CN101791815A - Polymethyl methacrylate simulated redwood composite material and preparation method thereof - Google Patents
Polymethyl methacrylate simulated redwood composite material and preparation method thereof Download PDFInfo
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- CN101791815A CN101791815A CN201010114192A CN201010114192A CN101791815A CN 101791815 A CN101791815 A CN 101791815A CN 201010114192 A CN201010114192 A CN 201010114192A CN 201010114192 A CN201010114192 A CN 201010114192A CN 101791815 A CN101791815 A CN 101791815A
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Abstract
The invention relates to a polymethyl methacrylate simulated redwood composite material and a preparation method thereof. The material is a composite material prepared by using softwood as a substrate and introducing a methyl methacrylate monomer to be soaked into the softwood. The preparation method comprises the following steps of: (1) soaking the softwood in an alkali liquor to perform reflux degreasing; (2) taking out the softwood after the degreasing, refluxing the softwood to remove the alkali liquor, and drying the softwood; (3) in a vacuum state at the normal temperature, soaking the softwood in solution of the methyl methacrylate monomer dissolved with a dye for 0.5 to 10 hours; and (4) putting the softwood into a drying apparatus, and performing polymerization to obtain the polymethyl methacrylate simulated redwood composite material. The polymethyl methacrylate simulated redwood composite material prepared by the method improves the density of woods, reduces the water absorption, the swell-shrink characteristics and the sensitivity to climates of the woods, and improves the dimensional stability and the balance of mechanical properties; besides, the preparation method is simple to operate and has a low cost and high economic benefits.
Description
Technical field
The invention belongs to imitating padauk composite material and preparation field thereof, particularly relate to a kind of polymethyl methacrylate simulated redwood composite material and preparation method thereof.
Background technology
Redwood is a class precious timber, mainly contain narra (RED SANDALWOOD, mainly originate in India, Vietnam, Thailand, Burma and the South Sea Islands), acid branch wood (BLACKWOOD, be distributed in the torrid zone and subtropical zone), rosewood (PADAUK is distributed in the global tropical area), Door frame etc.Redwood has characteristics such as the heavy firmly exquisiteness of compact structure, corrosion resistant, material, tool special aroma, color and luster deepness, is the elaboration in the timber, is subjected to people's favor for a long time always.
Redwood is longer growth period, and after through human long-term the felling, the redwood resource significantly reduces.Strengthen in various countries under the overall situation of the national forest reserves of protection, redwood becomes scarce resource gradually.Under this big situation, people begin to concentrate one's gaze on the imitative redwood material of manual manufacture.
Li Zongkui [Li Zongkui, imitative blackwood products and compacting tool set: 87213756.2[P thereof] .1987-09-23] a kind of method of making imitative blackwood products disclosed.Adopted the plastic fibre powder hot-forming in mould as raw material.People such as Zhou Youshen [Zhou Youshen etc., production technique of plastic fibre: 88105469[P] .1988-02-01] a kind of plastic fibre material manufacturing process disclosed.It is a filler with a large amount of thick wood chips and natural fiber, and adopts and fully be penetrated into fibrous inside with low amounts of resin, and then in the method for heating pressurized conditions compacted under, curing, so cost is low, and has the characteristic of moulded plastic.Compare with bakelite, fragility also improves.Goods for adding suitable pigment or dyestuff can be made into imitative redwood.Adopt Lauxite and be decorated with the light-colored plastifying fiber of wood grain on the surface, the suitable combination furniture of doing.Yang Hu [Yang Hu, the forming method of moulds for artificial decorative board: 96114110.7[P] .1996-12-24] invented a kind of forming method of moulds for artificial decorative board.It is with synthetic material or directly spraying of rubber, round brush or plastic uptake to plank that has wood grain or bag or the last moulding of slabstone, its product can be made various imitative redwood, nanmu, teak, Manchurian ash and marble, granite, decorative panel mould.Chen Kejian [Chen Kejian, thermosetting Linen down material: 89109454.7[P] .1989-12-26] production method of having invented a kind of thermosetting Linen down composite, can produce the mould pressing process product and the furniture of color such as imitative redwood.Concrete technology is for adopting the leftover bits and pieces fiber crops suede of flax spinning industry, and through removing, combing, soak with thermosetting resin, step-down removes solvent, cures, the mold pressing thermosetting forms, and can bear car, mills, machinings such as plane, brill.People such as Yang Guang [Yang Guang etc., a kind of artistic carved furniture and preparation method: 96118043.9[P] .1996-02-12] preparation method of having invented a kind of artistic carved furniture.It is to form being carved with on the mould of artistic carved pattern by prefabricated decoration paint film, organic lining and reinforcement material and the skeleton material one-step mould that contains a large amount of strings, its paint and furniture one-shot forming, organic lining and inorganic skeleton material closely wrap up, save back abrasive brush lacquer craftwork, can be made into multiple artistic carved furnitures such as copper modelled after an antique, imitative redwood.Chen Yu and wait people [Chen Yu and etc., the production method of paulownia single board imitating red sandalwood dyeing: 01114356.8[P] .2001-07-12] invented a kind of in the timber production and processing, being used for paulownia single board imitate the method that redwood dyes.Be that the paulownia single board of bleaching is put into dye vat, to pour in the dye vat by the dyeing liquor that acid scarlet, acid lake blue, acid light yellow and bleeding agent, salt and acetate are made, be warming up to 90 ℃ and keep circulation under constant temperature, dye and get rid of dye liquor after 4 hours, the washing back is dry to get final product.
Foregoing invention all claims and can produce imitative redwood material, but have just with wood staining, and major part is the compound of natural material such as timber, fiber-like and macromolecular material, comes down to mould Wood combined material.Open people such as copper seal [opening copper seal etc., new type environment-protecting plastic wood material and preparation method thereof: 01123791.0[P] .2001-08-01] invented a kind of environment-protecting plastic wood material.It is to adopt plastics, natural fiber and various auxiliary agent formulated.Its preparation method is: in high-speed mixer, natural fiber is added coupling agent carry out surface modification, add plastics and various auxiliary agent again, put into extruder after mixing and extrude, make difformity and quick cooling and shaping by mould, cut into section bar.People such as Zhao Maiqun [Zhao Maiqun etc., a kind of straw strengthens composite polyolefine material and manufacture method: 200710019100.9[P thereof] .2007-11-19] invented a kind of enhancing composite polyolefine material of forming by natural plants stalk, polyolefin plastics and processing aid.Processing aid is 2%～5% of a gross weight, and processing aid comprises any two or three mixing of coupling agent, compatilizer, lubricant.The preparation method is: straw mixes with processing aid after pulverizing oven dry, and then with polyolefin pellets blend, granulation, the plastic-wood material that extrude again, cooling and shaping, traction cuts into certain specification.People such as Gan Yili [Gan Yili etc., plastic-wood material and its production and application: 200710037114.3[P] .2007-02-02] a kind of preparation method of plastic-wood material disclosed.The component of said plastic-wood material and parts by weight ratio comprise: 35～50 parts of thermoplastics, 50～60 parts on string, 1～5 part of coupling agent.The plastic-wood material of invention can adopt extruding-out process to prepare section bar, sheet material, also can adopt injection moulding, blowing, die press technology for forming.People such as Ding Jiansheng [Ding Jiansheng etc., inorganic nano particle composite plastic-wood materials and preparation method thereof: 200610039984.X[P] .2006-04-28] invented a kind of inorganic nano particle composite plastic-wood materials, form by following each component: (A) plastics of mass percent 24-98%; (B) natural fiber of mass percent 0-70%; (C) inorganic nano-particle of mass percent 1-30%.With said components through high-speed mixing, extrude, operations such as injection moulding and mold pressing can make finished product.It is said that this inorganic nano particle composite plastic-wood materials compares common Wood plastic composite, impact strength can improve 10-20kJ/m2, and bending strength can improve 5-18MPa.Chen Kun [Chen Kun, a kind of antibiotic anion plastic-wood material: 200710073848.7[P] .2007-04-11] invented a kind of a kind of antibiotic anion plastic-wood material of making by carrying silver antimicrobials, compound preservative, wood fiber powder, anion mineral powder, high molecular polymer and auxiliary material etc.During preparation earlier with high molecular polymer under the effect of extruder temperature and extrusion pressure with carrying silver antimicrobials, complex antimicrobials, compound preservative, wood fiber powder and auxiliary material consolute.By the extrusion die vacuum forming, modes such as compression molding or roll-forming obtain antibiotic anion plastic-wood material.It is said that this material has antibiotic, far infrared emission, anion function and material antiseptic characteristic.People such as Zehner [Zehner et al., Synthetic wood composite material and method for molding, U.S.Pat.No.6780359] cellulose material and plastics are mixed the composite plastic plate of having invented a kind of cellulose enhancing.Earlier cellulose is smashed, granulation then enters mould and moulds moulding.People such as Liu [Liu et al., Fire retardant wood composite materials, U.S.Pat.No.6713168] have invented a kind of flame-retardant composite board material that is composited by wood fibre bundle and at least a organic phosphide class.In the process, crosslinked action and curing molding have taken place in the organic phosphide class in the composite board of this mechanics orientation under the thermal environment of pressurization.People such as Rosthauser are [Rosthauser et al., MixedPMDI/resole resin binders for the production of wood composite products, U.S.Pat.No.6641761 in similar 2 patents; Rosthauser et al., Mixed PMDI/solid novolac resin binders for the production of woodcomposite products, U.S.Pat.No.6641762] a kind of invention of timber and polyformaldehyde, polyphenyl isocyanates and phenolic resins being solidified composite molding in mould or under the pressure disclosed.People such as Black [Black et al., Wood compositeprepared with a B-stageable resin, U.S.Pat.No.6432254] have invented a kind of phenolic aldehyde Wood plastic composite.Earlier with phenolic resins coating on wooden device; Under 80～140 ℃, resin forms clad at device surface; In the superheated steam environment, make the resin solidification moulding again.The molecular weight of used phenolic resins is between 200～600, and the mol ratio of phenol and formaldehyde is 1.3: 1 to 2.0: 1.
More than the adding of the timber in the Wood plastic composite of Jie Shaoing form generally all enters to smash state, has easy to operate advantage.But well-known, most macromolecular materials all have creep, and promptly dimensional stability is relatively poor.Wood components in the above-mentioned composite can not play the effect that improves dimensional stability.
Summary of the invention
Technical problem to be solved by this invention provides a kind of polymethyl methacrylate simulated redwood composite material and preparation method thereof, this material has improved the density of timber, reduced timber water absorption rate, swell-shrink characteristic and to the sensitiveness of weather, dimensional stability improves, the harmony of mechanical property improves; The preparation method is simple to operate, and cost is low, the economic benefit height.
A kind of polymethyl methacrylate simulated redwood composite material of the present invention, this material is matrix with the soft wood, draw methyl methacrylate monomer and infiltrate through the composite that is polymerized behind the timber inside, the mass ratio of methyl methacrylate monomer and wooden unit is 0.3～2: 1.
Described soft wood refers to acerose timber alleged on the wood technology.
Described soft wood needs to carry out ungrease treatment with alkali lye before processing.
Described composite is the sheet material or the moulding device of arbitrary dimension.
The preparation method of a kind of polymethyl methacrylate simulated redwood composite material of the present invention comprises:
(1) soft wood is immersed in the degreasing that refluxes in the alkali lye;
(2) soft wood after the taking-up degreasing in 50～100 ℃ of following water backflow flush away alkali lye, is dried under 70 ± 20 ℃ of temperature;
(3) under the normal temperature vacuum state, soft wood is immersed in the methyl methacrylate monomer solution that is dissolved with dyestuff 0.5～10 hour, methyl methacrylate monomer and dyestuff penetration are gone in the soft wood;
(4) soft wood that will soak into methyl methacrylate monomer and dyestuff is placed in the baker, carries out the polymethyl methacrylate polymerization 1～5 hour under 70～120 ℃ of temperature, carries out surface finish after the taking-up and promptly gets imitating padauk composite material.
Alkali lye in the described step (1) is NaOH, Na
2CO
3, NaHCO
3In one or more mixing; The mass percent concentration of alkali lye is 1～10%.
The ungrease treatment time in the described step (1) is 1～20 hour, and temperature is 50～100 ℃.
Dyestuff in the described step (3) is one or more among disperse scarlet HBGL, disperse scarlet S-BWFL, disperse scarlet BWFL, Disperse Black EX-SF, disperse Black B 150 RFL, disperse brown 2B-FS, the disperse violet S-4B.
The methyl methacrylate monomer in the described step (3) and the mass ratio of dyestuff are 40～70: 1.
Of the present invention a kind of be that the imitating padauk composite material of reinforcing material can replace high-quality timber to be applied to fields such as furniture, building, art with the polymethyl methacrylate.
Imitating padauk composite material of the present invention adopts soft wood to hold polymethyl methacrylate for matrix plays, keep scantling stability, the effect of wooden lines is provided and presents with integrality, helps the stable of size; Soft wood refers to acerose timber alleged on the wood technology, and the main composition composition is a test-tube baby, and generally speaking, coniferous wood is soft than broad-leaved wood, and economic worth is also lower.Polymethyl methacrylate is to form in the timber interior polymeric, plays the effect of mechanical properties such as increasing the strength of materials, hardness, anti-bending strength, anti-wear performance.By with the Combined Processing of polymethyl methacrylate after, mechanical property strengthens greatly, has improved the value of soft wood.And the preparation method is simple to operate, and cost is low, the economic benefit height.
The adding of a small amount of dyestuff can make composite have the color and luster of redwood, can simulate various redwood (narra, acid branch wood, rosewood, Door frame etc.).
Imitating padauk composite material of the present invention has the same processability of natural timber, as: saw, cut, dig, nail, tenon etc., cut bonding etc.
Beneficial effect
(1) imitating padauk composite material employing soft wood of the present invention is a matrix.All there is the three major types natural defect usually in natural timber:
1. knaur, cross grain and because of growth stress or the defective that forms of damage naturally;
2. the biological defective that causes harm mainly contains rotten, variable color and damages by worms etc.;
3. the defective that causes of drying and machining.As dry and cracked, warpage, saw kerf wound etc.;
Above-mentioned defective has reduced the grade and the value of timber in varying degrees, and by with the Combined Processing of macromolecular material after, these defectives have all obtained overcoming;
(2) by to the Combined Processing of soft wood, improved the density of timber, reduced timber water absorption rate and swell-shrink characteristic, the sensitiveness of weather is reduced greatly, dimensional stability greatly improves;
(3) timber is anisotropic material, and the mechanical property of rift grain direction and band direction has very big difference.But after Combined Processing, the harmony of mechanical property greatly improves;
(4) the timber composition in the Wood plastic composite on the market generally all is to pulverize the back to add, and therefore graceful wooden lines is all gone, and the present invention has kept original wood grain owing to adopted original shape timber, has improved the application class of product;
(5) preparation method of the present invention is simple to operate, and cost is low, the economic benefit height.
Description of drawings
Fig. 1: raw material
Fig. 2: imitating padauk composite material
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) pine sheet material being immersed concentration is the ungrease treatment that refluxes in 1% the NaOH alkali lye, and the processing time is 10 hours, and treatment temperature is 80 ℃;
(2) take out timber,, under 60 ℃ of temperature, dry again in 60 ℃ of following water backflow flush away alkali lye;
(3) under the normal temperature, timber is under the vacuum state suction 1 hour, injects methyl methacrylate monomer and dyestuff (disperse violet S-4B) down in vacuum state again, the mass ratio of methyl methacrylate monomer and dyestuff is 40: 1, treat that the recession of solution submergence timber removes vacuum, keeps submergence 1 hour;
(4) timber that will soak into methyl methacrylate monomer and dyestuff is placed in the baker, carries out the polymethyl methacrylate polymerization 2 hours under 120 ℃ of temperature;
(5) carry out surface finish after the taking-up and promptly get imitating padauk composite material.
(6) after tested, the density value of imitating padauk composite material batten is from handling preceding 0.42g/cm
3Rise to the 0.76g/cm after the processing
3, improved 80%; Impact strength is from handling preceding 15.6kJ/m
2Rise to the 39.8kJ/m after the processing
2, improved 155%.
Embodiment 2
(1) fir wood plank being immersed concentration is the ungrease treatment that refluxes in 1.5% the NaOH alkali lye, and the processing time is 12 hours, and treatment temperature is 90 ℃;
(2) take out timber,, under 65 ℃ of temperature, dry again in 70 ℃ of following water backflow flush away alkali lye;
(3) under the normal temperature, timber is under the vacuum state suction 2 hours, injects methyl methacrylate monomer and dyestuff (Disperse Black EX-SF) down in vacuum state again, the mass ratio of methyl methacrylate monomer and dyestuff is 50: 1, treat that the recession of solution submergence timber removes vacuum, keeps submergence 2 hours;
(4) timber that will soak into methyl methacrylate monomer and dyestuff is placed in the baker, carries out polymethyl methacrylate polyase 13 hour under 110 ℃ of temperature;
(5) carry out surface finish after the taking-up and promptly get imitating padauk composite material.
Embodiment 3
(1) cypress sheet material being immersed concentration is 2% Na
2CO
3The ungrease treatment that refluxes in the alkali lye, the processing time is 15 hours, treatment temperature is 95 ℃;
(2) take out timber,, under 70 ℃ of temperature, dry again in 80 ℃ of following water backflow flush away alkali lye;
(3) under the normal temperature, timber is under the vacuum state suction 2.5 hours, inject methyl methacrylate monomer and dyestuff (disperse brown 2B-FS) down in vacuum state again, the mass ratio of methyl methacrylate monomer and dyestuff is 60: 1, treat that the recession of solution submergence timber removes vacuum, keeps submergence 2.5 hours;
(4) timber that will soak into methyl methacrylate monomer, catalyst and dye solution is placed in the baker, carries out the polymethyl methacrylate polymerization 4 hours under 100 ℃ of temperature;
(5) carry out surface finish after the taking-up and promptly get imitating padauk composite material.
Embodiment 4
(1) platane wood sheet material being immersed concentration is the ungrease treatment that refluxes in 2% the NaHCO3 alkali lye, and the processing time is 17 hours, and treatment temperature is 100 ℃;
(2) take out timber,, under 75 ℃ of temperature, dry again in 90 ℃ of following water backflow flush away alkali lye;
(3) under the normal temperature, timber is under the vacuum state suction 3 hours, inject methyl methacrylate monomer and dye solution (disperse scarlet HBGL) down in vacuum state again, the mass ratio of methyl methacrylate monomer and dyestuff is 70: 1, treat that the recession of solution submergence timber removes vacuum, keeps submergence 3 hours;
(4) timber that will soak into methyl methacrylate monomer, catalyst and dye solution is placed in the baker, carries out the polymethyl methacrylate polymerization 16 hours under 150 ℃ of temperature;
(5) carry out surface finish after the taking-up and promptly get imitating padauk composite material.
Claims (9)
1. polymethyl methacrylate simulated redwood composite material, this material is a matrix with the soft wood, draws methyl methacrylate monomer and infiltrates through the composite that is polymerized behind the timber inside, the mass ratio of methyl methacrylate monomer and wooden unit is 0.3～2: 1.
2. a kind of polymethyl methacrylate simulated redwood composite material according to claim 1 is characterized in that: described soft wood is acerose timber.
3. a kind of polymethyl methacrylate simulated redwood composite material according to claim 1 is characterized in that: described soft wood needs to carry out ungrease treatment with alkali lye before processing.
4. a kind of polymethyl methacrylate simulated redwood composite material according to claim 1 is characterized in that: described composite is the sheet material or the moulding device of arbitrary dimension.
5. the preparation method of a polymethyl methacrylate simulated redwood composite material comprises:
(1) soft wood is immersed in the degreasing that refluxes in the alkali lye;
(2) soft wood after the taking-up degreasing in 50～100 ℃ of following water backflow flush away alkali lye, is dried under 70 ± 20 ℃ of temperature;
(3) under the normal temperature vacuum state, soft wood is immersed in the methyl methacrylate monomer solution that is dissolved with dyestuff 0.5～10 hour, methyl methacrylate monomer and dyestuff penetration are gone in the soft wood;
(4) soft wood that will soak into methyl methacrylate monomer and dyestuff is placed in the baker, carries out the polymethyl methacrylate polymerization 1～5 hour under 70～120 ℃ of temperature, carries out surface finish after the taking-up and promptly gets imitating padauk composite material.
6. the preparation method of a kind of polymethyl methacrylate simulated redwood composite material according to claim 5, it is characterized in that: the alkali lye in the described step (1) is NaOH, Na
2CO
3, NaHCO
3In one or more mixing; The mass percent concentration of alkali lye is 1～10%.
7. the preparation method of a kind of polymethyl methacrylate simulated redwood composite material according to claim 5, it is characterized in that: the ungrease treatment time in the described step (1) is 1～20 hour, temperature is 50～100 ℃.
8. the preparation method of a kind of polymethyl methacrylate simulated redwood composite material according to claim 5, it is characterized in that: the dyestuff in the described step (3) is one or more among disperse scarlet HBGL, disperse scarlet S-BWFL, disperse scarlet BWFL, Disperse Black EX-SF, disperse Black B 150 RFL, disperse brown 2B-FS, the disperse violet S-4B.
9. the preparation method of a kind of polymethyl methacrylate simulated redwood composite material according to claim 5, it is characterized in that: the methyl methacrylate monomer in the described step (3) and the mass ratio of dyestuff are 40～70: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010114192A CN101791815A (en) | 2010-02-25 | 2010-02-25 | Polymethyl methacrylate simulated redwood composite material and preparation method thereof |
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|---|---|---|---|
| CN201010114192A CN101791815A (en) | 2010-02-25 | 2010-02-25 | Polymethyl methacrylate simulated redwood composite material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241037A (en) * | 2011-05-09 | 2011-11-16 | 中南林业科技大学 | Red washable timber and preparation method thereof |
| CN109648657A (en) * | 2018-12-11 | 2019-04-19 | 浙江大东吴绿家木业有限公司 | Modified wood skin, the method for modifying of wood skin, wood skin/stone plastic composite board and preparation method thereof |
| CN111775253A (en) * | 2020-07-17 | 2020-10-16 | 安徽三和工艺品有限公司 | Preparation method of impregnating resin for wickerwork |
-
2010
- 2010-02-25 CN CN201010114192A patent/CN101791815A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241037A (en) * | 2011-05-09 | 2011-11-16 | 中南林业科技大学 | Red washable timber and preparation method thereof |
| CN102241037B (en) * | 2011-05-09 | 2014-01-08 | 中南林业科技大学 | Red washable timber and preparation method thereof |
| CN109648657A (en) * | 2018-12-11 | 2019-04-19 | 浙江大东吴绿家木业有限公司 | Modified wood skin, the method for modifying of wood skin, wood skin/stone plastic composite board and preparation method thereof |
| CN111775253A (en) * | 2020-07-17 | 2020-10-16 | 安徽三和工艺品有限公司 | Preparation method of impregnating resin for wickerwork |
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Inventor after: Yang Qing Inventor after: Huang Xiucheng Inventor after: Zhang Yueting Inventor after: Gan Ju Inventor after: Su Feng Inventor after: Yuan Zengyi Inventor after: Zhao Jing Inventor after: Huang Liyuan Inventor before: Yang Qing Inventor before: Huang Xiucheng Inventor before: Zhang Yueting Inventor before: Gan Ju Inventor before: Su Feng Inventor before: Yuan Zengyi |
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Free format text: CORRECT: INVENTOR; FROM: YANG QING HUANG XIUCHENG ZHANG YUETING GAN JU SU FENG YUAN ZENGYI TO: YANGQING HUANG XIUCHENG ZHANG YUETING GAN JU SU FENG YUAN ZENGYI ZHAO JING HUANG LIYUAN |
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Application publication date: 20100804 |