CN101691054B - Method for preparing low-interlaminar-spacing polylactic-acid-base linen fiber composite plates - Google Patents
Method for preparing low-interlaminar-spacing polylactic-acid-base linen fiber composite plates Download PDFInfo
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Abstract
The invention belongs to the field of polymer materials and composite materials, and relates to a method for preparing low-interlaminar-spacing polylactic-acid-base linen fiber composite plates. The method comprises the following specific steps: grinding polylactic acid through a grinder to obtain powdery and granular polylactic acid; adopting a method of laying fabric-type linen fibers layer by layer; and obtaining the polylactic-acid-base linen fiber composite plates by utilizing the good mechanical properties, thermoplasticity, fiber-forming property, high transparency and other advantages of polylactic acid through a hot-press molding process. As the powdery and granular polylactic acid has good permeability and large specific surface area, and as the interfacial combination property of linen fibers and polylactic acid resinite is improved through chemical modification, the polylactic-acid-base linen fiber composite plates with low interlaminar properties and good interlaminar properties are obtained. The preparation method has the advantages of simple practicable property, raw materials capable of industrial production and good value of popularization and application.
Description
Technical field
The invention belongs to macromolecular material and technical field of composite materials, be specifically related to a kind of preparation method of low-interlaminar-spacing polylactic-acid-base linen fiber composite plates.
Background technology
The natural fiber reinforced composite adds the natural degradable composition in polymer: flaxen fiber, and the whole regenerability of composite is improved, be a kind of green ecological composite.Simultaneously because its specific strength and characteristics such as specific modulus is high, heat insulation, sound insulation property is good, energy absorption capability is good, shock-resistant, no brittle fracture have substituted glass fibre and carbon fiber, the particularly application on automobile in some application.Automobile mainly is a fabric fibre with natural fiber, like bluish dogbane, and hemp, flax, jute, flaxen fiber such as sisal hemp and coir fibre etc.The automaker of Germany comprises benz, BMW, Audi, masses, goes before aspect the automobile making in that string is applied to.1999, the auto industry chief engineer in Europe used 21000 tons of natural fibers, and wherein the motor corporation of Germany has just used 15500 tons of natural fibers, is three times before 5 years.The auto parts and components and the interior material that adopt the ecological ideas composite to make, environment compatibility is good, is easy to reclaim and recycling, can satisfy strategy of sustainable development needs in the world wide.The ramie output of China accounts for more than 90% of world's total amount, and flax output occupies the second place of the world, and yellow mestha accounts for 20% of world's total amount.The development of ramie product must help promoting the plantation of ramie product; This had both helped western eco-environment; Can build global green textile supply base again, especially can produce positive great function, simultaneously the protection timber resources had far reaching significance China's strategy to develop western regions.Therefore, it is just very urgent and important as the research and development of car body materials to carry out the ecological ideas composite.The ramee microstructure is unique; Cross section is oval shape or the polygonal that cavity is arranged; Horizontal joint and perpendicular line are vertically arranged, and be that fibre length is the longest in the flaxen fiber, the degree of crystallinity of fiber, the degree of orientation and longitudinal modulus of elasticity are all higher; Be fit to do the matrix of resin composite materials, therefore being equipped with composite with ramee as the enhancing system has very big development potentiality.
Document Huda, M.S., Drzal; L.T., Mohanty, A.K.; Misra, M..Composites Science andTechnology.2008,68; 424-432 has adopted the method for compacting layer by layer of polylactic acid film and bluish dogbane fabric to make polylactic acid substrate-shaped molding compound, and he has adopted the method for the flaxen fiber surface being carried out etching processing and silane coupler processing, and has adopted general hot pressing formation process.
Document Ochi, S.Mechanics of Materials.2008,40,446-452 adopts the flaxen fiber material without the component and the place of production, also is that the hot pressing formation process through polylactic acid film and bluish dogbane fabric makes polylactic acid substrate-shaped molding compound.
Plastic composite and automobile lightweight in the evolution of automotive material, energy-conservation and environmental protection have inseparable relation.At present, fiberglass reinforced plastics (FRP) along with the maturation of technology just in expanding application, be the main method of utilizing flaxen fiber with natural fiber and synthetic resin and the conventional automotive material of the compound replacement of plastics.Natural fiber has higher intensity, modulus and less density, is suitable as the enhancing body of polymer (comprising thermosetting and thermoplasticity) based composites.Through chemical modification, improved the combination interface property of flaxen fiber and resinite.Combine PLA good mechanical character, thermoplasticity, fibre forming property, synthetic exterior trim and the interior material that meets the new-energy automobile serviceability of transparency advantages of higher simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of low-interlaminar-spacing polylactic-acid-base linen fiber composite plates.
The present invention pulverizes powder-type and the corpuscular PLA that polylactic resin obtains with pulverizer; The method that adopts the textile type flaxen fiber to lay layer by layer; Utilize PLA good mechanical performance, thermoplasticity, fibre forming property, transparency advantages of higher to make polylactic-acid-base linen fiber composite plates through hot press forming technology; Because powder-type and corpuscular PLA good penetration property and bigger specific area; Through chemical modification, improved the interfacial bonding property of flaxen fiber and resinite, the polylactic-acid-base linen fiber composite plates that obtains having performance between low layer simultaneously with better mechanical property.
The preparation method of the low-interlaminar-spacing polylactic-acid-base linen fiber composite plates that the present invention proposes, concrete steps are following:
(1) be among 0.5%～10% the basic solvent B that contains alkaline matter A with concentration, add the textile type flaxen fiber, the reaction time is 10～30 minutes, and product cleans several times (being generally 3-6 time) with basic solvent B after proposing from alkaline solution A; Putting into concentration then is 0.05～3% silane coupler solution C, after product proposes, cleans several times with basic solvent B, puts into the vacuum drying oven drying, obtains the textile type flaxen fiber;
(2) will pass through the polylactic resin of double screw extruder additive package, pulverize or the flour mill abrasive dust, obtain granular pattern PLA or powder-type PLA through pulverizer;
(3) textile type flaxen fiber of step (1) gained being handled and step (2) gained granular pattern PLA or powder-type PLA adopt hot pressing formation process to make polylactic-acid-base linen fiber composite plates through laying layer by layer; Wherein: the mass ratio of PLA and textile type flaxen fiber is .6: 4-7: 3.
Among the present invention, alkaline matter A described in the step (1) is selected from NaOH, potassium hydroxide or the potassium permanganate one to several kinds.
Among the present invention, basic solvent B described in the step (1) is selected from absolute ethyl alcohol, acetone, benzene, toluene, chlorohydrocarbon, dimethyl formamide or the methyl-sulfoxide one to several kinds.
Among the present invention, silane coupler solution C described in the step (1) is selected from aminopropyl triethoxysilane (KH-550), γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560), γ-methacryloxypropyl trimethoxy silane (KH-570), tetra-sulfurized pair triethoxy trisilalkane (KH-845-4), N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan (KH-792), VTES (DL-151), vinyltrimethoxy silane (DL-171), N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane (DL-602) or the anilinomethyl triethoxysilane (ND-42) one to several kinds.
Among the present invention, described textile type flaxen fiber is in plain knit fabric, rib fabric, links links fabric, air layer kind fabric, tuck kind fabric, barring-on kind fabric, displaced stitch or the applique one to several kinds.
Among the present invention, textile type flaxen fiber described in the step (1) be in ramee, flax fiber, tossa, bastose, sisal fiber or the bamboo fibre in one to several kinds.
Among the present invention, additive is fire retardant or reinforcing agent described in the step (2).
Among the present invention, said fire retardant is in APP, red phosphorus, melamine, the acid of 2-carboxyethyl phenyl phosphinic acid, phenyl dichloro phosphine or the phenylphosphonyl dichloride one to several kinds.
Among the present invention, said reinforcing agent is in nano-calcium carbonate, nanometer calcium sulfate, nano titanium oxide, nano silicon, nano imvite or the CNT one to several kinds.
Among the present invention, the rotating speed of said double screw extruder is 50～250rpm.
The invention has the advantages that: resulting product has excellent biological degradability, satisfies the environmental protection demand.
The invention has the advantages that: raw material sources are extensive, but the equal suitability for industrialized production of used textile type flaxen fiber, PLA, and the preparation method is simple.
Description of drawings
Fig. 1 is the interfloor distance figure of particle powder type and film-type polylactic-acid-base linen fiber composite plates.Wherein: (A) be particle powder type polylactic-acid-base linen fiber composite plates, (B) be and the film-type polylactic-acid-base linen fiber composite plates.
Fig. 2 is a flaxen fiber stretching sectional drawing after treatment.(C) polylactic-acid-base linen fiber composite plates of untreatment fiber, (D) polylactic-acid-base linen fiber composite plates of processing back fiber.
The specific embodiment
Following examples are to further specify of the present invention, rather than limit scope of the present invention.
Embodiment 1: with PLA, plain cloth type flaxen fiber 30 ℃ of following vacuum drying 24 hours, to remove moisture.
1. dried PLA one or more mass ratios according to 95: 5 with ammonium polyphosphate flame retardant, red phosphorus, melamine, the acid of 2-carboxyethyl phenyl phosphinic acid, phenyl dichloro phosphine, phenylphosphonyl dichloride are evenly mixed; And then react in the double screw extruder; Product is through cooling; Pelletizing, oven dry.Screw speed is 50rpm, and the reaction extrusion temperature is 150 ℃.
2. polydactyl acid that step is obtained and the flaxen fiber in the step 1; It is hot-forming to adopt the technology of laying layer by layer to carry out, and wherein the weight ratio of PLA and flaxen fiber is 7: 3, and screw speed is 50～250rpm; The reaction extrusion temperature is 150 ℃; Obtain flaxen fiber/lactic acid composite material, its fire resistance reaches the V-0 grade standard of UL94 regulation, and its limited oxygen index reaches 35.6.Compare with the mechanical property of film-type polylactic-acid-base linen fiber composite plates, its hot strength is brought up to 73MPa by 31.98MPa, and its bending strength is brought up to 146.45MPa by 67.19MPa.
Embodiment 2:
With PLA, rib fabric type flaxen fiber 40 ℃ of following vacuum drying 20 hours, to remove moisture.
2. dried PLA one or more mass ratios according to 70: 30 with reinforcing agent nano-calcium carbonate, nanometer calcium sulfate, nano titanium oxide, nano silicon, nano imvite, CNT are evenly mixed; And then react in the double screw extruder; Product is through cooling; Pelletizing, oven dry.Screw speed is 50rpm, and the reaction extrusion temperature is 150 ℃.
3. polydactyl acid that step is obtained and the flaxen fiber in the step 1; It is hot-forming to adopt the technology of laying layer by layer to carry out, and wherein the weight ratio of PLA and flaxen fiber is 6: 4, and screw speed is 50～250rpm; The reaction extrusion temperature is 150 ℃, obtains flaxen fiber/lactic acid composite material.Compare with the mechanical property of film-type polylactic-acid-base linen fiber composite plates, its impact strength is by 7.43kJ/m
2Bring up to 15.67kJ/m
2
Claims (5)
1. the preparation method of a low-interlaminar-spacing polylactic-acid-base linen fiber composite plates is characterized in that concrete steps are following:
(1) be among 0.5%～10% the basic solvent B that contains alkaline matter A with concentration, add the textile type flaxen fiber, the reaction time is 10～30 minutes, after product proposes from alkaline solution A, with basic solvent B cleaning 3-6 time; Putting into concentration then is 0.05～3% silane coupler solution C, after product proposes, cleans several times with basic solvent B, puts into the vacuum drying oven drying, obtains the textile type flaxen fiber;
(2) will pass through the polylactic resin of double screw extruder additive package, pulverize or the flour mill abrasive dust, obtain granular pattern PLA or powder-type PLA through pulverizer;
(3) textile type flaxen fiber of step (1) gained being handled and step (2) gained granular pattern PLA or powder-type PLA adopt hot pressing formation process to make polylactic-acid-base linen fiber composite plates through laying layer by layer; Wherein: the mass ratio of PLA and textile type flaxen fiber is 6: 4-7: 3;
Wherein: alkaline matter A described in the step (1) is selected from NaOH, potassium hydroxide or the potassium permanganate one to several kinds; Said basic solvent B is selected from absolute ethyl alcohol, acetone, benzene, toluene, chlorohydrocarbon, dimethyl formamide or the methyl-sulfoxide one to several kinds, and said silane coupler solution C is selected from aminopropyl triethoxysilane, γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, tetra-sulfurized pair triethoxy trisilalkane, N-β-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan, VTES, vinyltrimethoxy silane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane or the anilinomethyl triethoxysilane one to several kinds.
2. the preparation method of low-interlaminar-spacing polylactic-acid-base linen fiber composite plates according to claim 1 is characterized in that described textile type flaxen fiber is in plain knit fabric, rib fabric, links links fabric, air layer kind fabric, tuck kind fabric, barring-on kind fabric, displaced stitch or the applique one to several kinds.
3. the preparation method of low-interlaminar-spacing polylactic-acid-base linen fiber composite plates according to claim 1 is characterized in that textile type flaxen fiber described in the step (1) is in ramee, flax fiber, tossa, bastose, sisal fiber or the bamboo fibre one to several kinds.
4. the preparation method of low-interlaminar-spacing polylactic-acid-base linen fiber composite plates according to claim 1 is characterized in that additive is fire retardant or reinforcing agent described in the step (2).
5. the preparation method of low-interlaminar-spacing polylactic-acid-base linen fiber composite plates according to claim 4; It is characterized in that said fire retardant is in APP, red phosphorus, melamine, the acid of 2-carboxyethyl phenyl phosphinic acid, phenyl dichloro phosphine or the phenylphosphonyl dichloride one to several kinds, said reinforcing agent is in nano-calcium carbonate, nanometer calcium sulfate, nano titanium oxide, nano silicon, nano imvite or the CNT one to several kinds.
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| CN101880448A (en) * | 2010-07-06 | 2010-11-10 | 奇瑞汽车股份有限公司 | Nano modified polylactic acid and preparation method thereof |
| CN107310011B (en) * | 2017-08-17 | 2019-12-20 | 常德碳汇工艺品科技有限公司 | Isotropic wood particle board |
| CN107599229A (en) * | 2017-09-18 | 2018-01-19 | 湖南鑫泰麻业股份有限公司 | A kind of production technology of elastic soft flaxen fiber core plate new material |
| CN107936508A (en) * | 2017-12-12 | 2018-04-20 | 芜湖环瑞汽车内饰件有限公司 | A kind of preparation method of automotive trim microcapsule aromatic type composite material |
| CN110343380B (en) * | 2019-08-20 | 2021-08-24 | 吉林大学 | Plant fiber composite material and preparation method and application thereof |
| CN111574754A (en) * | 2020-06-13 | 2020-08-25 | 嘉善天惠服饰有限公司 | Basic formula of full-biodegradable button |
| CN114106537B (en) * | 2021-12-13 | 2022-09-02 | 苏州中达航材料科技有限公司 | Degradable PPC composite board and preparation method thereof |
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