and 2-100 parts of lignin, sulfate 5-
100 parts, 2-15 parts of heat stabilizer, 0.1-10 parts of lubricant, 1-20 parts of anti-impact modifier, 1-15 parts of foaming agent, foaming is adjusted
8-25 parts of agent.Patent CN201710659376.7 discloses a kind of enhanced Wood-plastic material of lignin and preparation method thereof, wood moulding
Composite material by one of plant fiber, lignin, recycled thermoplastics, minerals powder, processing aid or it is a variety of form,
Extrusion process is granulated using screw rod to be process.Lignin and plant are added in the wood plastic composite of the above patent disclosure
Fiber is to improve mechanical property, thermal stability or the anti-aging property of composite material, but lignin and plant fiber are each other
Between compatibility it is poor, although they all contain hydroxyl, hydrogen bond can be formed and generate certain affinity, still fallen within weaker
Interface cohesion, so exist formed Wood plastic furniture material interface stress transfer it is bad, cause composite material impact resistance it is poor,
The problems such as poor dimensional stability, rigidity and toughness are unbalanced.And lignin is to handle to obtain by strong acid and strong base, active group
Less, interface binding power is caused further to decline.
In addition, with the rise of outdoor activities, especially outdoor furniture, such as it is plastic table, beach chair easy cleaning, easily contained
Product is generally welcomed by the people, but also consequent is influenced by chronic sun exposure, material aging, and mechanical performance is continuous
The problems such as reduction, white or light-colored product surface shows yellowing, is increasingly prominent, this service life for directly resulting in product constantly shortens,
Seriously affect the use value of product.In the prior art since lignin and plant fiber interface binding power are weak, wood is also resulted in
Plastic composite materials anti-aging property is deteriorated.Therefore, while the problem of improving the mechanical property and ageing-resistant performance of product need to solve
Certainly.
Summary of the invention
Wood plastic composite impact resistance, dimensional stability and resistance to ag(e)ing cannot in order to solve in the prior art by the present invention
Meet actual demand, and it is an object of the present invention to provide a kind of anti-aging impact-resistant modified wood plastic composite, excellent combination property can
Greatly improve the anti-aging property, impact resistance and dimensional stability of outdoor Wood plastic furniture, guarantee composite material rigidity and
Toughness is balanced, guarantees the beauty of outdoor furniture, prolongs the service life.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of anti-aging impact-resistant modified wood plastic composite, the raw material including following parts by weight: 20-50 parts of polyolefin,
Enzymatic hydrolysis (EH) lignin modified plant fiber 30-70 parts, 1-3.5 parts of newtrex, 0.1-10 parts of inorganic filler, antioxidant 0.1-4
Part, 0.1-3 parts of anti ultraviolet agent；
The enzymatic hydrolysis (EH) lignin modified plant fiber is to be obtained by enzymolysis xylogen and plant fiber by anhydride reaction.
The enzymolysis xylogen is to stalk etc. by microbial enzyme rich in separation and Extraction after lignocellulosic material enzymatic hydrolysis
It obtains, is handled during the preparation process without alkali acid, content of ashes is low in enzymolysis xylogen, preferably remains its chemical activity
And molecular structure.
The microbial enzyme is at least one of cellulase, hemicellulase and lignoenzyme, the microbial enzyme
Dosage is the 2-5wt% of stalk.
Present invention employs enzymatic hydrolysis (EH) lignin modified plant fibers, on the one hand consume a large amount of poles that plant fiber contains
Property group, make the reduction of its polarity, improve and the compatibility of non-polar, polyolefin resin, on the other hand, enzymolysis xylogen and plant
Fiber is the macromolecular substances with reticular structure, generates connection and certain winding by acid anhydrides, is formed compound netted
Structure, when material internal generates stress, this composite mesh structure can uniformly dissipate stress, be not in stress concentrate with
And stress concentrates caused interface premature failure that the dimensional stability of product is made to be deteriorated.Finally, enzymolysis xylogen preferably retains
Active group, is effectively promoted the binding force at interface, and facilitate the fixation of composite material each additive, auxiliary agent, from
And the intensity of composite material is improved, and at the same time improving the ageing resistance of composite material, reduces precipitation bring and unsightly ask
Topic.
Specifically, the preparation method of the enzymolysis xylogen the following steps are included:
Straw is smashed, plant straw powder pulp mixture is obtained, microbial enzyme is added and sufficiently digests, enzymatic hydrolysis is produced later
Object, which is filtered, dries and grinds, obtains residue powder, is extracted using the abundant dissolved residue powder of organic solvent, is filtered while hot
Filtrate is added water, stands precipitation enzymolysis xylogen sediment, obtains enzymolysis xylogen using filter, washing and drying.
Extraction preparation manipulation condition to enzymolysis xylogen is it is known in the art, in the above method, and described is organic
There is no particular limitation for solvent, as long as having certain solubility to destination agent, will not generate unfavorable shadow to raw material, product, reaction
Loud solvent can adducible example include but is not limited to be selected from dioxane, tetrahydrofuran, chloroform, dichloromethane
One of alkane, dimethylformamide, cyclohexanone, ethyl alcohol, isopropanol and acetone or more than one.
It controlled at 20-50 DEG C, pH 4-6, enzymolysis time 2-6h, preferably temperature is 30-40 DEG C when enzymatic hydrolysis, pH is
4.5-6.3 enzymolysis time 3-5h.
In enzymolysis xylogen preparation method of the present invention, mass ratio is used as the cellulose of 15-25:10-20:1-3
The compounding of enzyme, hemicellulase and lignoenzyme.Inventor it has been unexpectedly found that when compounding microbial enzyme cellulase,
The ratio of hemicellulase and lignoenzyme within the above range, the preparation enzymatic hydrolysis (EH) lignin modified plant fiber of gained and resin and
Compatibility between other compositions is best, can effectively improve the impact property and dimensional stability of composite material.
Preferably, there is no particular limitation that preferably flaxen fiber, the example of flaxen fiber includes but unlimited for the plant fiber
In one of ramie, flax, jute, hemp, mestha, coir, monkey grass, bamboo fibre or several.
The acid anhydrides is selected from maleic anhydride, alkylene succinic anhydride, methyl tetrahydro phthalic anhydride, glutaric anhydride, tetrahydro benzene
At least one of acid anhydride, hexahydrophthalic anhydride and dodecenylsuccinic acid acid anhydride.
The mass ratio of the enzymolysis xylogen, plant fiber and acid anhydrides is 10-15:8-12:2-4.
The preparation method of the enzymatic hydrolysis (EH) lignin modified plant fiber, includes the following steps:
(1) it is sufficiently swollen into 8-12 parts of plant fiber powders added with solvent；
(2) 10-15 parts of enzymolysis xylogens are added in the system being swollen to step (1), are stirred until homogeneous, are gradually added dropwise dissolved with 1-
The organic solvent solution of 10 parts of catalyst and 2-4 parts of acid anhydrides, isothermal reaction 2-6h；
(3) step (2) mixed system is filtered, is washed with deionized, it is dry, and be dried in vacuo again, control moisture
In 0.01-3%, enzymatic hydrolysis (EH) lignin modified plant fiber powder is obtained.
The catalyst is to dimethylamino naphthyridine or polyfluoro butyl sulfonic acid ammonium.
The organic solvent is selected from dioxane, tetrahydrofuran, chloroform, methylene chloride, dimethylformamide, ring
One of hexanone, ethyl alcohol, isopropanol and acetone or more than one.
Preferably, the plant fiber powder partial size of the step (1) is 50-100 mesh, and swelling temperature is 40-90 DEG C, when swelling
Between be 2-6h.
There is no particular limitation for polyolefin used in the present invention, and common polyolefin is all in quilt in wood plastic composite
In invention scope, the adducible example of polyolefin includes but is not limited to polyethylene, polypropylene or ethylene-propylene copolymer,
Molecular weight is 100,000-100 ten thousand.
Newtrex is based on dimer, and with lighter color, acid value is low, large viscosity, do not crystallize, softening point is high, compatibility
The features such as good, anti-oxidant excellent, durability is strong, newtrex partial size used is preferably 10-50 mesh in the present invention.
The inorganic filler is at least one of nano silica, nano-titanium dioxide, nanometer calcium carbonate, and inorganic fills out
Material is amino-alkyl silicane coupling agent for nano silica, nano-titanium dioxide modified coupling agent by coupling agent modified,
Such as the mixture of KH-550 or A-1110 or both；Modifying agent for nanometer calcium carbonate is titanate coupling agent, such as
Isopropyl tri(dioctylphosphato)titanate, three (dioctyl, pyrophosphoric acid oxygroup) isopropyl titanates and two (dioctyl phosphinylidyne oxygen
Base) metatitanic acid second diester；Preferably, the inorganic filler is at least one of nano silica and nano-titanium dioxide and receives
The compounding of rice calcium carbonate, wherein nano silica and/or nano-titanium dioxide and the mass ratio of nanometer calcium carbonate are 1:1-3.
The anti ultraviolet agent is hindered amines organic matter, including but not limited to 622,770,944,783,791,3853,292
And at least one of light stabilizer 123；And/or the antioxidant includes p-alkoxy phenol and Hinered phenols organic matter, packet
Include but be not limited at least one in p-alkoxy phenol, antioxidant 1010, antioxidant 1098, antioxidant 264 and antioxidant 300
Kind.
As currently preferred technical solution, in addition to above-mentioned main component, wood plastic composite of the invention can be with
Contain other auxiliary components, including but not limited to lubricant, compatilizer, heat stabilizer, toughener；The dosage of the auxiliary agent is such as
Lower mass parts: 2-10 parts of lubricants, 1-8 parts of compatilizers, 1-10 parts of heat stabilizers and 3-6 parts of toughener；The lubricant includes
At least one of stearic acid, calcium stearate, zinc stearate or PE wax；And/or the compatilizer is modified by maleic acid anhydride graft
The combination of polypropylene or modified by maleic acid anhydride graft polyethylene or both；And/or the heat stabilizer is organic tin thermostabilization
At least one of agent, metal soap thermal stabilizers；And/or the toughener be selected from ethylene-vinyl acetate copolymer, hydrogenation
Ethylene-butadiene-styrene copolymer, styrene-butadiene-styrene, hydrogenation styrene-butadiene-benzene second
Alkene copolymer, ethylene propylene diene rubber and the numerous at least one of polyurethane.
The present invention also provides the preparation methods of above-mentioned anti-aging impact-resistant modified wood plastic composite, including walk as follows
It is rapid:
Inorganic filler, anti ultraviolet agent, antioxidant, enzymatic hydrolysis (EH) lignin modified plant fiber are sufficiently mixed uniformly, mixed
Material 1；The polyethylene is added to mixing machine and obtains mixing 2, mixing 2 is input to mixing in mixing device；What mixing generated
Material strip obtains the anti-aging impact-resistant modified wood plastic composite through supercooling, granulation, drying process step.
Compared with prior art the invention has the advantages that
One, anti-aging impact-resistant modified wood plastic composite provided by the present invention, by using addition enzymolysis xylogen
Modified plant fibers significantly improve plant fiber and resin base material interface binding power in composite material, so that the wood moulding formed
Furniture material excellent combination property is embodied in affinity height between plant fiber and plastics, and interfacial stress transmitting is good, into
And dimensional stability is high, rigidity and toughness are balanced, while ageing resistance also has promotion.As furniture composite material, surface aesthetic,
It is environmentally friendly, durable, pollution-free simultaneously.
Two, the present invention is creatively utilized enzymolysis xylogen and removes modified plant fibers, that is, efficiently solves wood plastics composite
The weak problem of the affinity of plant fiber and resin base material in material, while the enzymolysis xylogen introduced is natural products, it is nontoxic
Evil, obtained wood plastic composite be it is a kind of it is environmentally protective, using safe material, meet modern furniture and add to chemistry is reduced
Add the requirement of agent dosage.Enzymatic hydrolysis (EH) lignin modified plant fiber, which can not only improve, to be also beneficial to improve and modified inorganic object is consolidated
It is fixed, it reduces the migration of inorganic matter and migrates bring unsightly problem.
Three, a certain amount of lignoenzyme is added it has been unexpectedly found that during preparing enzymolysis xylogen in inventor,
It can be improved the impact resistance and dimensional stability of wood plastic composite prepared by enzymatic hydrolysis (EH) lignin modified plant fiber.
Four, lignin is from a wealth of sources, and storage is abundant, cheap and easy to get.Stalk of China's processing at present rich in lignin is made
If owner burns, the serious wasting of resources and problem of environmental pollution are caused.It is provided by the invention to utilize lignin modification plant
Fiber process makes full use of Liginon Resource, turns waste into wealth, and realizes the comprehensive utilization of Liginon Resource.
Specific embodiment
Below in conjunction with specific embodiment to the anti-aging impact-resistant modified wood plastic composite of one kind provided by the invention do into
The explanation and illustration of one step.Number described in embodiment is unless otherwise specified parts by weight.If reagent without specified otherwise,
It is the commercially available reagent in this field.
Special emphasis is specific plant fiber and additive used in the embodiment of the present invention, such as antioxygen
The type of agent, anti ultraviolet agent, modifying agent and lubricant etc. is to probe into enzymatic hydrolysis (EH) lignin modified plant fiber to composite material
Performance influence, therefore, the type of specific plant fiber and additive used in embodiment etc. should not be constituted to the present invention
A kind of limitation of protection scope, those skilled in the art will be seen that, the fiber of separate sources, as long as being total to plant fiber
Same structure division may be by the modification that method provided by the invention carries out enzymolysis xylogen, in addition, with similar functions
The purpose of the present invention also can be achieved in other auxiliary agents such as antioxidant, anti ultraviolet agent, lubricant, also in protection scope of the present invention
It is interior.
Hemicellulase used in following embodiment of the present invention is the production of Hubei Kang Baotai Fine Chemical Co., Ltd, enzyme activity
Ten thousand U/g of 350-500；Ten thousand u/kg of lignoenzyme enzyme activity 50-150, ten thousand u/kg of cellulose enzyme activity 100-300 used, be Ningxia and
The production of Shi Bi Bioisystech Co., Ltd.
The preparation of the enzymatic hydrolysis (EH) lignin modified plant fiber of preparation example
Preparation example 1
1) preparation of enzymolysis xylogen
(1) corn stover is smashed, obtains straw slurry；
(2) by the vitamins enzyme and hexa-hydrochloride buffer (pH=5.4) of slurry obtained by step (1), compounding
It is added to enzymatic hydrolysis room, hydrolysis temperature is at 37 DEG C, sufficiently enzymatic hydrolysis 6h；It is 15:20 that wherein the microbial enzyme of the compounding, which is mass ratio:
1 cellulase, hemicellulase and lignoenzyme, compounding microbial enzyme dosage are the 5wt% of corn stover.
(3) step (2) enzymolysis product is squeezed, is filtered, is dried in vacuo and ground and obtain residue powder, gained filtrate is used
In distillation separating alcohol；
(4) 40 DEG C are heated in circulation microwave using organic solvent, abundant dissolved residue powder is extracted, and filters to obtain filter while hot
Liquid is added excessive deionized water, stands precipitation enzymolysis xylogen sediment, obtains enzymolysis xylogen using filter, washing and drying.
2) preparation of enzymatic hydrolysis (EH) lignin modified plant fiber
(1) 250 parts of dioxane are added into 80 parts of 10-30 mesh ramee powder, 60 DEG C of constant temperature, 6h carries out sufficiently molten
It is swollen；
(2) 100 parts of enzymolysis xylogens are added to step (1) mixed system, are stirred until homogeneous, are gradually added dropwise and are urged dissolved with 5 parts
Dioxane solution of the agent to dimethylamino naphthyridine and 20 parts of glutaric anhydrides, isothermal reaction 5h；
(3) step (2) mixed system is filtered, be washed with deionized and dry to obtain enzymatic hydrolysis (EH) lignin modified ramie fibre
Dimension, is ground to 50-200 mesh, is dried in vacuo again, controls moisture in 0.01%-3%, obtains enzymatic hydrolysis (EH) lignin modified ramie for use
Fiber powder, referred to as modified fibre 1.
Preparation example 2
Remaining is identical as preparation example 1, and difference is to compound microbial enzyme cellulase, hemicellulase and lignoenzyme
Mass ratio be 15:20:3, obtain enzymatic hydrolysis (EH) lignin modified plant fiber, hereinafter referred to as modified fibre 2.
Compare preparation example 1
Remaining is identical as preparation example 1, and difference, which is to compound in microbial enzyme, does not add lignoenzyme, cellulase, half fiber
The mass ratio for tieing up plain enzyme is 15:20, obtains enzymatic hydrolysis (EH) lignin modified plant fiber, hereinafter referred to as modified fibre 3.
Preparation example 3
Remaining is identical as preparation example 1, and difference is that straw is flax, obtains enzymatic hydrolysis (EH) lignin modified plant fiber,
Hereinafter referred to as modified fibre 4.
Compare preparation example 2
Remaining is identical as preparation example 1, and difference is to compound microbial enzyme cellulase, hemicellulase and lignoenzyme
Mass ratio be 15:20:0.5, obtain enzymatic hydrolysis (EH) lignin modified plant fiber, hereinafter referred to as modified fibre 5.
Compare preparation example 3
Remaining is identical as preparation example 1, and difference is to compound microbial enzyme cellulase, hemicellulase and lignoenzyme
Mass ratio be 15:20:6, obtain enzymatic hydrolysis (EH) lignin modified plant fiber, hereinafter referred to as modified fibre 6.
Preparation example 4
Remaining is identical as preparation example 1, and difference is that the dosage for compounding microbial enzyme is the 2wt% of corn stover, hereinafter referred to as
For modified fibre 7.
The preparation of embodiment wood plastic composite
Embodiment 1
Formula: molecular weight is 40 parts of polyethylene of 500,000,60 parts of modified fibres 1,1 part of newtrex, 0.5 part of hindered amine light
622,0.5 part of antioxidant 1010 of stabilizer, 0.8 part of A-1110 modified manometer silicon dioxide, KH-550 modified nano-titanium dioxide 1
Part, 1 part of titanate coupling agent modified nanometer calcium carbonate, 0.5 part of p-alkoxy phenol, 3 parts of MA-g-PP compatilizer, calcium stearate 2
Part, 3 parts of ethylene-vinyl acetate copolymer.
Preparation method: mixing: A-1110 modified manometer silicon dioxide, KH-550 modified nano-titanium dioxide, titanate esters are even
Join agent modified nano calcium carbonate, antioxidant 1010, p-alkoxy phenol, hindered amine light stabilizer 622, calcium stearate, modified fibre
Mixing machine is added in dimension 1, and with 1000r/min, mixed at high speed is uniform at 90 DEG C, and incorporation time 15min obtains mixing 1；
The polyethylene and MA-g-PP compatilizer are added in mixing machine it is uniform with 1500r/min mixed at high speed,
Mixed at high speed is uniform at 120 DEG C, and incorporation time 30min obtains mixing 2；
Mixing 1 and mixing 2 are input in mixing device by screw conveying pipe after mixing；
Mixing: the mixture is smelted in mixing device, then exports strip material by die head；
Pre-cooling: the strip material conveys under the action of pulling equipment and material strip guide rail along cooling bath length direction, is set to
Pre-cooling pipe above cooling bath carries out material strip to spray preliminary cooling；
It is cooling: to complete tentatively cooling material strip and enter cooling tube, the cooling tube is interior by pumping conveying coolant for ice chest
Bulging die carries out package cooling to strip material, while carrying out compactly extruding to strip material；
It is gradually cold: to complete the cooling strip material into gradually cold pipe and carry out spraying cooling to room temperature；
It is granulated: completing gradually cold material strip input stock-cutter and carry out blank, it is multiple to obtain the anti-aging impact-resistant modified wood moulding
Condensation material.
Embodiment 2
Other are same as Example 1, and difference is in formula that modified fibre 1 is 80 parts.
Embodiment 3
Other are same as Example 1, and difference is in formula that modified fibre 1 is 100 parts.
Embodiment 4
Other are same as Example 2, and difference is in formula that modified fibre 1 replaces with modified fibre 2.
Embodiment 5
Other are same as Example 2, and difference is in formula that modified fibre 1 replaces with modified fibre 4.
Embodiment 6
Other are same as Example 2, and difference is in formula that modified fibre 1 replaces with modified fibre 7.
Comparative example 1
Other are same as Example 2, and difference is that fiber used is modified fibre 3.
Comparative example 2
Other are same as Example 2, and difference is nano silica in formula, nano-titanium dioxide, titanium nano-calcium carbonate
Calcium is without coupling agent modified.
Comparative example 3
Other are same as Example 2, difference be to be formulated in modified fibre 1 used replace with 80 parts of 10-30 mesh ramie
Powder and 100 parts of enzymolysis xylogens.
Comparative example 4
Other are same as Example 2, and difference is that fiber used is modified fibre 5.
Comparative example 5
Other are same as Example 2, and difference is that fiber used is modified fibre 6.
Mechanics Performance Testing, xenon lamp accelerated ageing and dimensional stability are carried out to above embodiments and comparative example resulting materials
Test, detailed test method is as follows, and test result is shown in Table 1.
Tensile property test
Tensile property GB/T 1040-2006 specimen shape is dumbbell shape, and rate of extension 50mm/min, specimen width is
10mm(±0.3mm)。
Impact property test
Impact property GB/T1043.1-2008 test, non-notch, Charpy impact energy are 2J, impact velocity 2.9m/
Sec, 130 ° of pendulum angle, specimen size 80mm × 10mm × 4mm.
Xenon lamp accelerated ageing test
Xenon lamp radiation spectral power distribution and daylight are close, working condition influenced by change of external conditions it is small, therefore can
For testing the durability energy of wood plastic composite.Testing procedure: standard batten is put into accelerated ageing in xenon lamp aging case, always
Changing the time is four periods (one week is a cycle), and experimental situation is air atmosphere, 55 DEG C of cavity temperature, outside wall temperature 38
DEG C, cavity humidity (50 ± 5) %, lamp source test coupon 10cm, xenon lamp wavelength are 290mm-800mm, and xenon lamp power of lamp tube is
1800W, power density 1.10W/m2。
Dimensional shrinkage under heat test
The degree of change in size is characterized using Dimensional shrinkage under heat after heated, and sample full-length is 250mm,
Two stripe pitch are drawn on visible surface as defined in sample as the graticule of 200mm, one end spacing of each of them graticule and sample is
25mm.It is 100 DEG C that sample, which is placed vertically, and sets temperature (62 ± 1) heating temperature, heating time 60min.Dimensional shrinkage under heat
Formula are as follows: DEG C, standing time (24 ± 0.5) h.
R- Dimensional shrinkage under heat in formula, %；
L0Heat the distance between preceding two fulcrum, mm；
L1Distance after heating between two fulcrums, mm；
Cold-resistant thermal cycle test
Reference standard: GB/T 24508-2009, specimen size 40mm × 40mm × 5mm.Test method:
It is dipped in a little ethyl alcohol with absorbent gauze and is cleaned surface of test piece and dried.It is drawn on each sample and is parallel to length direction
Center line, and measuring center line length L1。
Carry out high/low temperature 3 periodic tests repeatedly.It is as follows:
Then it is placed 6 hours or more at a temperature of (23 ± 2) DEG C, tries appearance, and measuring center with range estimation under available light
Length L2。
The change in size △ L of each sample is calculated by formula,
△ L=L2-L1
In formula:
The variation of △ L- specimen size, mm；
The size of L2- sample after experiment, mm；
The size of L1- sample before the test, mm；
Table 1
As can be seen from Table 1 using the composite material tensile strength of enzymatic hydrolysis (EH) lignin modified plant fiber, elongation at break
It is all obviously improved with impact strength, the phenomenon that toughness promotion, rigid sacrificial is not occurred, the shock resistance of composite material,
Anti-aging property is preferably and dimensional stability is relatively good.Inventor it has been unexpectedly found that when being digested to lignin,
A certain amount of lignoenzyme is added, the affinity that can be effectively improved between lignin and plant fiber, to wood plastic composite
Mechanical property and anti-aging property have clear improvement.Without adding, lignoenzyme or lignoenzyme additive amount be excessive or mistake
It is few, it all cannot achieve the effect of wood plastic composite overall performance optimization of the present invention.Meanwhile the present invention also carries out inorganic filler
The modification of coupling agent, and the preferred wherein type of inorganic filler proportion and coupling agent so that composite material anti-aging and
Mechanical performance is improved.The anti-aging and shock resistance of composite material prepared by unmodified plant fiber is relatively modified
Inorganic filler or modification plant fiber preparation composite material be greatly reduced.The use of enzymatic hydrolysis (EH) lignin modified plant fiber
Amount has significant impact to the anti-aging property of composite material.
Above-mentioned detailed description is illustrating for one of them possible embodiments of the present invention, and preferred embodiment is not
To limit the scope of the patents of the invention, all equivalence enforcements or change without departing from carried out by the present invention are intended to be limited solely by the present invention
In the range of technical solution.
Claims (10)
1. a kind of anti-aging impact-resistant modified wood plastic composite, which is characterized in that the raw material including following parts by weight: polyolefin
20-50 parts, enzymatic hydrolysis (EH) lignin modified plant fiber 30-70 parts, 1-3.5 parts of newtrex, 0.1-10 parts of inorganic filler are anti-oxidant
0.1-4 parts of agent, 0.1-3 parts of anti ultraviolet agent, the enzymatic hydrolysis (EH) lignin modified plant fiber are fine by enzymolysis xylogen and plant
Dimension is obtained by anhydride reaction.
2. modified composite material of woods and plastics as described in claim 1, which is characterized in that the enzymolysis xylogen is to pass through microbial enzyme
Obtained to rich in separation and Extraction after lignocellulosic material enzymatic hydrolysis, the microbial enzyme be cellulase, hemicellulase and
At least one of lignoenzyme, the microbial enzyme dosage are the 2-5wt% of stalk；Preferably, microbial enzyme is cellulose
The mixture that enzyme, hemicellulase and lignoenzyme are 15-25:10-20:1-3 according to mass ratio.
3. modified composite material of woods and plastics as claimed in claim 2, which is characterized in that the preparation method packet of the enzymolysis xylogen
Include following steps:
Straw is smashed, plant straw powder pulp mixture is obtained, microbial enzyme is added and sufficiently digests, enzymolysis product was carried out
Filter, dry and grinding obtain residue powder；
It is extracted using the abundant dissolved residue powder of organic solvent, is filtered to get filtrate while hot, it is wooden that water, standing precipitation enzymatic hydrolysis is added
Plain sediment obtains enzymolysis xylogen using filter, washing and drying.
4. modified composite material of woods and plastics as described in claim 1, which is characterized in that in the enzymatic hydrolysis (EH) lignin modified plant fiber
Plant fiber be flaxen fiber, preferably ramie, flax, jute, hemp, mestha, coir, monkey grass, in bamboo fibre
It is one or several kinds of.
5. modified composite material of woods and plastics as described in claim 1, which is characterized in that the acid anhydrides is selected from maleic anhydride, alkene
In hydrocarbyl succinimide acid anhydrides, methyl tetrahydro phthalic anhydride, glutaric anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and dodecenylsuccinic acid acid anhydride extremely
Few one kind.
6. modified composite material of woods and plastics as described in claim 1, which is characterized in that the enzymolysis xylogen, plant fiber and acid
The mass ratio of acid anhydride is 10-15:8-12:2-4.
7. modified composite material of woods and plastics as described in claim 1, which is characterized in that the polyolefin includes polypropylene, polyethylene
And at least one of ethylene-propylene copolymer, molecular weight are 100,000-100 ten thousand.
8. modified composite material of woods and plastics as described in claim 1, which is characterized in that the inorganic filler by coupling agent modified,
For at least one of nano silica, nano-titanium dioxide, nanometer calcium carbonate, preferably nano silica and nanometer two
The compounding of at least one of titanium oxide and nanometer calcium carbonate, wherein nano silica and/or nano-titanium dioxide and nanometer
The mass ratio of calcium carbonate is 1:1-3；It is described to be selected from ammonia alkyl for the coupling agent of nano silica and/or nano-titanium dioxide
Silane coupling agent, the coupling agent for nanometer calcium carbonate are selected from titanate coupling agent.
9. modified composite material of woods and plastics as described in claim 1, which is characterized in that the wood plastic composite further includes 2-10 parts
Lubricant, 1-8 part compatilizer, 1-10 parts of heat stabilizers and 3-6 parts of toughener.
10. the preparation method of wood plastic composite, includes the following steps: as described in claim 1-9
(1) inorganic filler, anti ultraviolet agent, antioxidant, enzymatic hydrolysis (EH) lignin modified plant fiber and other auxiliary agents are sufficiently mixed
Uniformly, mixing 1 is obtained；Polyolefin is added in mixing machine and is mixed to get mixing 2, mixing 1 and mixing 2 are input to mixing dress
Set interior mixing；
(2) it is multiple through supercooling, granulation, drying process step to obtain the anti-aging impact-resistant modified wood moulding for the material strip that mixing generates
Condensation material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662108A (en) * | 2020-12-23 | 2021-04-16 | 安徽绿之态新材料有限公司 | Whisker reinforced straw fiber environment-friendly furniture material and furniture |
| CN112708257A (en) * | 2020-12-31 | 2021-04-27 | 宁波能之光新材料科技股份有限公司 | High-elasticity wear-resistant outdoor wood-plastic surface layer material and preparation method thereof |
| CN113305959A (en) * | 2021-06-24 | 2021-08-27 | 东北林业大学 | Method for improving size stability of fast-growing wood by using lignin-based modified liquid medicine |
| CN113480780A (en) * | 2021-06-07 | 2021-10-08 | 山东路德新材料股份有限公司 | Bio-based three-dimensional geonet pad and preparation method thereof |
| CN118063873A (en) * | 2024-04-24 | 2024-05-24 | 泉州兴源新材料科技有限公司 | Composite anti-aging agent modified polyethylene material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982322A (en) * | 2005-09-05 | 2007-06-20 | 福州大学 | Method for organically separating and extracting enzymic lignin |
| CN102051002A (en) * | 2010-12-02 | 2011-05-11 | 东北林业大学 | Zymolytic lignin-wood fiber-polyolefin hybrid composite material and preparation method thereof |
| CN103224661A (en) * | 2013-04-26 | 2013-07-31 | 华南理工大学 | Polyolefin/enzymatic-hydrolyzed lignin composite material and preparation method thereof |
| CN106189325A (en) * | 2016-08-04 | 2016-12-07 | 南京工业大学 | Lignin-enhanced wood-plastic material and preparation method thereof |
| CN106883376A (en) * | 2017-02-21 | 2017-06-23 | 江苏迪因生物科技有限公司 | The preparation method of enzymolysis xylogen base epoxy |
| CN108117652A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of extracting method of enzymolysis xylogen |
| CN109294055A (en) * | 2018-08-30 | 2019-02-01 | 福建工程学院 | A kind of preparation method of the modified tossa PP composite material of lignin-graphene |
-
2019
- 2019-07-22 CN CN201910659537.1A patent/CN110283472B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982322A (en) * | 2005-09-05 | 2007-06-20 | 福州大学 | Method for organically separating and extracting enzymic lignin |
| CN102051002A (en) * | 2010-12-02 | 2011-05-11 | 东北林业大学 | Zymolytic lignin-wood fiber-polyolefin hybrid composite material and preparation method thereof |
| CN103224661A (en) * | 2013-04-26 | 2013-07-31 | 华南理工大学 | Polyolefin/enzymatic-hydrolyzed lignin composite material and preparation method thereof |
| CN106189325A (en) * | 2016-08-04 | 2016-12-07 | 南京工业大学 | Lignin-enhanced wood-plastic material and preparation method thereof |
| CN108117652A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of extracting method of enzymolysis xylogen |
| CN106883376A (en) * | 2017-02-21 | 2017-06-23 | 江苏迪因生物科技有限公司 | The preparation method of enzymolysis xylogen base epoxy |
| CN109294055A (en) * | 2018-08-30 | 2019-02-01 | 福建工程学院 | A kind of preparation method of the modified tossa PP composite material of lignin-graphene |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662108A (en) * | 2020-12-23 | 2021-04-16 | 安徽绿之态新材料有限公司 | Whisker reinforced straw fiber environment-friendly furniture material and furniture |
| CN112662108B (en) * | 2020-12-23 | 2023-08-15 | 安徽绿之态秸秆制品有限公司 | Whisker reinforced straw fiber environment-friendly furniture material and furniture |
| CN112708257A (en) * | 2020-12-31 | 2021-04-27 | 宁波能之光新材料科技股份有限公司 | High-elasticity wear-resistant outdoor wood-plastic surface layer material and preparation method thereof |
| CN112708257B (en) * | 2020-12-31 | 2022-06-17 | 宁波能之光新材料科技股份有限公司 | High-elasticity wear-resistant outdoor wood-plastic surface layer material and preparation method thereof |
| CN113480780A (en) * | 2021-06-07 | 2021-10-08 | 山东路德新材料股份有限公司 | Bio-based three-dimensional geonet pad and preparation method thereof |
| CN113480780B (en) * | 2021-06-07 | 2022-09-02 | 山东路德新材料股份有限公司 | Bio-based three-dimensional geotechnical net pad and preparation method thereof |
| CN113305959A (en) * | 2021-06-24 | 2021-08-27 | 东北林业大学 | Method for improving size stability of fast-growing wood by using lignin-based modified liquid medicine |
| CN113305959B (en) * | 2021-06-24 | 2022-02-25 | 东北林业大学 | Method for improving size stability of fast-growing wood by using lignin-based modified liquid medicine |
| WO2022267319A1 (en) * | 2021-06-24 | 2022-12-29 | 东北林业大学 | Method for improving dimensional stability of fast-growing wood by using lignin-based modified liquor |
| CN118063873A (en) * | 2024-04-24 | 2024-05-24 | 泉州兴源新材料科技有限公司 | Composite anti-aging agent modified polyethylene material and preparation method thereof |
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