CN105255207A - Modified natural fibrous composite and preparation method thereof - Google Patents
Modified natural fibrous composite and preparation method thereof Download PDFInfo
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- CN105255207A CN105255207A CN201510661321.0A CN201510661321A CN105255207A CN 105255207 A CN105255207 A CN 105255207A CN 201510661321 A CN201510661321 A CN 201510661321A CN 105255207 A CN105255207 A CN 105255207A
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Abstract
The invention provides a modified natural fibrous composite and a processing method thereof, and belongs to the field of composites. The composition is prepared by compounding modified natural fibers and UPE/polypropylene. The modified natural fibers are prepared in the mode that natural fibers are firstly placed in a NaOH solution to be treated, and then placed in a cationic surface active agent solution for chemical modification, and then the natural fibers are placed in air and dried. The invention further provides a preparation method of the natural fibrous composite. The natural fibers are modified through a water phase method, chemical modification is carried out on the fibers through sodium hydroxide and the cationic surface active agent solution, the hydrophobicity of the fibers is improved, and therefore the moisture absorption performance and interface performance of the natural fibrous composite are improved, and meanwhile the mechanical properties of the composite can be improved.
Description
Technical field
The present invention relates to field of compound material, be specifically related to a kind of modified natural fibers matrix material and preparation method thereof.
Background technology
Natural-fiber composite material is with resin or plastics for matrix, take natural fiber as a kind of matrix material of strongthener.Natural fiber mainly contains mestha, jute, flax, hemp, sisal hemp, abaca, kendir, ramie, hemp, xylon, bamboo fibers, 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, wheat stalk, and take Mierocrystalline cellulose as naturally existing or cloth that the fiber of growth or fibrage obtain of major ingredient.Have that density is little, price is low, degradable, recyclable regenerative, the advantage such as to processing units loss little, aboundresources, power consumption of polymer processing low, energy-conserving and environment-protective non-stimulated to health, and have the strength and stiffness of general fiber, and specific tenacity, proportion are less, specific rigidity is all higher.Be that the composites strengthening base has excellent performance with natural fiber, along with the extension of this theme of raw material Sustainable development, natural fiber plays more and more important role in reinforced composite field.The matrix material of current use natural fiber compound has been applied in the fields such as automobile, building materials, furniture, wrapping material, dress material.(see Ni Jingda, Yu Husheng, the research application of natural plant fibre reinforced composite, chemical fibre and textile technology, 2006,2:29)
The cellulosic content of natural fiber main component accounts for more than 50%, plays main mechanical support effect.But due on cellulose chain with more hydroxyl, so have very strong wetting ability and water absorbability.
Plastics can be divided into thermoplastics and thermosetting resin by physical and chemical performance classification.The molecular structure of thermoplastics is linear or branched chain type structure, the fusible cooling solidifiable when being heated, and can soften again when being heated to certain temperature hardening after cooling, this process can be carried out repeatedly.As: polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyoxymethylene.Thermosetting resin also can soften when being heated, and sizing of will hardening when being heated to certain temperature, reheats and also can not soften, and its molecular structure is finally three dimensional structure.As: resol, epoxy resin, unsaturated polyester.
Polypropylene and unsaturated polyester are typical thermoplasticity and thermosetting resin respectively.
Polypropylene is that monomer polymerization forms with propylene.Be a kind of important general-purpose plastics, have that nontoxicity, transparency are high, resistance to chemical attack, density is little, relative hardness is high, and have good injection moulding performance, its Application Areas constantly expands, and is widely used in the fields such as automobile, building materials, weaving, household electrical appliances wrapping material.Liu Xiaoye, Dai Gance first carries out NaOH process to fiber surface in the research of the surface treatment of jute felt and the mechanical property of reinforced polypropylene compound material thereof, carry out the process of MAPP emulsion again, make the untreated increase by 68% of bending strength ratio, tensile strength is than untreated increase by 48%.Illustrate that MAPP emulsion is the good interfacial compatibilizer between flaxen fiber and polypropylene.But its complex production process, the percentage of grafting of MAPP emulsion be only about 5% (see Liu Xiaoye, Dai Gance. the surface treatment of jute felt and the mechanical property of reinforced polypropylene compound material thereof, 2006,23 (5): 63-69).
Unsaturated polyester (UPE) resin is generally synthesize the linear polymer with ester bond unsaturated link(age) through polycondensation by the saturated dibasic alcohol of undersaturated diprotic acid or the unsaturated dibasic alcohol of monounsaturated dicarboxylic acid.The usage quantity of UPE resin in thermosetting resin is very large, and the usage quantity simultaneously in glass fiber reinforcement engineering plastics are produced is also very large.Unsaturated polyester resin has formability and manufacturability is good, and viscosity, thixotropy, working life, dry air etc. are all adjustable; There are good mechanical property, corrosion resistance nature and electric property; Painted freedom; Be easy to different strongthener, composite product that filler combination obtains different qualities; Cheap and reduce costs a series of way and be easy to the advantages such as investment and production.Be widely used in fields such as building, chemical industry, boats and ships, automobile, tables and chairs, sanitary ware.(see Zhang little Ping, unsaturated polyester resin and new development thereof, 2008,2:23-29.See Song Yubo, the production of unsaturated polyester resin and application, 1999,20 (3): 20-23)
Summary of the invention
The invention provides a kind of natural-fiber composite material and preparation method thereof, this natural-fiber composite material has good hygroscopic property and mechanical property.
First the present invention provides a kind of natural-fiber composite material, and modified natural fiber and unsaturated polyester (UPE)/polypropylene composite materials obtain by this matrix material;
Described modified natural fiber is first placed in NaOH solution by natural fiber to react, then be placed in cationic surfactant solution and react, and then places in atmosphere, then dry and obtain.
Preferably, the source of described natural fiber is mestha, jute, flax, hemp, sisal hemp, abaca, kendir, ramie, hemp, xylon, bamboo fibers, 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, described cats product is eight alkyl trimethyl ammonium chlorides, decyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, two octyl alkyl dimethyl ammonium chloride, didecyl Dimethy ammonium chloride, distearyl dimethyl ammonium chloride, triethyl methyl ammonium chloride, tripropyl ammonio methacrylate, tributyhnethylammonium chloride, tri-n-octyl methyl ammonium chloride, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, tetramethyl-Ammonium hydrogen sulfate, Tetrabutyl amonium bromide, 4-propyl bromide, tetraethylammonium bromide, 4 bromide, tributyl-methyl phosphonium brometo de amonio, tricaprylmethyl brometo de amonio, DDA, didodecyldimethylammbromide bromide, didecyl Dimethy brometo de amonio, Cetyltrimethylammonium bromide, cetyl trimethylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, eight alkyl trimethyl ammonium bromides, ten alkyl trimethyl ammonium bromides, Trimethyllaurylammonium bromide, N, N-diethyl-(3 ＇-anisole oxygen ethyl) benzyl ammonium chloride etc.More preferably Cetyltrimethylammonium bromide.
Preferably, described NaOH solution massfraction is 1-5% and cationic surfactant solution massfraction is 2-6%.Preferably, the described reaction times is respectively as 5-60min.
The present invention also provides a kind of preparation method of natural-fiber composite material, comprising:
Step one: natural fiber is first placed in NaOH solution and carries out modification, then be placed in cationic surfactant solution and carry out modification, then place in atmosphere, then dry the natural fiber obtaining modification;
Step 2: by the natural fiber of modification and UPE/ polypropylene composite materials, obtain natural-fiber composite material.
Preferably, the natural fiber of described modification and the method for UPE compound are:
By UPE resin, solidifying agent, promotor and defoamer mixing, obtain mixture, mixture is coated on the natural fiber of modification, after curing molding, obtains natural-fiber composite material.
Preferably, described UPE resin, solidifying agent, promotor and defoamer, according to mass fraction meter, comprising:
UPE resin 90-100 part, solidifying agent 0.10-3 part, promotor 0.01-0.5 part, defoamer 0-10 part.
Preferably; described solidifying agent comprises methylethyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, benzoyl peroxide, peroxidation first isobutyl ketone, isopropyl benzene hydroperoxide, tertbutyl peroxide, 2,4-dichlorobenzoperoxides or dilauroyl peroxide.
Preferably, the described natural fiber through modification and the method for polypropylene composite materials are:
The natural fiber of polypropylene, coupling agent and modification is obtained natural-fiber composite material by pressure sintering processing.
Preferably, described coupling agent is maleic anhydride inoculated polypropylene, maleic anhydride grafted ABS, maleic anhydride grafted polyethylene, dimerization di (isooctyl) phosphate Magnesium Stearate, DL series aluminate coupling agent, powder silane coupling agent XH-820 series, maleic anhydride graft EVA, TC-130, aminopropyl triethoxysilane, methacryloxypropyl trimethoxy silane, glycydoxy Trimethoxy silane, vinyltriethoxysilane, ethylenediaminepropyltriethoxysilane, dredge propyl trimethoxy silicane, quadrol hydroxypropyl methyl dimethoxysilane.
Beneficial effect of the present invention
The present invention first provides a kind of natural-fiber composite material, and the natural fiber of modification and UPE/ polypropylene composite materials obtain by this matrix material; The natural fiber of described modification is first placed in NaOH solution by natural fiber to carry out chemical modification, then be placed in cationic surfactant solution and carry out chemical modification process, then places in atmosphere, then dry and obtain.Natural fiber of the present invention adopts Aqueous phase to process, by sodium hydroxide and cationic surfactant solution, the hydrophobicity that chemical modification increases fiber is carried out to fiber, thus improve moisture absorption and the interface performance of natural-fiber composite material, also make the mechanical property of matrix material be improved simultaneously.
The present invention also provides a kind of working method of natural-fiber composite material, and this working method raw material is easy to get, technique simple, and prepared matrix material has good hygroscopic property and mechanical property.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of modified natural fibers linen and the untreated linen obtained in the embodiment of the present invention 1,2.
Fig. 2 is the water-intake 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 matrix material water-intake rate figure in the embodiment of the present invention 1,2.
Fig. 4 is modified natural fibers linen and untreated linen/PP matrix material water-intake rate figure in comparative example 2 of the present invention and embodiment 5.
Embodiment
First the present invention provides a kind of natural-fiber composite material, and the natural fiber of modification and UPE/ polypropylene composite materials obtain by this matrix material;
The natural fiber of described modification is first placed in NaOH solution by natural fiber to react, then be placed in cationic surfactant solution and react, and then places in atmosphere, then to dry and obtain.
According to the present invention, described natural fiber be with Mierocrystalline cellulose be major ingredient naturally there is or grow the cloth that the fiber that obtains or fibrage obtains.Source is preferably flaxen fiber, straw fiber or cellulosic fibre, and described flaxen fiber is preferably flax, hemp, ramie, hemp, jute, mestha, sisal hemp, abaca or kendir; Cellulosic fibre is preferably cotton, bombax cotton, coir, bamboo fibers or xylon; Straw fiber is 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, the natural fiber of described finishing process is first placed on by natural fiber in NaOH solution to soak or stir, be placed on again in cationic surfactant solution and soak or stir, in described solution, the concentration of NaOH is preferably 1-5%, the concentration of cats product is preferably 2%-6%, described immersion or the time of stirring are preferably 5-60min respectively, then immersion or stirred natural fiber are placed in atmosphere, described storage period is preferably 7-12h, finally put into baking oven again to dry, obtain the natural fiber of finishing process, described bake out temperature is 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, reacts further with cats product, and long hydrocarbon chain is received on fibrous texture.By improving the hydrophobicity of fiber, improving the interface binding power of fiber and polymeric matrix, thus improving the water absorbability of matrix material.
The present invention also provides a kind of preparation method of natural-fiber composite material, comprising:
Step one: natural fiber is first placed in NaOH solution and reacts, then be placed on modification in cationic surfactant solution, then place in atmosphere, then dry the natural fiber obtaining finishing process;
Step 2: by the natural fiber of modification and UPE/ polypropylene composite materials, obtain natural-fiber composite material.
According to the present invention, the natural fiber of described modification and the method for UPE compound are:
By UPE resin, solidifying agent, promotor and defoamer mixing, obtain mixture, mixture is stirred, preferably put into baking oven and vacuumize 0-5min, put into ultrasonic mixing 0-5min again, mixture is coated on the natural fiber cloth of modification, then puts into steel plate mould, after curing molding, obtain natural-fiber composite material.
According to the present invention, described UPE resin, solidifying agent, promotor and defoamer, according to mass fraction meter, comprising:
UPE resin 90-100 part, solidifying agent 0.10-3 part, promotor 0.01-0.5 part, defoamer 0-10 part.
According to the present invention, the type of described UPE resin is not particularly limited, preferably include bisphenol A-type and vinyl ester type, m-phthalic acid type (abbreviation metaphenylene), O-phthalic acid type (being called for short adjacent benzene-type), halo unsaturated polyester resin, be more preferably O-phthalic acid type.Described solidifying agent is not particularly limited, preferably include methylethyl ketone peroxide, isopropyl benzene hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, peroxidation first isobutyl ketone, tertbutyl peroxide, dibenzoyl peroxide, 2,4-dichlorobenzoperoxide or dilauroyl peroxide, be more preferably methylethyl ketone peroxide; Described promotor is not particularly limited, and preferably includes isocyanic acid cobalt, lauryl mercaptan, cobalt iso-octoate, cobalt octoate, DMA or cobalt naphthenate, is more preferably isocyanic acid cobalt; Described is not particularly limited defoamer, preferably includes BYK-A555, BYK-051, BYK-052, BYK-053, BYK-054, BYK-055, BYK-056, BYK-057, BYK-1752 or BYK-A535, is more preferably BYK-A555.Preferably, the natural fiber of described modification and the method for polypropylene composite materials are:
The natural fiber of polypropylene, coupling agent and modification is obtained natural-fiber composite material by pressure sintering processing.
According to the present invention, described pressure sintering is first by polypropylene and coupling agent mixing, is put in pulverizer and pulverizes, obtain mixture; Described polypropylene and the mass percent of coupling agent are preferably (95-99): (1-5), is more preferably 98:2; The natural fiber cloth layering of mixture and finishing process is taped against in steel mould tool, be put in vulcanizing press, preferred elder generation is in 180-195 DEG C in preheating 1-5min, then hot pressing 3-7min at pressure 9-11MPa, temperature are 180-200 DEG C, cold pressing 0.5-2min again, obtains natural-fiber composite material.
According to the present invention, described coupling agent preferably includes maleic anhydride inoculated polypropylene (MAPP), maleic anhydride grafted polyethylene (MAPE), maleic anhydride grafted ABS or maleic anhydride graft EVA, aminopropyl triethoxysilane, glycydoxy Trimethoxy silane, methacryloxypropyl trimethoxy silane, vinyltriethoxysilane, dredges propyl trimethoxy silicane, ethylenediaminepropyltriethoxysilane, quadrol hydroxypropyl methyl dimethoxysilane, more preferably MAPP.
Below in conjunction with specific embodiment, technical scheme of the present invention is described in further detail.Object is to make those skilled in the art have understanding and cognition clearly to the application.Following specific embodiment should not be understood or be interpreted as the restriction to the application's claims request protection domain in any degree.
Comparative example 1
Take 95gUPE, 0.13g isocyanic acid cobalt, 0.18g methylethyl ketone peroxide, 5g defoamer (BYKA555) are put in the UPE weighed up, stir, vacuumize after keeping 2min in vacuum drying oven, be put into ultrasonic in fully mix 2min, be cast to by UPE in steel plate mould (12cm × 7.5cm × 3mm), curing molding, obtains UPE resin.Be 37MPa by the breaking tenacity of comparative example 1 resulting materials, tensile modulus is 1.55GPa, and shock strength is 2.14KJ/m
2, the thermal weight loss temperature of 5% is 238 DEG C.
Embodiment 1
Linen is cut into 12cm × 7.5cm rectangular block to clean, naturally dries 8h, then dry 6h in the electric drying oven with forced convection being placed on 100 DEG C, obtain clean linen.
Take 95gUPE, 0.13g isocyanic acid cobalt, 0.18g methylethyl ketone peroxide and 5g defoamer (BYKA555) are put in the UPE weighed up, stir, vacuumize after keeping 2min in vacuum drying oven, be put into ultrasonic in fully mix 2min, be put in steel plate mould (12cm × 7.5cm × 3mm) at untreated four pieces of linen last layer one decks processed by UPE even application, curing molding, obtains natural-fiber composite material.Be 33.12MPa by the breaking tenacity of embodiment 1 gained matrix material, tensile modulus is 3.12GPa, and shock strength is 7.52KJ/m
2, the thermal weight loss temperature of 5% is 224 DEG C.
Embodiment 2
Linen is cut into 12cm × 7.5cm rectangular block, first being placed on concentration is in the NaOH solution of 2%, soaking at room temperature 30min afterwash, being placed on concentration is again in the Cetyltrimethylammonium bromide solution of 5%, at 60 DEG C of Water Unders bath 30min afterwash, naturally dry 8h, then dry 6h in the electric drying oven with forced convection being placed on 100 DEG C, obtain the linen of alkylation process, the hygroscopic property of the linen after modification is improved.
Take 95gUPE, 0.13g isocyanic acid cobalt, 0.18g methylethyl ketone peroxide and 5g defoamer (BYKA555) are put in the UPE weighed up, stir, vacuumize after keeping 2min in vacuum drying oven, be put into ultrasonic in fully mix 2min, be put in steel plate mould (12cm × 7.5cm × 3mm) by UPE even application four pieces of linen last layer one decks in alkylation process, curing molding, obtains natural-fiber composite material.Be 39MPa by the breaking tenacity of embodiment 2 gained matrix material, tensile modulus is 2.91GPa, and shock strength is 9.18KJ/m
2, the thermal weight loss temperature of 5% is 220 DEG C.
Fig. 1 is the burlap of the chemical modification that the embodiment of the present invention 2 and embodiment 1 obtain and the infrared spectrogram of untreated burlap, and wherein, solid line is untreated burlap, and dotted line is the burlap of chemical modification, as seen from the figure, through the fiber of chemical modification at 2927cm
-1and 2861cm
-1appearance-CH
2-CH
2-two vibration peak, illustrate and fibrous texture molecule connected alkyl.And untreatment fiber is at 1739cm
-1and 1238cm
-1two vibration peak weaken, illustrate that the impurity such as xylogen and hemicellulose after NaOH solution process in fiber is removed.
Fig. 2 is the burlap of the chemical modification that the embodiment of the present invention 2 and embodiment 1 obtain and the water absorbability of untreated burlap, and wherein, the water-intake rate through alkylating burlap F1 reduces 30% than the water-intake rate of untreated burlap F.By cats product, modification is carried out to the surface of fiber, improve fibrous hydrophobic thus improve the water absorbability of fiber.Through alkylating burlap/UPE(UPEF1 in Fig. 3) the water-intake rate of matrix material than untreated burlap/UPE(UPEF) the water-intake rate of matrix material reduce 31%.Result shows, treatment process of the present invention successfully improves the hydrophobicity of natural fiber, improves the interface binding power between fiber and matrix, and successfully improves water absorbability and the mechanical property of matrix material.
Embodiment 3
Gunny cloth is cut into 12cm × 7.5cm rectangular block, first being placed on concentration is in the NaOH solution of 5%, soaking at room temperature 30min afterwash, being placed on concentration is again in the Trimethyllaurylammonium bromide solution of 6%, at 60 DEG C of Water Unders bath 30min afterwash, naturally dry 8h, then dry 6h in the electric drying oven with forced convection being placed on 100 DEG C, obtain the linen of alkylation process, the hygroscopic property of the linen after modification is improved.
Take 90gUPE, 0.13g isocyanic acid cobalt, 0.18g methylethyl ketone peroxide and 10g defoamer (BYKA555) are put in the UPE weighed up, stir, vacuumize after keeping 2min in vacuum drying oven, be put into ultrasonic in fully mix 2min, be taped against in steel mould tool (12cm × 7.5cm × 3mm) on four pieces of linen of alkylation process by UPE even application, curing molding, obtains natural-fiber composite material.
Embodiment 4
Linen is cut into 12cm × 7.5cm rectangular block, first being placed on concentration is in the NaOH solution of 1%, soaking at room temperature 30min afterwash, being placed on concentration is again in the cetyl trimethylammonium bromide solution of 2%, at 60 DEG C of Water Unders bath 30min afterwash, naturally dry 8h, then dry 6h in the electric drying oven with forced convection being placed on 100 DEG C, obtain the linen of alkylation process, the hygroscopic property of the linen after modification is improved.
Take 95gUPE, 0.13g isocyanic acid cobalt, 0.18g methylethyl ketone peroxide and 5g defoamer (BYKA555) are put in the UPE weighed up, stir, vacuumize after keeping 2min in vacuum drying oven, be put into ultrasonic in fully mix 2min, be put in steel plate mould (12cm × 7.5cm × 3mm) by UPE even application four pieces of linen last layer one decks in alkylation process, curing molding, obtains natural-fiber composite material.By the breaking tenacity 36.5MPa of embodiment 4 gained matrix material, tensile modulus 2.59GPa, shock strength 8.67KJ/m
2, the thermal weight loss temperature of 5% is 221 DEG C.
Comparative example 2
Linen is cut into 12cm × 7.5cm rectangular block to clean, naturally dries 8h, then dry 6h in the electric drying oven with forced convection being placed on 100 DEG C, obtain clean linen.By PP and MAPP according to mass ratio be 98:2 put into pulverizer pulverize, obtain mixture.
Take the mixture after 100g pulverizing and two pieces of untreated linen processed, layering is taped against in steel mould tool (60mm × 120mm × 3mm), be put into preheating 3min in the vulcanizing press of 189 DEG C, then pressure 10MPa and temperature hot pressing 5min at 189 DEG C is remained on, cold pressing 1min again, obtains natural-fiber composite material.Be 5.02KJ/m by the shock strength of comparative example 2 gained matrix material
2, the thermal weight loss temperature of 5% is 353 DEG C.
Embodiment 5
Linen is cut into 12cm × 7.5cm rectangular block, first being placed on concentration is in the NaOH solution of 2%, soaking at room temperature 30min afterwash, being placed on concentration is again in the Cetyltrimethylammonium bromide solution of 5%, at 60 DEG C of Water Unders bath 30min afterwash, naturally dry 8h, then dry 6h in the electric drying oven with forced convection being placed on 100 DEG C, obtain the linen of alkylation process, the hygroscopic property of the linen after modification is improved.
By PP and MAPP according to mass ratio be 98:2 put into pulverizer pulverize, obtain mixture.
Take the linen of the mixture after 100g pulverizing and two pieces of alkylation process, layering is taped against in steel mould tool (60mm × 120mm × 3mm), be put into preheating 3min in the vulcanizing press of 189 DEG C, then pressure 10MPa and temperature hot pressing 5min at 189 DEG C is remained on, cold pressing 1min again, obtains natural-fiber composite material.Be 7.4KJ/m by the shock strength of embodiment 5 gained matrix material
2, improve 48% than comparative example 2, the matrix material obtained 5% thermal weight loss temperature be 318 DEG C.
Fig. 4 is modified natural fibers linen/PP(PPF1 in the embodiment of the present invention 5) and comparative example 2 in untreated linen/PP(PPF) matrix material water-intake rate figure.Wherein, alkylating burlap/PP matrix material water-intake rate reduces 28% than untreated burlap/PP matrix material water-intake rate, and the inventive method successfully improves water absorbability and the mechanical property of matrix material.
Comparative example 3
Linen is cut into 12cm × 7.5cm rectangular block to clean, naturally dries 8h, then dry 6h in the electric drying oven with forced convection being placed on 100 DEG C, obtain clean linen.By PP and MAPP according to mass ratio be 98:2 put into pulverizer pulverize, obtain mixture.
Take the mixture after 100g pulverizing and four pieces of untreated linen processed, layering is taped against in steel mould tool (60mm × 120mm × 3mm), be put into preheating 3min in the vulcanizing press of 189 DEG C, then pressure 10MPa and temperature hot pressing 5min at 189 DEG C is remained on, cold pressing 1min again, obtains natural-fiber composite material.Be 28.68MPa by the breaking tenacity of comparative example 3 gained matrix material, tensile modulus is 2.31GPa, shock strength 6.75KJ/m
2, the thermal weight loss temperature of 5% is 312 DEG C.
Embodiment 6
Linen is cut into 12cm × 7.5cm rectangular block, first being placed on concentration is in the NaOH solution of 2%, soaking at room temperature 30min afterwash, being placed on concentration is again in the Cetyltrimethylammonium bromide solution of 5%, at 60 DEG C of Water Unders bath 30min afterwash, naturally dry 8h, then dry 6h in the electric drying oven with forced convection being placed on 100 DEG C, obtain the linen of alkylation process, the hygroscopic property of the linen after modification is improved.
By PP and MAPP according to mass ratio be 98:2 put into pulverizer pulverize, obtain mixture.
Take the linen of the mixture after 100g pulverizing and four pieces of alkylation process, layering is taped against in steel mould tool (60mm × 120mm × 3mm), be put into preheating 3min in the vulcanizing press of 189 DEG C, then pressure 10MPa and temperature hot pressing 5min at 189 DEG C is remained on, cold pressing 1min again, obtains natural-fiber composite material.By the breaking tenacity 31.94MPa of the matrix material of embodiment 6 gained, tensile modulus 2.89MPa, shock strength 8.26KJ/m
2, improve 11.4%, 25.1% and 22.4% respectively than comparative example 3.We have carried out hot pressing equally to PP, and have carried out Mechanics Performance Testing, and the breaking tenacity obtaining PP is 23.2MPa, and tensile modulus is 0.74GPa, and shock strength is 3.39KJ/m
2.Therefore visible, the breaking tenacity through the natural-fiber composite material of the inventive method process adds 37.6% than pure PP, and shock strength adds 143%, and mechanical property has had large increase.Prove that the inventive method successfully can improve water absorbability and the interface performance of natural fiber, and then improve the mechanical property of natural-fiber composite material.The matrix material obtained by embodiment 6 5% thermal weight loss temperature be 290 DEG C.
Embodiment 7
Cambric is cut into 12cm × 7.5cm rectangular block, first being placed on concentration is in the NaOH solution of 1%, soaking at room temperature 30min afterwash, being placed on concentration is again in the tetradecyl trimethyl ammonium chloride solution of 4%, at 60 DEG C of Water Under bath 30min afterwash, naturally dry 8h, then dry 12h in the electric drying oven with forced convection being placed on 80 DEG C, obtain the cambric of alkylation process.
By PP and MAPE according to mass ratio be 99:1 put into pulverizer pulverize, obtain mixture.
The cambric layering taking the mixture after 100g pulverizing and four pieces of alkylation process is taped against in steel mould tool (60mm × 120mm × 3mm), be put into preheating 3min in the vulcanizing press of 189 DEG C, then pressure 10MPa and temperature hot pressing 5min at 189 DEG C is remained on, cold pressing 1min again, obtains natural-fiber composite material.
Embodiment 8
Gunny cloth is cut into 12cm × 7.5cm rectangular block, first being placed on concentration is in the NaOH solution of 5%, soaking at room temperature 30min afterwash, being placed on concentration is again in the Dodecyl trimethyl ammonium chloride solution of 6%, at 60 DEG C of Water Under bath 30min afterwash, naturally dry 8h, then dry 2h in the electric drying oven with forced convection being placed on 120 DEG C, obtain the gunny cloth of alkylation process.
By PP and MAPP according to mass ratio be 95:5 put into pulverizer pulverize, obtain mixture;
The gunny cloth layering taking the mixture after 100g pulverizing and four pieces of alkylation process is taped against in steel mould tool (60mm × 120mm × 3mm), be put into preheating 5min in the vulcanizing press of 180 DEG C, then pressure 10MPa and temperature hot pressing 7min at 180 DEG C is remained on, cold pressing 1min again, obtains natural-fiber composite material.
Embodiment 9
Linen is cut into 12cm × 7.5cm rectangular block, first being placed on concentration is in the NaOH solution of 2%, soaking at room temperature 30min afterwash, being placed on concentration is again in the cetyl trimethylammonium bromide solution of 5%, at 60 DEG C of Water Under bath 30min afterwash, naturally dry 8h, then dry 6h in the electric drying oven with forced convection being placed on 100 DEG C, obtain the linen of alkylation process.
By PP and MAPP according to mass ratio be 98:2 put into pulverizer pulverize, obtain mixture.The linen layering taking the mixture after 100g pulverizing and four pieces of alkylation process is taped against in steel mould tool (60mm × 120mm × 3mm), be put into preheating 3min in the vulcanizing press of 189 DEG C, then pressure 10MPa and temperature hot pressing 5min at 189 DEG C is remained on, cold pressing 1min again, obtains natural-fiber composite material.Be 30.5MPa by the breaking tenacity of embodiment 9 gained matrix material, tensile modulus is 2.59GPa, and shock strength is 8.03KJ/m
2, mechanical property is better than PP.By embodiment 9 gained matrix material 5% thermal weight loss temperature be 305 DEG C.
Claims (10)
1. a natural-fiber composite material, is characterized in that, this matrix material obtains through the natural fiber of modification and UPE/ polypropylene composite materials;
Described moisture-absorption modified natural fiber is first placed in NaOH solution by natural fiber to react, then be placed in cationic surfactant solution and carry out modification, then places in atmosphere, then dry and obtain.
2. a kind of natural-fiber composite material according to claim 1, it is characterized in that, described natural fiber source is jute, mestha, sisal hemp, abaca, flax, kendir, hemp, hemp, ramie, bamboo fibers, coir, xylon, cotton, bombax cotton, wheat stalk, triticale stalk, maize straw, straw straw, jowar stalk, hemp stalk, sunflower stalk, Cotton Stalk, cigarette stalk, millet stalk or soya bean stalk.
3. cats product according to claim 1, is characterized in that, described cats product is eight alkyl trimethyl ammonium chlorides, decyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, two octyl alkyl dimethyl ammonium chloride, didecyl Dimethy ammonium chloride, distearyl dimethyl ammonium chloride, triethyl methyl ammonium chloride, tripropyl ammonio methacrylate, tributyhnethylammonium chloride, tri-n-octyl methyl ammonium chloride, tetramethyl ammonium chloride, etamon chloride, tetrabutylammonium chloride, benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, tetramethyl-Ammonium hydrogen sulfate, Tetrabutyl amonium bromide, 4-propyl bromide, tetraethylammonium bromide, 4 bromide, tributyl-methyl phosphonium brometo de amonio, tricaprylmethyl brometo de amonio, DDA, didodecyldimethylammbromide bromide, didecyl Dimethy brometo de amonio, Cetyltrimethylammonium bromide, cetyl trimethylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, eight alkyl trimethyl ammonium bromides, ten alkyl trimethyl ammonium bromides, Trimethyllaurylammonium bromide, N, N-diethyl-(3-anisole oxygen ethyl) benzyl ammonium chloride etc.
4. a kind of natural-fiber composite material according to claim 1, is characterized in that, described NaOH solution massfraction is 1-5%, and cationic surfactant solution massfraction is 2-6%.
5. a kind of natural-fiber composite material according to claim 1, is characterized in that, described reacts in NaOH solution, and the time of reacting in cationic surfactant solution is respectively 5-60min.
6. a preparation method for natural-fiber composite material, is characterized in that, comprising:
Step one: natural fiber is carried out modification in NaOH solution, then be placed in cationic surfactant solution and carry out modification, then place in atmosphere, then dry the natural fiber obtaining modification;
Step 2: by modified natural fiber and UPE/ polypropylene composite materials, obtain natural-fiber composite material.
7. the working method of a kind of natural-fiber composite material according to claim 5, is characterized in that, described modified natural fiber and the method for UPE compound are:
By UPE resin, solidifying agent, promotor and defoamer mixing, obtain mixture, mixture is coated on the natural fiber of modification, after curing molding, obtains natural-fiber composite material.
8. the preparation method of a kind of natural-fiber composite material according to claim 6, is characterized in that, described UPE resin, solidifying agent, promotor and defoamer, according to mass fraction meter, comprising:
UPE resin 89-100 part, solidifying agent 0.10-3 part, promotor 0.01-0.5 part, defoamer 0-10 part.
9. the working method of a kind of natural-fiber composite material according to claim 5, is characterized in that, the natural fiber of described modification and the method for polypropylene composite materials are:
The natural fiber of polypropylene, coupling agent and modification is obtained natural-fiber composite material by pressure sintering processing.
10. the working method of a kind of natural-fiber composite material according to claim 9, it is characterized in that, described coupling agent is maleic anhydride inoculated polypropylene, maleic anhydride grafted ABS, maleic anhydride grafted polyethylene, maleic anhydride graft EVA, dimerization di (isooctyl) phosphate Magnesium Stearate, DL series aluminate coupling agent, TC-130, powder silane coupling agent XH-820 series, aminopropyl triethoxysilane, methacryloxypropyl trimethoxy silane, glycydoxy Trimethoxy silane, vinyltriethoxysilane, ethylenediaminepropyltriethoxysilane, dredge propyl trimethoxy silicane, quadrol hydroxypropyl methyl dimethoxysilane.
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