CN1760266A - Method for preparing composite material of poly lacltic acid enhanced by ramie fiber - Google Patents
Method for preparing composite material of poly lacltic acid enhanced by ramie fiber Download PDFInfo
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- CN1760266A CN1760266A CN 200510110181 CN200510110181A CN1760266A CN 1760266 A CN1760266 A CN 1760266A CN 200510110181 CN200510110181 CN 200510110181 CN 200510110181 A CN200510110181 A CN 200510110181A CN 1760266 A CN1760266 A CN 1760266A
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Abstract
A ramie fiber reinforced polylactic acid composition is prepared through respectively dissolving the prepolymer of polylactic acid polycaprolactone in organic solvent, immersing the ramie fibers in the solution of polycaprolactone, adding another solution, sealing, and in-situ polymerizing at 60-100 deg.C for 0.5-4 hr. It has excellent interface and mechanical performance.
Description
Technical field
The present invention relates to the preparation method of a kind of high molecular polymer and fiber-resin composite, particularly relate to a kind of surface treatment of ramee and the preparation method that ramee strengthens thermoplastic resin.
Background technology
Lactic acid polymer (claims again: poly(lactic acid), Polylactic acid; Be called for short: main production raw material PLA) derives from plant resourceses such as corn, potato.This polymkeric substance and post-treatment product thereof have favorable biological degradability and recyclability.Ramee also is a biodegradable material, also has the high and resourceful advantage of specific tenacity simultaneously, and composite material of poly lacltic acid enhanced by ramie fiber is to meet the human environment protection and the strategy of sustainable development, and therefore very fine application prospect is arranged.Countries in the world are more and more to the research of natural fiber reinforced composite at present, but main concentrating strengthens nondegradable thermoplastic resin and thermosetting resin.
Domestic research natural-fiber composite material is mainly by Zhongshan University, the National University of Defense technology and Tianjin University of Technology, wherein Zhongshan University mainly is a research sisal fibers matrix material, and the enhanced matrix resin has mainly been applied for " sisal fibers reinforced polypropylene compound material sheet compacting Preparation Method " patent by polyvinyl chloride, polypropylene, Resins, epoxy, resol and unsaturated polyester and in June, 2003.The National University of Defense technology and Tianjin University of Technology are mainly studied is ramie and flax fiber matrix material, and wherein Tianjin University of Technology has applied for the manufacture method of non-woven fabric and matrix material thereof " one grow flax " patent in April, 2004.But their enhanced matrix resin and Zhongshan University is similar, all be can not Biodegradable resin, and they does not have well to solve the interface problem between flaxen fiber and the matrix resin.
The starting of foreign study natural-fiber composite material is morning, but the enhanced matrix also is mainly non-biodegradable resin, is the interface problem that does not have between fine solution natural fiber and the resin too.Wherein study the maximum of flax fiber reinforced polypropylene matrix material, and be applied to the interior trim of automobile.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of composite material of poly lacltic acid enhanced by ramie fiber, to remedy the deficiencies in the prior art and defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of composite material of poly lacltic acid enhanced by ramie fiber comprises the steps:
(1) be that the poly(lactic acid) prepolymer of 1000-80000 and polycaprolactone that viscosity-average molecular weight is 400-2000 are dissolved in respectively in the organic solvent with viscosity-average molecular weight, described poly(lactic acid) prepolymer and polycaprolactone weight ratio are: 1～9: 1;
(2) ramee is immersed in the polycaprolactone solution, again two kinds of solution is mixed and good seal;
(3) in-situ polymerization made described matrix material in 0.5～4 hour under 60～100 ℃ temperature condition.
As optimized technical scheme: described organic solvent is a kind of in chloroform, tetrahydrofuran (THF), the acetone; Described polycaprolactone is the polycaprolactone of two ends band isocyanate groups; Ramee handle through (KH550) r-aminopropyl triethyl silicane or (KH560) r-(2.3 glycidoxy) propyl trimethoxy silicane carry out surface treatment; The length of ramee is 1～30 millimeter; The content of ramee is 5%-80%; Ramee and poly(lactic acid) all are biodegradable material.
Ultimate principle of the present invention is: by selecting KH550 (r-aminopropyl triethyl silicane) or KH560 (r-(2.3 glycidoxy) propyl trimethoxy silicane) coupling agent for use ramee is carried out surface treatment, prepare the complete biodegradable composite material of poly lacltic acid enhanced by ramie fiber by in-situ method again, in position in the polymeric process, isocyanate groups on the matrix resin and the reaction of the silane coupling agent of fiber surface form the chemical bond bonding, thereby make described composite material of poly lacltic acid enhanced by ramie fiber.Be about to viscosity-average molecular weight and be the poly(lactic acid) prepolymer of 1000-80000 and polycaprolactone that viscosity-average molecular weight is 400-2000 two ends band isocyanate groups and be dissolved in organic solvent respectively, simultaneously the ramee of handling well is immersed in the organic solvent of polycaprolactone.The polycaprolactone solution of poly(lactic acid) pre-polymer solution and immersion ramee is poured in the glass reactor again, reacted in Water Tank with Temp.-controlled, the organic solvent distillation is reclaimed afterwards again, reaction mechanism is as follows:
1, polylactic acid poly caprolactone copolyreaction
2, the reaction of fiber and resin
The invention has the beneficial effects as follows: the matrix material that utilizes method of the present invention to make has complete biodegradable but also has excellent interface performance and mechanical property, has actual using value.
Description of drawings
The impact section electromicroscopic photograph of the matrix material that Fig. 1 makes with untreated ramee
The matrix material that the ramee that Fig. 2 handled with KH550 makes impacts the electromicroscopic photograph of section
The matrix material that the ramee that Fig. 3 handled with KH560 makes impacts the electromicroscopic photograph of section
Embodiment
Below in conjunction with specific embodiment the present invention is done into one not elaborate.With reference to accompanying drawing 1-3
Embodiment 1
Take by weighing the 42.0g viscosity-average molecular weight respectively and be 25000 poly(lactic acid) prepolymer (PLA) and 18.0g viscosity-average molecular weight and be 1000 polycaprolactone (PCL) (PLA/PCL=7: 3), respectively they are made into the chloroformic solution of 0.1g/ml again, the ramee that afterwards that drying is good KH550 handled is immersed in the chloroformic solution of PCL, then they is poured into good seal in the glass reactor of 1000ml.Stirring reaction 2 hours at the uniform velocity in 80 ℃ water bath with thermostatic control and simultaneously, reducing pressure distills chloroform again.So a spot of chloroform in the product is vapored away and promptly obtain ramee enhancing PLA-PCL copolymer composite.Strengthen PLA-PCL with undressed ramie preparation and use the ramee preparation of handling through KH560 to strengthen the PLA-PCL matrix material according to top same step again.
The product that makes is above put into the mould standard that is pressed into impact batten and tensile bars under 150 ℃ of conditions, record mechanical property such as table 1.
Table 1 coupling agent treatment strengthens the influence of PLA-PCL composite materials property to ramee
| Coupling agent | Staple length mm | Fibre content % | Tensile strength Mpa | Shock strength J/m | |
| Fiber crops strengthen PLA-PCL | Do not have | 5-6 | 15 | 12.14 | 30.0 |
| Fiber crops strengthen PLA-PCL | KH550 | 5-6 | 15 | 23.45 | 88.9 |
| Fiber crops strengthen PLA-PCL | KH560 | 5-6 | 15 | 16.01 | 55.6 |
Embodiment 2
Take by weighing the 42.0g viscosity-average molecular weight respectively and be 80000 PLA and 42.0g viscosity-average molecular weight and be 400 gPCL (PLA/PCL=7: 3), respectively they are made into the tetrahydrofuran solution of 0.1g/ml again, afterwards that drying is good length is that the ramee of 1mm is immersed in the chloroformic solution of PCL, then they is poured into good seal in the glass reactor of 1000ml.Stirring reaction 2 hours at the uniform velocity in 80 ℃ water bath with thermostatic control and simultaneously, reducing pressure distills tetrahydrofuran (THF) again.So a spot of chloroform in the product is vapored away and promptly obtain ramee enhancing PLA-PCL copolymer composite.Prepare the ramee enhancing PLA-PCL matrix material that staple length is 5mm and 30mm according to top same step again, the product that makes is pressed into the standard batten at 150 ℃ of condition counterdies, record mechanical property such as table 2.
The different staple lengths of table 2 strengthen the influence of PLA-PCL composite materials property to ramee
| Coupling agent | Staple length mm | Fibre content % | Tensile strength Mpa | Shock strength J/m | |
| Fiber crops strengthen PLA-PCL | KH550 | 1 | 15 | 16.18 | 27.3 |
| Fiber crops strengthen PLA-PCL | KH550 | 5 | 15 | 23.45 | 88.9 |
| Fiber crops strengthen PLA-PCL | KH550 | 30 | 15 | 25.73 | 61.0 |
Embodiment 3
Take by weighing the 162.0g viscosity-average molecular weight respectively and be 1000 PLA and 18.0g viscosity-average molecular weight and be 2000 gPCL (PLA/PCL=7: 3), respectively they are made into the acetone soln of 0.1g/ml again, to account for gross weight afterwards and be immersed in the chloroformic solution of PCL, then they be poured into good seal in the glass reactor of 1000ml than 15% ramee.Stirring reaction 2 hours at the uniform velocity in 80 ℃ water bath with thermostatic control and simultaneously, reducing pressure distills acetone again.So a spot of chloroform in the product is vapored away and promptly obtain ramee enhancing PLA-PCL copolymer composite.Prepare fibre content according to top same step again and be respectively 5%, 20%, 25%, 80% ramee and strengthen the PLA-PCL matrix material, again product is pressed into the standard batten at 150 ℃ of condition counterdies, record mechanical property such as table 3.
Table 3 fibre content strengthens the influence of PLA-PCL composite materials property to ramee
| Coupling agent | Staple length mm | Fibre content % | Tensile strength Mpa | Shock strength J/m | |
| PLA-PCL | - | - | - | 14.36 | 21.0 |
| Fiber crops strengthen PLA-PCL | KH550 | 5-6 | 5 | 23.45 | 88.9 |
| Fiber crops strengthen PLA-PCL | KH550 | 5-6 | 20 | 25.3 | 79.8 |
| Fiber crops strengthen PLA-PCL | KH550 | 5-6 | 25 | 32.3 | 99.34 |
| Fiber crops strengthen PLA-PCL | KH550 | 5-6 | 80 | 30.5 | 91.3 |
Claims (7)
1, a kind of preparation method of composite material of poly lacltic acid enhanced by ramie fiber is characterized in that, comprises the steps:
(1) be that the poly(lactic acid) prepolymer of 1000-80000 and polycaprolactone that viscosity-average molecular weight is 400-2000 are dissolved in respectively in the organic solvent with viscosity-average molecular weight, described poly(lactic acid) prepolymer and polycaprolactone weight ratio are: 1～9: 1;
(2) ramee is immersed in the polycaprolactone solution, again two kinds of solution is mixed and good seal;
(3) in-situ polymerization made described matrix material in 0.5～4 hour under 60～100 ℃ temperature condition.
2, preparation method according to claim 1 is characterized in that: described organic solvent is a kind of in chloroform, tetrahydrofuran (THF), the acetone.
3, preparation method according to claim 1 is characterized in that: described polycaprolactone is the polycaprolactone of two ends band isocyanate groups.
4, preparation method according to claim 1 is characterized in that: ramee handles through r-aminopropyl triethyl silicane or r-(2.3 glycidoxy) propyl trimethoxy silicane carries out surface treatment.
5, preparation method according to claim 1 is characterized in that: the length of ramee is 1～30 millimeter.
6, preparation method according to claim 1 is characterized in that: the content of ramee is 5%-80%.
7, according to any described preparation method in the claim 1 to 6, it is characterized in that: ramee and poly(lactic acid) all are biodegradable material.
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| CN 200510110181 CN1760266A (en) | 2005-11-10 | 2005-11-10 | Method for preparing composite material of poly lacltic acid enhanced by ramie fiber |
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| CN 200510110181 CN1760266A (en) | 2005-11-10 | 2005-11-10 | Method for preparing composite material of poly lacltic acid enhanced by ramie fiber |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386702B (en) * | 2007-09-11 | 2011-03-02 | 比亚迪股份有限公司 | Polylactic acid composite material and method for preparing same |
| CN101691045B (en) * | 2009-10-14 | 2012-08-22 | 奇瑞汽车股份有限公司 | Plate and manufacture method thereof |
| CN102717558A (en) * | 2012-07-04 | 2012-10-10 | 北京汽车股份有限公司 | Environment-friendly vehicle natural fiber composite material and preparation method as well as application thereof |
| CN104313876A (en) * | 2014-10-15 | 2015-01-28 | 四川大学 | Method for modifying natural fibers for anion polymer nylon 6 reaction |
| CN110699947A (en) * | 2019-10-23 | 2020-01-17 | 台州市旭泓服饰有限公司 | Preparation method of hemp composite fiber special for paper diaper surface layer |
| CN112853609A (en) * | 2020-12-29 | 2021-05-28 | 东华大学 | Water-repellent laminated jute non-woven fabric packaging bag material and preparation method thereof |
-
2005
- 2005-11-10 CN CN 200510110181 patent/CN1760266A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386702B (en) * | 2007-09-11 | 2011-03-02 | 比亚迪股份有限公司 | Polylactic acid composite material and method for preparing same |
| CN101691045B (en) * | 2009-10-14 | 2012-08-22 | 奇瑞汽车股份有限公司 | Plate and manufacture method thereof |
| CN102717558A (en) * | 2012-07-04 | 2012-10-10 | 北京汽车股份有限公司 | Environment-friendly vehicle natural fiber composite material and preparation method as well as application thereof |
| CN102717558B (en) * | 2012-07-04 | 2015-04-29 | 北京汽车研究总院有限公司 | Environment-friendly vehicle natural fiber composite material and preparation method as well as application thereof |
| CN104313876A (en) * | 2014-10-15 | 2015-01-28 | 四川大学 | Method for modifying natural fibers for anion polymer nylon 6 reaction |
| CN110699947A (en) * | 2019-10-23 | 2020-01-17 | 台州市旭泓服饰有限公司 | Preparation method of hemp composite fiber special for paper diaper surface layer |
| CN110699947B (en) * | 2019-10-23 | 2022-08-12 | 管星星 | Preparation method of hemp composite fiber special for paper diaper surface layer |
| CN112853609A (en) * | 2020-12-29 | 2021-05-28 | 东华大学 | Water-repellent laminated jute non-woven fabric packaging bag material and preparation method thereof |
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