CN105255207B - A kind of modified natural fibers composite and preparation method thereof - Google Patents
A kind of modified natural fibers composite and preparation method thereof Download PDFInfo
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- CN105255207B CN105255207B CN201510661321.0A CN201510661321A CN105255207B CN 105255207 B CN105255207 B CN 105255207B CN 201510661321 A CN201510661321 A CN 201510661321A CN 105255207 B CN105255207 B CN 105255207B
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Abstract
The present invention provides a kind of modified natural fibers composite and its processing method, belongs to field of compound material.The composite is to obtain natural fiber after modified and UPE/ polypropylene composite materials；The natural fiber of described modification is first to be placed on natural fiber in NaOH solution to be handled, then is placed in cationic surfactant solution and carries out chemical modification, is then placed in atmosphere, then dry and obtain.The present invention also provides a kind of preparation method of natural-fiber composite material.The natural fiber of the present invention is modified using Aqueous phase, carrying out chemical modification to fiber by sodium hydroxide and aqueous solution of cationic surfactant active increases the hydrophobicity of fiber, so as to improve the moisture pick-up properties of natural-fiber composite material and interface performance, while also it is improved the mechanical property of material.
Description
Technical field
The present invention relates to field of compound material, and in particular to a kind of modified natural fibers composite and preparation method thereof.
Background technology
Natural-fiber composite material is a kind of composite wood using natural fiber as reinforcing material using resin or plastics as matrix
Material.Natural fiber mainly has mestha, jute, flax, hemp, sisal hemp, abaca, bluish dogbane, ramie, hemp, wood-fibred, bamboo fine
Dimension, coir, cotton, bombax cotton, soya bean stalk, millet stalk, cigarette stalk, Cotton Stalk, sunflower stalk, hemp stalk, sorghum stalk, straw wheat
Stalk, maize straw, triticale stalk, wheat stalk, and using cellulose as the naturally occurring of Main Ingredients and Appearance or the fiber of growth
Or the cloth that fibrage obtains.With density is small, price is low, degradable, non-stimulated to body, recyclable regenerative, to processing set
Standby the advantages that low small, aboundresources, power consumption of polymer processing, energy-conserving and environment-protective are lost, and the strength and stiffness with general fiber, and than strong
Degree, proportion is smaller, specific stiffness is higher.Composites using natural fiber as enhancing base have excellent performance, with
The extension of this theme of raw material sustainable development, natural fiber play more and more important angle in field of compound material is strengthened
Color.At present automobile, building materials, furniture, packaging material, dress material etc. are had been applied in using the compound composite of natural fiber
Field.(referring to Ni Jingda, Yu Husheng, natural plant fibre strengthens the research application of composite, chemical fibre and textile technology,
2006,2：29)
The content of natural fiber main component cellulose accounts for more than 50%, plays main mechanical support.But due to fiber
More hydroxyl is carried on plain chain, so with very strong hydrophily and hygroscopicity.
Plastics can be classified as thermoplastic and thermosetting plastics by physical and chemical performance classification.Thermoplastic
Molecular structure is linear or branched chain type structure, the fusible cooling solidifiable when heated, again can be soft when being heated to certain temperature
It is being hardened after changing cooling, this process can be repeated.Such as：Polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyformaldehyde.
Thermosetting plastics can also soften when heated, and sizing will be hardened when being heated to certain temperature, and reheating will not also soften, its
Molecular structure is finally three-dimensional-structure.Such as：Phenolic resin, epoxy resin, unsaturated polyester (UP).
Polypropylene and unsaturated polyester (UP) are typical thermoplasticity and thermosetting resin respectively.
Polypropylene is polymerized by monomer of propylene.A kind of important general-purpose plastics, have non-toxic, transparency is high,
It is resistant to chemical etching, density is small, relative hardness is high, and has good injection performance, its application field constantly expands, is widely used in
The fields such as automobile, building materials, weaving, household electrical appliances packaging material.The surface treatment and its enhancing of Liu Xiaoye, Dai Gance in jute felt
NaOH processing is first carried out in the research of the mechanical property of PP composite material to fiber surface, then carries out MAPP emulsion processing,
Make the untreated increase by 68% of bending strength ratio, tensile strength is than untreated increase by 48%.Illustrate MAPP emulsions be flaxen fiber with
Good interfacial compatibilizer between polypropylene.But its complex production process, the grafting rates of MAPP emulsions be only 5% or so (referring to
Liu Xiaoye, wears the surface treatment of dry plan jute felts and its mechanical property of reinforced polypropylene compound material, and 2006,23
(5)：63-69).
Unsaturated polyester (UP)（UPE）Resin is usually the dihydric alcohol or monounsaturated dicarboxylic acid insatiable hunger by undersaturated binary acid saturation
With dihydric alcohol through linear polymer of the polycondensation synthesis with ester bond unsaturated bond.Usage amount of the UPE resins in thermosetting resin
It is very big, while the usage amount in the production of glass fiber reinforcement engineering plastics is also very big.Unsaturated polyester resin has mouldability
And manufacturability is good, viscosity, thixotropy, working life, being air-dried property etc. are all adjustable；There is preferable mechanical property, corrosion-resistant
Performance and electric property；Coloring is freely；It is easy to different reinforcing materials, filler combination obtains the composite product of different qualities；
It is cheap and reduce a series of methods of cost and be easy to investment and production.It has been widely used in building, chemical industry, ship
The fields such as oceangoing ship, automobile, tables and chairs, sanitary ware.（Referring to Zhang little Ping, unsaturated polyester resin and its new development, 2008,2：23-
29.Referring to Song Yubo, the production and application of unsaturated polyester resin, 1999,20 (3)：20-23）
The content of the invention
The present invention provides a kind of natural-fiber composite material and preparation method thereof, and the natural-fiber composite material has good
Moisture pick-up properties and mechanical property.
Present invention firstly provides a kind of natural-fiber composite material, the composite is not by modified natural fiber and not
Saturated polyester（UPE）Obtained from/polypropylene composite materials；
Described modified natural fiber is first to be placed on natural fiber in NaOH solution to react, then is placed on cation
React in surfactant solution, then place in atmosphere, then dry and obtain.
Preferably, the source of described natural fiber be mestha, jute, flax, hemp, sisal hemp, abaca, bluish dogbane,
Ramie, hemp, wood-fibred, bamboo fibre, coir, cotton, bombax cotton, soya bean stalk, millet stalk, cigarette stalk, Cotton Stalk, sunflower
Stalk, hemp stalk, sorghum stalk, straw straw, maize straw, triticale stalk or wheat stalk.More preferably flax.
Preferably, the cationic surfactant be eight alkyl trimethyl ammonium chlorides, decyl trimethyl ammonium chloride,
DTAC, tetradecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl
Ammonium chloride, double octyl alkyl dimethyl ammonium chlorides, didecyl Dimethy ammonium chloride, dioctadecyl dimethyl ammonium chloride, three second
Methyl ammonium, tripropyl ammonio methacrylate, tributyhnethylammonium chloride, tri-n-octyl methyl ammonium chloride, tetramethyl ammonium chloride,
Etamon chloride, tetrabutylammonium chloride, benzyltriethylammoinium chloride, benzyltrimethylammonium chloride, tetramethyl Ammonium hydrogen sulfate, four
Butylammonium bromide, 4-propyl bromide, tetraethylammonium bromide, 4 bromide, tributyl-methyl phosphonium ammonium bromide, tricaprylmethyl
Ammonium bromide, DDA, didodecyldimethylammbromide bromide, didecyl Dimethy ammonium bromide, ten
Eight alkyl trimethyl ammonium bromides, cetyl trimethylammonium bromide, TTAB, eight alkyl trimethyl brominations
Ammonium, ten alkyl trimethyl ammonium bromides, DTAB, N, N- diethyl-（3 ＇-methoxybenzene oxygen ethyl）Benzyl
Ammonium chloride etc..More preferably Cetyltrimethylammonium bromide.
Preferably, described NaOH solution mass fraction is 1-5% and cationic surfactant solution mass fraction is
2-6%.Preferably, the described reaction time is 5-60min.
The present invention also provides a kind of preparation method of natural-fiber composite material, including：
Step 1：Natural fiber is first placed in NaOH solution and is modified processing, then is placed on cation surface activating
Processing is modified in agent solution, is then placed in atmosphere, then dries the natural fiber being modified；
Step 2：By the natural fiber being modified and UPE/ polypropylene composite materials, natural-fiber composite material is obtained.
Preferably, the described natural fiber being modified and the compound methods of UPE are：
UPE resins, curing agent, accelerator and defoamer are mixed, mixture is obtained, mixture is coated in modified mistake
Natural fiber on, natural-fiber composite material is obtained after curing molding.
Preferably, described UPE resins, curing agent, accelerator and defoamer be according to mass fraction meter, including：
UPE resin 90-100 parts, curing agent 0.10-3 parts, accelerator 0.01-0.5 parts, defoamer 0-10 parts.
Preferably, described curing agent includes methyl ethyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, mistake
BP, peroxidating first isobutyl ketone, isopropyl benzene hydroperoxide, TBHP, 2,4- dichlorobenzoperoxides
Or dilauroyl peroxide.
Preferably, the described natural fiber of modified mistake and the method for polypropylene composite materials are：
Polypropylene, coupling agent and the natural fiber that was modified are processed by pressure sintering to obtain natural-fiber composite material.
Preferably, described coupling agent is that maleic anhydride inoculated polypropylene, maleic anhydride grafted ABS, maleic anhydride connect
Branch polyethylene, dimerization di (isooctyl) phosphate magnesium stearate, DL series aluminate coupling agent, powder silane coupler XH-820 systems
Row, maleic anhydride grafting EVA, TC-130, aminopropyl triethoxysilane, methacryloxypropyl trimethoxy silane,
Glycydoxy trimethoxy silane, VTES, ethylenediaminepropyltriethoxysilane, thin third
Base trimethoxy silane, ethylenediamine hydroxypropyl methyl dimethoxysilane.
Beneficial effects of the present invention
The present invention first provides a kind of natural-fiber composite material, and the composite is the natural fiber and UPE/ that will be modified
Obtained from polypropylene composite materials；The described natural fiber being modified is first to be placed on natural fiber in NaOH solution to be changed
Learn and be modified, then be placed in cationic surfactant solution progress chemical modification processing, then place in atmosphere, then dry and
.The natural fiber of the present invention is handled using Aqueous phase, by sodium hydroxide and cationic surfactant solution to fibre
Dimension carries out the hydrophobicity of chemical modification increase fiber, so as to improve the moisture absorption of natural-fiber composite material and interface performance, simultaneously
Also the mechanical property of composite is made to be improved.
The present invention also provides a kind of processing method of natural-fiber composite material, and the processing method raw material is easy to get, technique letter
Single, prepared composite has good moisture pick-up properties and mechanical property.
Brief description of the drawings
Fig. 1 is the infrared of obtained modified natural fibers linen and untreated linen in the embodiment of the present invention 1,2
Spectrogram.
Fig. 2 is the water absorption rate figure of modified natural fibers linen and untreated linen in the embodiment of the present invention 1,2.
Fig. 3 is modified natural fibers linen and untreated linen/UPE composite woods in the embodiment of the present invention 1,2
Expect water absorption rate figure.
Fig. 4 is that modified natural fibers linen and untreated linen/PP are multiple in comparative example 2 of the present invention and embodiment 5
Condensation material water absorption rate figure.
Embodiment
Present invention firstly provides a kind of natural-fiber composite material, the composite be the natural fiber that will be modified and
Obtained from UPE/ polypropylene composite materials；
The described natural fiber being modified is first to be placed on natural fiber in NaOH solution to react, then is placed on cation
React in surfactant solution, then place in atmosphere, then dry what is obtained.
According to the present invention, described natural fiber is the fibre obtained using cellulose as the naturally occurring of Main Ingredients and Appearance or growth
The cloth that dimension or fibrage obtain.Source is preferably flaxen fiber, cane fiber or cellulose fibre, and described flaxen fiber is preferred
For flax, hemp, ramie, hemp, jute, mestha, sisal hemp, abaca or bluish dogbane；Cellulose fibre is preferably cotton, kapok fibre
Dimension, coir, bamboo fibre or wood-fibred；Cane fiber be preferably soya bean stalk, millet stalk, cigarette stalk, Cotton Stalk, sunflower stalk,
Hemp stalk, sorghum stalk, straw straw, maize straw, triticale stalk or wheat stalk.According to the present invention, described surface modification
Treated natural fiber is first to be placed on natural fiber in NaOH solution to soak or stir, then is placed on cation surface activating
Soak or stir in agent solution, in described solution, NaOH concentration is preferably 1-5%, and the concentration of cationic surfactant is excellent
Elect 2%-6% as, the time of described immersion or stirring is respectively preferably 5-60min, then will immersion or stirred natural fibre
Dimension is placed in atmosphere, and described standing time is preferably 7-12h, finally places into baking oven and dries, obtains at surface modification
The natural fiber managed, described drying temperature are preferably 80-120 DEG C.Drying time is preferably 2-12h.
Sodium hydroxide of the present invention can obtain negative oxygen ion with the hydroxyl reaction on fiber, further with cation
Surfactant reacts, and long hydrocarbon chain is connected on fibre structure.By improving the hydrophobicity of fiber, fiber and polymer matrix are improved
The interface binding power of body, so as to improve the hygroscopicity of composite.
The present invention also provides a kind of preparation method of natural-fiber composite material, including：
Step 1：Natural fiber is first placed in NaOH solution and reacted, then is placed in cationic surfactant solution
It is modified, then place in atmosphere, then dry to obtain the treated natural fiber of surface modification；
Step 2：By the natural fiber being modified and UPE/ polypropylene composite materials, natural-fiber composite material is obtained.
According to the present invention, the described natural fiber being modified and the compound methods of UPE are：
UPE resins, curing agent, accelerator and defoamer are mixed, obtain mixture, is stirred the mixture for uniformly, preferably
It is put into baking oven and vacuumizes 0-5min, place into and 0-5min is mixed in ultrasound, mixture is coated in the natural fiber being modified
On cloth, it is then placed in steel plate mould, natural-fiber composite material is obtained after curing molding.
According to the present invention, described UPE resins, curing agent, accelerator and defoamer, according to mass fraction meter, including：
UPE resin 90-100 parts, curing agent 0.10-3 parts, accelerator 0.01-0.5 parts, defoamer 0-10 parts.
According to the present invention, the type of described UPE resins is not particularly limited, and preferably includes bisphenol A-type and vinyl esters
Type, M-phthalic acid type（Abbreviation metaphenylene）, O-phthalic acid type（Referred to as adjacent benzene-type）, halo unsaturated polyester resin, it is more excellent
Choosing for O-phthalic acid type.Described curing agent is not particularly limited, and preferably includes methyl ethyl ketone peroxide, isopropylbenzene peroxidating
Hydrogen, benzoyl peroxide, cyclohexanone peroxide, peroxidating first isobutyl ketone, TBHP, dibenzoyl peroxide, 2,
4- dichlorobenzoperoxides or dilauroyl peroxide, more preferably methyl ethyl ketone peroxide；Described accelerator does not have special limit
System, preferably includes isocyanic acid cobalt, lauryl mercaptan, cobalt iso-octoate, cobalt octoate, DMA or cobalt naphthenate, more
Preferably isocyanic acid cobalt；Described is not particularly limited to defoamer, preferably include BYK-A555, BYK-051, BYK-052,
BYK-053, BYK-054, BYK-055, BYK-056, BYK-057, BYK-1752 or BYK-A535, more preferably BYK-A555.
Preferably, the method for the described natural fiber being modified and polypropylene composite materials is：
Polypropylene, coupling agent and the natural fiber that was modified are processed by pressure sintering to obtain natural-fiber composite material.
According to the present invention, described pressure sintering is first to mix polypropylene and coupling agent, is put into pulverizer and crushes, obtains
Mixture；Described polypropylene and the mass percent of coupling agent are preferably（95-99）：（1-5）, more preferably 98：2；Will be mixed
The natural fiber cloth layering that compound treats with surface modification is taped against in steel mould tool, is put into vulcanizing press, is preferably first existed
Preheat in 1-5min, hot pressing 3-7min at being then 180-200 DEG C in pressure 9-11MPa, temperature, then be cold-pressed in 180-195 DEG C
0.5-2min, obtain natural-fiber composite material.
According to the present invention, described coupling agent preferably includes maleic anhydride inoculated polypropylene（MAPP）, maleic anhydride grafting
Polyethylene（MAPE）, maleic anhydride grafted ABS or maleic anhydride grafting EVA, aminopropyl triethoxysilane, glycidyl ether oxygen
Base propyl trimethoxy silicane, methacryloxypropyl trimethoxy silane, VTES, thin propyl group three
Methoxy silane, ethylenediaminepropyltriethoxysilane, ethylenediamine hydroxypropyl methyl dimethoxysilane, more preferably MAPP.
Technical scheme is described in further detail with reference to specific embodiment.Purpose is to make this
Art personnel are more clearly understood and recognized to the application.Following specific embodiment should not in any degree quilt
Understand or be construed to that the application claims are claimed the limitation of scope.
Comparative example 1
95g UPE are weighed, by 0.13g isocyanic acids cobalt, 0.18g methyl ethyl ketone peroxides, 5g defoamers（BYK A555）It is put into
Into the UPE weighed up, stir, vacuumized in vacuum drying oven after keeping 2 min, be put into ultrasound and be sufficiently mixed 2min,
UPE is cast to steel plate mould（12cm×7.5cm×3mm）In, curing molding, obtain UPE resins.By the gained material of comparative example 1
The fracture strength of material is 37 MPa, stretch modulus 1.55GPa, impact strength 2.14KJ/m2, 5% thermal weight loss temperature is
238℃。
Embodiment 1
Linen is cut into 12cm × 7.5cm rectangular blocks to clean, naturally dry 8h, then is placed on 100 DEG C of electric heating air blast
6h is dried in drying box, obtains clean linen.
95g UPE are weighed, by 0.13g isocyanic acids cobalt, 0.18g methyl ethyl ketone peroxides and 5g defoamers（BYK A555）It is put into
In the UPE weighed up, stir, vacuumized in vacuum drying oven after keeping 2 min, be put into ultrasound and be sufficiently mixed 2min, will
UPE even applications are put into steel plate mould in untreated one layer treated of four pieces of linen last layers（12cm×7.5cm×3mm）
In, curing molding, obtain natural-fiber composite material.It is 33.12 MPa by the fracture strength of the gained composite of embodiment 1,
Stretch modulus is 3.12GPa, impact strength 7.52KJ/m2, 5% thermal weight loss temperature is 224 DEG C.
Embodiment 2
Linen is cut into 12cm × 7.5cm rectangular blocks, is firstly placed in the NaOH solution that concentration is 2%, soaking at room temperature
Clean, then be placed in the Cetyltrimethylammonium bromide solution that concentration is 5%, the water-bath 30min under the conditions of 60 DEG C after 30min
After clean, naturally dry 8h, then be placed in 100 DEG C of electric drying oven with forced convection and dry 6h, obtain the treated flax of alkylation
Cloth, the moisture pick-up properties of the linen after modification are improved.
95g UPE are weighed, by 0.13g isocyanic acids cobalt, 0.18g methyl ethyl ketone peroxides and 5g defoamers（BYK A555）It is put into
In the UPE weighed up, stir, vacuumized in vacuum drying oven after keeping 2 min, be put into ultrasound and be sufficiently mixed 2min, will
UPE even applications are put into steel plate mould in one layer treated of four pieces of linen last layers of alkylation（12cm×7.5cm×3mm）
In, curing molding, obtain natural-fiber composite material.It is 39 MPa by the fracture strength of the gained composite of embodiment 2, stretching
Modulus is 2.91GPa, impact strength 9.18KJ/m2, 5% thermal weight loss temperature is 220 DEG C.
Fig. 1 is the burlap of chemical modification and the infrared light of untreated burlap that the embodiment of the present invention 2 and embodiment 1 obtain
Spectrogram, wherein, solid line is untreated burlap, and dotted line is the burlap of chemical modification, and as seen from the figure, chemically modified fiber exists
2927cm-1And 2861cm-1Appearance-CH2-CH2- two vibration peaks, illustrate to have connected alkyl on fibre structure molecule.And do not locate
Fiber is managed in 1739 cm-1With 1238 cm-1Two vibration peaks weaken, illustrate the wood in fiber after NaOH solution is handled
The impurity such as quality and hemicellulose is removed.
Fig. 2 is the moisture absorption of the burlap and untreated burlap for the chemical modification that the embodiment of the present invention 2 and embodiment 1 obtain
Property, wherein, the water absorption rate of the burlap F1 by alkylation reduces 30% than untreated burlap F water absorption rate.Pass through cation
Surfactant carries out modification to the surface of fiber, improves fibrous hydrophobic so as to improve the hygroscopicity of fiber.In Fig. 3
By burlap/UPE of alkylation（UPEF1）Composite water absorption rate than untreated burlap/UPE（UPEF）Composite wood
The water absorption rate of material reduces 31%.As a result show, processing method of the invention successfully improves the hydrophobicity of natural fiber, improves
Interface binding power between fiber and matrix, and successfully improve the hygroscopicity and mechanical property of composite.
Embodiment 3
Gunny cloth is cut into 12cm × 7.5cm rectangular blocks, is firstly placed in the NaOH solution that concentration is 5%, soaking at room temperature
Clean, then be placed in the DTAB solution that concentration is 6%, the water-bath 30min under the conditions of 60 DEG C after 30min
After clean, naturally dry 8h, then be placed in 100 DEG C of electric drying oven with forced convection and dry 6h, obtain the treated flax of alkylation
Cloth, the moisture pick-up properties of the linen after modification are improved.
90gUPE is weighed, by 0.13g isocyanic acids cobalt, 0.18g methyl ethyl ketone peroxides and 10g defoamers（BYK A555）It is put into
In the UPE weighed up, stir, vacuumized in vacuum drying oven after keeping 2 min, be put into ultrasound and be sufficiently mixed 2min, will
UPE even applications are taped against steel mould tool on four pieces of treated linen of alkylation（12cm×7.5cm×3mm）In, solidification
Shaping, obtains natural-fiber composite material.
Embodiment 4
Linen is cut into 12cm × 7.5cm rectangular blocks, is firstly placed in the NaOH solution that concentration is 1%, soaking at room temperature
Clean, then be placed in the cetyl trimethylammonium bromide solution that concentration is 2%, the water-bath 30min under the conditions of 60 DEG C after 30min
After clean, naturally dry 8h, then be placed in 100 DEG C of electric drying oven with forced convection and dry 6h, obtain the treated flax of alkylation
Cloth, the moisture pick-up properties of the linen after modification are improved.
95g UPE are weighed, by 0.13g isocyanic acids cobalt, 0.18g methyl ethyl ketone peroxides and 5g defoamers（BYK A555）It is put into
In the UPE weighed up, stir, vacuumized in vacuum drying oven after keeping 2 min, be put into ultrasound and be sufficiently mixed 2min, will
UPE even applications are put into steel plate mould in one layer treated of four pieces of linen last layers of alkylation（12cm×7.5cm×3mm）
In, curing molding, obtain natural-fiber composite material.By the MPa of fracture strength 36.5 of the gained composite of embodiment 4, stretching
Modulus 2.59GPa, impact strength 8.67KJ/m2, 5% thermal weight loss temperature is 221 DEG C.
Comparative example 2
Linen is cut into 12cm × 7.5cm rectangular blocks to clean, naturally dry 8h, then is placed on 100 DEG C of electric heating air blast
6h is dried in drying box, obtains clean linen.By PP and MAPP according to mass ratio be 98:2 are put into pulverizer crushing, obtain
Mixture.
Mixture and two pieces of untreated treated linen after 100g is crushed are weighed, layering is taped against steel mould tool
（60mm×120mm×3mm）In, it is put into 189 DEG C of vulcanizing press and preheats 3min, is then maintained at pressure 10MPa and temperature
Degree hot pressing 5min at 189 DEG C, then 1min is cold-pressed, obtain natural-fiber composite material.By rushing for the gained composite of comparative example 2
Hit intensity is 5.02KJ/m2, 5% thermal weight loss temperature is 353 DEG C.
Embodiment 5
Linen is cut into 12cm × 7.5cm rectangular blocks, is firstly placed in the NaOH solution that concentration is 2%, soaking at room temperature
Clean, then be placed in the Cetyltrimethylammonium bromide solution that concentration is 5%, the water-bath 30min under the conditions of 60 DEG C after 30min
After clean, naturally dry 8h, then be placed in 100 DEG C of electric drying oven with forced convection and dry 6h, obtain the treated flax of alkylation
Cloth, the moisture pick-up properties of the linen after modification are improved.
By PP and MAPP according to mass ratio be 98:2 are put into pulverizer crushing, obtain mixture.
Weigh the mixture after 100g is crushed and two pieces are alkylated treated linen, layering is taped against steel mould tool
（60mm×120mm×3mm）In, it is put into 189 DEG C of vulcanizing press and preheats 3min, is then maintained at pressure 10MPa and temperature
Degree hot pressing 5min at 189 DEG C, then 1min is cold-pressed, obtain natural-fiber composite material.By rushing for the gained composite of embodiment 5
Hit intensity is 7.4KJ/m2, 48% is improved than comparative example 2,5% thermal weight loss temperature of resulting composite is 318 DEG C.
Fig. 4 is modified natural fibers linen/PP in the embodiment of the present invention 5（PPF1）With it is untreated in comparative example 2
Linen/PP（PPF）Composite water absorption rate figure.Wherein, the burlap of alkylation/PP composites water absorption rate is than untreated fiber crops
Cloth/PP composite water absorption rates reduce 28%, and the inventive method successfully improves the hygroscopicity and mechanical property of composite.
Comparative example 3
Linen is cut into 12cm × 7.5cm rectangular blocks to clean, naturally dry 8h, then is placed on 100 DEG C of electric heating air blast
6h is dried in drying box, obtains clean linen.By PP and MAPP according to mass ratio be 98:2 are put into pulverizer crushing, obtain
Mixture.
Mixture and four pieces of untreated treated linen after 100g is crushed are weighed, layering is taped against steel mould tool
（60mm×120mm×3mm）In, it is put into 189 DEG C of vulcanizing press and preheats 3min, is then maintained at pressure 10MPa and temperature
Degree hot pressing 5min at 189 DEG C, then 1min is cold-pressed, obtain natural-fiber composite material.By the disconnected of the gained composite of comparative example 3
Resistance to spalling is 28.68 MPa, stretch modulus 2.31GPa, impact strength 6.75KJ/m2, 5% thermal weight loss temperature is 312 DEG C.
Embodiment 6
Linen is cut into 12cm × 7.5cm rectangular blocks, is firstly placed in the NaOH solution that concentration is 2%, soaking at room temperature
Clean, then be placed in the Cetyltrimethylammonium bromide solution that concentration is 5%, the water-bath 30min under the conditions of 60 DEG C after 30min
After clean, naturally dry 8h, then be placed in 100 DEG C of electric drying oven with forced convection and dry 6h, obtain the treated flax of alkylation
Cloth, the moisture pick-up properties of the linen after modification are improved.
By PP and MAPP according to mass ratio be 98:2 are put into pulverizer crushing, obtain mixture.
Weigh the mixture after 100g is crushed and four pieces are alkylated treated linen, layering is taped against steel mould tool
（60mm×120mm×3mm）In, it is put into 189 DEG C of vulcanizing press and preheats 3min, is then maintained at pressure 10MPa and temperature
Degree hot pressing 5min at 189 DEG C, then 1min is cold-pressed, obtain natural-fiber composite material.By the composite obtained by embodiment 6
Fracture strength 31.94 MPa, stretch modulus 2.89MPa, impact strength 8.26KJ/m2, 11.4% has been respectively increased than comparative example 3,
25.1% and 22.4%.We are same to PP to have carried out hot pressing, and has carried out Mechanics Performance Testing, and the fracture strength for obtaining PP is
23.2 MPa, stretch modulus 0.74GPa, impact strength 3.39KJ/m2.Thus, it could be seen that treated by the inventive method
The fracture strength of natural-fiber composite material add 37.6% than pure PP, impact strength adds 143%, and mechanical property has
Large increase.Prove that the inventive method can successfully improve the hygroscopicity and interface performance of natural fiber, and then improve natural fiber
The mechanical property of composite.It it is 290 DEG C by 5% thermal weight loss temperature of the composite obtained by embodiment 6.
Embodiment 7
Cambric is cut into 12cm × 7.5cm rectangular blocks, is firstly placed in the NaOH solution that concentration is 1%, soaking at room temperature
Clean, then be placed in the tetradecyl trimethyl ammonium chloride solution that concentration is 4%, the water-bath 30min under the conditions of 60 DEG C after 30min
After clean, naturally dry 8h, then be placed in 80 DEG C of electric drying oven with forced convection and dry 12h, obtain the treated hemp of alkylation
Cloth.
By PP and MAPE according to mass ratio be 99:1 is put into pulverizer crushing, obtains mixture.
Weigh the mixture after 100g is crushed and four pieces are alkylated treated cambric layering and are taped against steel mould tool（60mm
×120mm×3mm）In, it is put into 189 DEG C of vulcanizing press and preheats 3min, is then maintained at pressure 10MPa and temperature exists
Hot pressing 5min at 189 DEG C, then 1min is cold-pressed, obtain natural-fiber composite material.
Embodiment 8
Gunny cloth is cut into 12cm × 7.5cm rectangular blocks, is firstly placed in the NaOH solution that concentration is 5%, soaking at room temperature
Clean, then be placed in the DTAC solution that concentration is 6%, the water-bath 30min under the conditions of 60 DEG C after 30min
After clean, naturally dry 8h, then be placed in 120 DEG C of electric drying oven with forced convection and dry 2h, obtain the treated jute of alkylation
Cloth.
By PP and MAPP according to mass ratio be 95:5 are put into pulverizer crushing, obtain mixture；
Weigh the mixture after 100g is crushed and four pieces are alkylated treated gunny cloth layering and are taped against steel mould tool（60mm
×120mm×3mm）In, it is put into 180 DEG C of vulcanizing press and preheats 5min, is then maintained at pressure 10MPa and temperature exists
Hot pressing 7min at 180 DEG C, then 1min is cold-pressed, obtain natural-fiber composite material.
Embodiment 9
Linen is cut into 12cm × 7.5cm rectangular blocks, is firstly placed in the NaOH solution that concentration is 2%, soaking at room temperature
Clean, then be placed in the cetyl trimethylammonium bromide solution that concentration is 5%, the water-bath 30min under the conditions of 60 DEG C after 30min
After clean, naturally dry 8h, then be placed in 100 DEG C of electric drying oven with forced convection and dry 6h, obtain the treated flax of alkylation
Cloth.
By PP and MAPP according to mass ratio be 98:2 are put into pulverizer crushing, obtain mixture.After weighing 100g crushing
The linen layering that mixture and four pieces of alkylations treat is taped against steel mould tool（60mm×120mm×3mm）In, it is put into 189
DEG C vulcanizing press in preheat 3min, be then maintained at pressure 10MPa and temperature the hot pressing 5min at 189 DEG C, then be cold-pressed
1min, obtain natural-fiber composite material.It is 30.5 MPa by the fracture strength of the gained composite of embodiment 9, stretch modulus
For 2.59GPa, impact strength 8.03KJ/m2, mechanical property is better than PP.By 5% heat of the composite of the gained of embodiment 9
Weightless temperature is 305 DEG C.
Claims (6)
1. a kind of natural-fiber composite material, it is characterised in that the composite is to gather modified natural fiber and UPE/
Propylene is compound and obtains；
Described modified natural fiber is first to be placed on natural fiber in NaOH solution to react, then is placed on cationic surface
It is modified in activator solution, then places in atmosphere, then dries to obtain；
Described modified natural fiber and the compound methods of UPE are：
UPE resins, curing agent, accelerator, defoamer are mixed, obtain mixture, by mixture coated in surface modification processing
On the natural fiber crossed, natural-fiber composite material is obtained after curing molding；Described UPE resins, curing agent, accelerator and disappear
Infusion, according to mass fraction meter, including：
UPE resin 89-100 parts, curing agent 0.10-3 parts, accelerator 0.01-0.5 parts, defoamer 5-10 parts；
Described curing agent includes methyl ethyl ketone peroxide or cyclohexanone peroxide；
Described accelerator includes isocyanic acid cobalt, cobalt naphthenate or cobalt iso-octoate；
Described modified natural fiber and the method for polypropylene composite materials are：
The natural fiber that polypropylene, coupling agent and surface modification treat is processed to obtain day by pressure sintering or melt-blending process
Right fibrous composite；
The mass ratio of described polypropylene, coupling agent and modified natural fiber natural fiber is（49-89）：（1-5）：（10-
50）；
Described coupling agent is maleic anhydride inoculated polypropylene.
2. a kind of natural-fiber composite material according to claim 1, it is characterised in that described natural fiber source is
Jute, mestha, sisal hemp, abaca, flax, bluish dogbane, hemp, hemp, ramie, bamboo fibre, coir, wood-fibred, cotton, Wheat Straw
Stalk, maize straw, straw straw, sorghum stalk, hemp stalk, sunflower stalk, Cotton Stalk, cigarette stalk, millet stalk or soya bean stalk.
A kind of 3. natural-fiber composite material according to claim 1, it is characterised in that the cationic surfactant
For eight alkyl trimethyl ammonium chlorides, decyl trimethyl ammonium chloride, DTAC, tetradecyltrimethylammonium chlorine
Change ammonium, hexadecyltrimethylammonium chloride, OTAC, double octyl alkyl dimethyl ammonium chlorides, double ten alkyl
Alkyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, triethyl methyl ammonium chloride, tripropyl ammonio methacrylate, tributyl
Ammonio methacrylate, tri-n-octyl methyl ammonium chloride, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, benzyl triethyl ammonium
Ammonium chloride, benzyltrimethylammonium chloride, tetramethyl Ammonium hydrogen sulfate, TBAB, 4-propyl bromide, tetraethyl bromination
Ammonium, 4 bromide, tributyl-methyl phosphonium ammonium bromide, tricaprylmethyl ammonium bromide, DDA, double ten
Dialkyl dimethyl ammonium bromide, didecyl Dimethy ammonium bromide, Cetyltrimethylammonium bromide, cetyl trimethyl bromine
Change ammonium, TTAB, eight alkyl trimethyl ammonium bromides, ten alkyl trimethyl ammonium bromides, dodecyl front three
Base ammonium bromide, N, N- diethyl-（3-methoxybenzene oxygen ethyl）Benzyl ammonium chloride.
A kind of 4. natural-fiber composite material according to claim 1, it is characterised in that described NaOH solution quality point
Number is 1-5%, and cationic surfactant solution mass fraction is 2-6%.
5. a kind of natural-fiber composite material according to claim 1, it is characterised in that described anti-in NaOH solution
Should, and the time reacted in cationic surfactant solution is respectively 5-60 min.
A kind of 6. preparation method of natural-fiber composite material as claimed in claim 1, it is characterised in that including：
Step 1：Natural fiber is modified to processing in NaOH solution, then is placed in cationic surfactant solution
Row modification, is then placed in atmosphere, then dries the natural fiber being modified；
Step 2：By modified natural fiber and UPE/ polypropylene composite materials, natural-fiber composite material is obtained.
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