CN103073863A - Natural fiber/thermosetting polylactic acid composite material and preparation method thereof - Google Patents
Natural fiber/thermosetting polylactic acid composite material and preparation method thereof Download PDFInfo
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- CN103073863A CN103073863A CN2013100415908A CN201310041590A CN103073863A CN 103073863 A CN103073863 A CN 103073863A CN 2013100415908 A CN2013100415908 A CN 2013100415908A CN 201310041590 A CN201310041590 A CN 201310041590A CN 103073863 A CN103073863 A CN 103073863A
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Abstract
The invention belongs to the technical field of a high molecular material and particularly relates to a natural fiber/thermosetting polylactic acid composite material and a preparation method thereof. The material is formed by natural fibers and thermosetting polylactic acid. The specific preparation method comprises the following steps of: carrying out surface treatment on the natural fibers and uniformly dispersing into a star-shaped polylactic acid melt modified by an unsaturated anhydride terminal group; and initiating a polymerization reaction by radiation or thermally initiating the polymerization reaction by a free radical initiator to carry out cross-linking and curing to obtain the natural fiber/thermosetting polylactic acid composite material. Compared with the pure polylactic acid, the mechanical property and the heat stability of the composite material are greatly improved; and the composite material can be used for preparing engineering plastic with demanding requirements. After being abandoned, the composite material disclosed by the invention can be completely degraded in a natural environment, belongs to an environment-friendly material and has a wide application prospect.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of natural fiber/thermosetting polylactic acid matrix material and preparation method thereof.
Background technology
Poly(lactic acid) (PLA) conduct is a kind of fully biodegradable, eco-friendly aliphatic polyester series macromolecular material, derive from renewable resources, it can be degradable by the occurring in nature microorganism after using, free from environmental pollution, have simultaneously the advantages such as good mechanical property and easy processing, make it become most widely used biodegradated polymer materal.Polylactic acid plastic, fiber or film are applied in industrial or agricultural and the daily life, can solve " white pollution " problem, satisfy the requirement of environmental protection aspect.Yet the shortcoming such as poly(lactic acid) matter is crisp, toughness is relatively poor, heat-drawn wire is low has limited it and has used in field widely.Especially the material of the use such as automobile, aircraft needs higher mechanical property and resistance toheat.For improving the high temperature dimensional stability of plastics, the method that usually adopts has: 1, improve second-order transition temperature; 2, improve degree of crystallinity; 3 and fiber composite.For poly(lactic acid), with fiber composite may be more effective a kind of method.
Natural fiber nature especially in plant resource very abundant.It is low to have price, low density, and readily biodegradable, CO2 emissions is low, and is heat insulation, sound-proofing properties is excellent, the specific modulus advantages of higher.At present, mainly adopt natural plant fibre as strongthener for the research of natural fiber reinforced composite, the petroleum base derivatives resin is as matrix.Germany BASF company adopts the jute reinforced polypropylene compound material to produce internal decoration of car spare, inhales noise plate wheel cover for subsequent use, adopts sisal hemp/compound polyurethane material to produce the sedan door trim panel, inhales the noise plate.At home, the mechanisms such as Zhongshan University, the National University of Defense technology also are studied natural fiber and the compound of unsaturated polyester and urethane, have obtained certain breakthrough at aspects such as material mechanical performance, resistance toheats.But the shortcoming of these material maximums is can't be degradable.For substituting these petroleum base materials, poly(lactic acid) is used in more wide field, adopting natural fiber that poly(lactic acid) is carried out enhancing modified is the problem that is worth research.Chinese invention patent 200710171660.6 and 200710171659.3 adopts respectively twin screw extruder to prepare natural fiber enhancing commercialization polylactic resin and natural fibre/montmorillonite soil/lactic acid composite material resin, and discovery can improve resistance toheat and the mechanical property of poly(lactic acid) to a certain extent.
Yet above several method is all more limited to the lifting of poly(lactic acid) thermostability, thus need to seek other terms of settlement, such as crosslinking curing.Chinese patent 200810050975.X adopts the method for adding silane coupling agent in polylactic resin, makes silane coupling agent crosslinked in hot water, improves the mechanical property of its lactic acid; Chinese patent 200810050603.7 adopts poly(lactic acid) and triallyl isocyanurate blend, and then irradiation makes polymerization of vinyl monomer crosslinked, forms heat-resisting polylactic acid based resin.But in the material of these two kinds of method preparations, polylactic acid molecule does not occur crosslinked, only be that the polyfunctional monomer that adds has participated in crosslinking reaction, both blend mainly are to form island structure, can improve to a certain extent impact resistance and the tensile strength of poly(lactic acid), but the method cross-linking density is low, regularity and the homogeneity of crosslinking structure are uncontrollable, and employing is commercial high-molecular-weight thermoplastic poly(lactic acid), melt viscosity is large, is unfavorable for evenly mixing and composite material forming.These materials can not be at last truly thermosetting polylactic acid.Chinese patent 201110004315.X and 201110168622.1 adopts respectively ring-opening polymerization and polycondensation to prepare the star polylactic acid of terminal groups modification, then utilize the radical polymerization of end group to realize the crosslinked of poly(lactic acid), thereby prepared thermosetting polylactic acid truly.The thermotolerance of this thermosetting polylactic acid has significantly raising, but its fragility is improved not quite, still is not suitable for use in engineering plastics.
In order to develop all good fully bio-degradable type engineering plastics of a kind of high-temperature stability, toughness and mechanical property, the present invention proposes a kind of method that adopts natural fiber to strengthen thermosetting polylactic acid.The present invention uses for reference the preparation method of preparation thermosetting polylactic acid in the existing technology, adopting the star polylactic acid of unsaturated acid anhydride modification is raw material, before it solidifies with natural fiber carry out compound, and then crosslinking curing, form mix, matrix material that cross-linking density is controlled.This matrix material can be used for preparing the engineering plastics of requirement harshness, and such as aircraft or materials used in auto manufacturing, and use also can be degradable in physical environment after discarded, belongs to eco-friendly green material, has broad application prospects.
Summary of the invention
The object of the present invention is to provide a kind of natural fiber with excellent mechanical performances and stable on heating excellent performance/thermosetting polylactic acid matrix material and preparation method thereof.
Natural fiber provided by the invention/thermosetting polylactic acid matrix material, first natural fiber to be carried out surface treatment, then evenly spread in the star polylactic acid melt behind the unsaturated acid anhydride terminal groups modification, and by radiation initiation or radical initiator thermal-initiated polymerization reaction and crosslinking curing, obtain natural fiber/thermosetting polylactic acid matrix material, the weight percent of each component is as follows in this matrix material:
When adopting radiation to cause:
Weight percentages of components wt%
Natural fiber 5 ~ 50
Poly(lactic acid) 50 ~ 95
Its total amount satisfies 100%;
When adopting radical initiator to carry out thermal initiation,
Weight percentages of components wt%
Natural fiber 5 ~ 50
Poly(lactic acid) 50 ~ 95
Radical initiator 0.1 ~ 3
Its total amount satisfies 100%.
Among the present invention, described natural fiber/thermosetting polylactic acid matrix material, it is characterized in that described poly(lactic acid) is the star polylactic acid of terminal groups modification, its terminal hydroxy group is because being replaced by unsaturated group with unsaturated acid anhydride generation esterification, can pass through to cause the two key generation Raolical polymerizables of C=C and crosslinking curing, the weight-average molecular weight of uncured front star polylactic acid is 1 * 10
3~ 3 * 10
5
Among the present invention, described natural fiber/thermosetting polylactic acid matrix material is characterized in that described natural fiber is any in chopped natural fiber or the natural macrofiber.
Among the present invention, described natural fiber/thermosetting polylactic acid matrix material is characterized in that described natural fiber is one to several in ramee, flax fiber, sisal fibers, jute fibre, hemp fibre or the bamboo fibers.
Among the present invention; described natural fiber/thermosetting polylactic acid matrix material, it is characterized in that described thermal initiation solidify employed radical initiator be in peroxidized t-butyl perbenzoate, isopropyl benzene hydroperoxide, tertbutyl peroxide, dicumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide or the dilauroyl peroxide any.
A kind of natural fiber that the present invention proposes/thermosetting polylactic acid composite manufacture method, concrete steps are as follows:
(1) be that 5 ~ 100 natural fiber is immersed in (aqueous solution of 0.1 ~ 5wt%) silane coupling agent, (aqueous solution of 1 ~ 10wt%) sodium hydroxide or (in the acetone soln of 0.1 ~ 5wt%) potassium permanganate 1 ~ 6 hour with length-to-diameter ratio, washing, drying obtains the natural fiber of surface modification;
(2) be in the star polylactic acid melt after the natural fiber of the surface modification of 5 ~ 50wt% joins terminal groups modification, 60 ~ 140 ℃ of lower stirrings 5 ~ 30 minutes, to obtain homodisperse compound resin melt with massfraction;
(3) the compound resin melt is poured in the mould, any carries out crosslinking curing in the following ways:
1. irradiation causes curing: step (2) gained compound resin melt is poured in the mould, with cobalt source radiation 50 ~ 100kGy dosage, namely get desired product after the curing.
2. thermal initiation solidifies: the extra thermal initiator that adds 0.1 ~ 3wt% in step (2), after being uniformly dispersed, the compound resin melt is poured in the mould and 130 ~ 170 ℃ of lower insulations 1 ~ 3 hour, 180 ~ 300 ℃ of lower curing 0.5 ~ 2 hour, namely get desired product at last.
With respect to scheme of the prior art, the invention has the advantages that: the matrix material that adopts this kind method to make, the control of melt viscosity before can realizing by the adjusting to the star polylactic acid structure cross-linking density, solidifying, thus realize that natural fiber mixes with the even of poly(lactic acid); The surface treatment of natural fiber and the curing of poly(lactic acid) can be avoided the phase-splitting of matrix material, improve its permanent stability; Crosslinking curing can significantly promote thermostability and the dimensional stability of poly(lactic acid), and natural fiber strengthens can promote its toughness and mechanical property again, thereby obtains all good matrix materials of over-all properties; Natural fiber and poly(lactic acid) all are degradation materials, thus can be degradable in physical environment after this matrix material use is discarded, belong to eco-friendly green material, have broad application prospects.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Embodiment 1:
(1) be that 15 ramee is immersed in the aqueous sodium hydroxide solution that concentration is 8wt% 2 hours with length-to-diameter ratio, be washed to neutrality, air drying, again vacuum-drying obtains the ramie staple fibre of surface modification;
(2) be in the star polylactic acid melt after the ramie staple fibre of the surface modification of 30wt% joins terminal groups modification, 100 ℃ of lower stirrings 20 minutes, to obtain homodisperse compound resin melt with massfraction;
(3) step (2) gained compound resin melt is poured in the mould, with cobalt source radiation 90kGy dosage, namely get ramee/thermosetting polylactic acid matrix material after the curing.Mechanical property: tensile strength 90MPa, shock strength 9.74KJm
-2Thermostability: sample can maintain the original state indeformable under 200 ℃.
Embodiment
2:
(1) be that 5 jute fibre is immersed in the Silane coupling agent KH550 aqueous solution that concentration is 0.2wt% 3 hours with length-to-diameter ratio, washing, air drying, again vacuum-drying obtains the jute fibre of silane surface modification;
(2) be in the star polylactic acid melt after the isopropyl benzene hydroperoxide of the jute fibre of silane surface modification of 20wt% and 1wt% joins terminal groups modification, 80 ℃ of lower stirrings 15 minutes, to obtain homodisperse compound resin melt with massfraction;
(3) step (2) gained compound resin melt is poured in the mould, and 160 ℃ of lower insulations 2 hours, 200 ℃ of lower curing 1 hour, namely get jute fibre/thermosetting polylactic acid matrix material at last.Mechanical property: tensile strength 67MPa, shock strength 13.65KJm
-2Thermostability: sample can maintain the original state indeformable under 200 ℃.
Embodiment
3:
(1) be that 20 bamboo fibers is immersed in the silane coupling agent KH560 aqueous solution that concentration is 0.4wt% 2 hours with length-to-diameter ratio, washing, air drying, again vacuum-drying obtains the bamboo fibers of silane surface modification;
(2) be in the star polylactic acid melt after the bamboo fibers of the silane surface modification of 25wt% joins terminal groups modification, 110 ℃ of lower stirrings 10 minutes, to obtain homodisperse compound resin melt with massfraction;
(3) step (2) gained compound resin melt is poured in the mould, with cobalt source radiation 60kGy dosage, namely get bamboo fibers/thermosetting polylactic acid matrix material after the curing.Mechanical property: tensile strength 87MPa, shock strength 11.78KJm
-2Thermostability: sample can maintain the original state indeformable under 200 ℃.
Embodiment
4:
(1) be that 40 flax fiber is immersed in the aqueous sodium hydroxide solution that concentration is 6wt% 4 hours with length-to-diameter ratio, be washed to neutrality, air drying, again vacuum-drying obtains the flax fiber of surface modification;
(2) be in the star polylactic acid melt after the peroxidized t-butyl perbenzoate of the flax fiber of surface modification of 35wt% and 1.5wt% joins terminal groups modification, 90 ℃ of lower stirrings 20 minutes, to obtain homodisperse compound resin melt with massfraction;
(3) step (2) gained compound resin melt is poured in the mould, and 140 ℃ of lower insulations 1 hour, 190 ℃ of lower curing 1.5 hours, namely get flax fiber/thermosetting polylactic acid matrix material at last.Mechanical property: tensile strength 85MPa, shock strength 11.65KJm
-2Thermostability: sample can maintain the original state indeformable under 200 ℃.
Embodiment
5:
(1) be that 80 sisal fibers is immersed in the acetone soln of potassium permanganate that concentration is 0.2wt% 3 hours with length-to-diameter ratio, washing, air drying, again vacuum-drying obtains the sisal fibers of surface modification;
(2) be in the star polylactic acid melt after the sisal fibers of the surface modification of 10wt% joins terminal groups modification, 120 ℃ of lower stirrings 25 minutes, to obtain homodisperse compound resin melt with massfraction;
(3) step (2) gained compound resin melt is poured in the mould, with cobalt source radiation 100kGy dosage, namely get sisal fibers/thermosetting polylactic acid matrix material after the curing.Mechanical property: tensile strength 65MPa, shock strength 13.27KJm
-2Thermostability: sample can maintain the original state indeformable under 200 ℃.
Embodiment
6:
(1) be that 30 hemp fibre is immersed in the Silane coupling agent KH550 aqueous solution that concentration is 1wt% 2 hours with length-to-diameter ratio, washing, air drying, again vacuum-drying obtains the hemp fibre of silane surface modification;
(2) be in the star polylactic acid melt after the dicumyl peroxide of the hemp fibre of silane surface modification of 20wt% and 1.8wt% joins terminal groups modification, 80 ℃ of lower stirrings 15 minutes, to obtain homodisperse compound resin melt with massfraction;
(3) step (2) gained compound resin melt is poured in the mould, and 150 ℃ of lower insulations 2 hours, 180 ℃ of lower curing 2 hours, namely get hemp fibre/thermosetting polylactic acid matrix material at last.Mechanical property: tensile strength 76MPa, shock strength 12.05KJm
-2Thermostability: sample can maintain the original state indeformable under 200 ℃.
Above-described embodiment only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with technique can understand content of the present invention and according to this enforcement, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (6)
1. natural fiber/thermosetting polylactic acid matrix material, it is characterized in that: natural fiber is carried out surface treatment, then evenly spread in the star polylactic acid melt behind the unsaturated acid anhydride terminal groups modification, and by radiation initiation or radical initiator thermal-initiated polymerization reaction and crosslinking curing, obtain natural fiber/thermosetting polylactic acid matrix material, the weight percent of each component is as follows in this matrix material:
When adopting radiation to cause:
Weight percentages of components wt%
Natural fiber 5 ~ 50
Poly(lactic acid) 50 ~ 95
Its total amount satisfies 100%;
When adopting radical initiator to carry out thermal initiation,
Weight percentages of components wt%
Natural fiber 5 ~ 50
Poly(lactic acid) 50 ~ 95
Radical initiator 0.1 ~ 3
Its total amount satisfies 100%.
2. natural fiber according to claim 1/thermosetting polylactic acid matrix material is characterized in that described poly(lactic acid) is the star polylactic acid of terminal groups modification, and the weight-average molecular weight of uncured front star polylactic acid is 1 * 10
3~ 3 * 10
5
3. natural fiber according to claim 1/thermosetting polylactic acid matrix material is characterized in that described natural fiber is any in chopped natural fiber or the natural macrofiber.
4. natural fiber according to claim 1/thermosetting polylactic acid matrix material is characterized in that described natural fiber is one to several in ramee, flax fiber, sisal fibers, jute fibre, hemp fibre or the bamboo fibers.
5. natural fiber according to claim 1/thermosetting polylactic acid matrix material, it is characterized in that described thermal initiation solidify employed radical initiator be in peroxidized t-butyl perbenzoate, isopropyl benzene hydroperoxide, tertbutyl peroxide, dicumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide or the dilauroyl peroxide any.
6. natural fiber as claimed in claim 1/thermosetting polylactic acid composite manufacture method is characterized in that concrete steps are as follows:
(1) with length-to-diameter ratio be in the acetone soln of the aqueous solution of 5 ~ 100 the natural fiber aqueous solution that is immersed in 0.1 ~ 5wt% silane coupling agent, 1 ~ 10wt% sodium hydroxide or 0.1 ~ 5wt% potassium permanganate 1 ~ 6 hour, washing, drying obtains the natural fiber of surface modification;
(2) be in the star polylactic acid melt after the natural fiber of the surface modification of 5 ~ 50wt% joins terminal groups modification, 60 ~ 140 ℃ of lower stirrings 5 ~ 30 minutes, to obtain homodisperse compound resin melt with massfraction;
(3) the compound resin melt is poured in the mould, any carries out crosslinking curing in the following ways:
1. irradiation causes curing: step (2) gained compound resin melt is poured in the mould, with cobalt source radiation 50 ~ 100kGy dosage, namely get desired product after the curing;
2. thermal initiation solidifies: the extra thermal initiator that adds 0.1 ~ 3wt% in step (2), after being uniformly dispersed, the compound resin melt is poured in the mould and 130 ~ 170 ℃ of lower insulations 1 ~ 3 hour, 180 ~ 300 ℃ of lower curing 0.5 ~ 2 hour, namely get desired product at last.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106147164A (en) * | 2015-04-23 | 2016-11-23 | 上海微创医疗器械（集团）有限公司 | A kind of medical composite material and preparation method thereof |
| CN107033564A (en) * | 2017-03-20 | 2017-08-11 | 同济大学 | Fine and polylactic acid blend composite the preparation method of bamboo fibre length after surface-modified |
| CN107841904A (en) * | 2017-10-19 | 2018-03-27 | 袁玲燕 | A kind of preparation method of bamboo fibre conducting polymer paper |
| CN108164867A (en) * | 2017-12-11 | 2018-06-15 | 许水仙 | A kind of preparation method of bending-resistant type bamboo-plastic composite material |
| CN111825845A (en) * | 2020-06-23 | 2020-10-27 | 东华大学 | Polylactic acid graft modified natural fiber and PLA composite material and preparation method thereof |
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| CN102120817A (en) * | 2011-01-11 | 2011-07-13 | 同济大学 | Crosslinking polylactic acid and preparation method thereof |
| CN102717577A (en) * | 2012-07-04 | 2012-10-10 | 北京汽车股份有限公司 | Environment-friendly composite material for automobile decoration and preparation method as well as application thereof |
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| CN101003667A (en) * | 2006-01-20 | 2007-07-25 | 东丽纤维研究所（中国）有限公司 | Composite material of poly lactic acid / natural faric, and production method |
| CN102120817A (en) * | 2011-01-11 | 2011-07-13 | 同济大学 | Crosslinking polylactic acid and preparation method thereof |
| CN102717577A (en) * | 2012-07-04 | 2012-10-10 | 北京汽车股份有限公司 | Environment-friendly composite material for automobile decoration and preparation method as well as application thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106147164A (en) * | 2015-04-23 | 2016-11-23 | 上海微创医疗器械（集团）有限公司 | A kind of medical composite material and preparation method thereof |
| CN106147164B (en) * | 2015-04-23 | 2018-05-01 | 上海微创医疗器械（集团）有限公司 | A kind of medical composite material and preparation method thereof |
| CN107033564A (en) * | 2017-03-20 | 2017-08-11 | 同济大学 | Fine and polylactic acid blend composite the preparation method of bamboo fibre length after surface-modified |
| CN107841904A (en) * | 2017-10-19 | 2018-03-27 | 袁玲燕 | A kind of preparation method of bamboo fibre conducting polymer paper |
| CN108164867A (en) * | 2017-12-11 | 2018-06-15 | 许水仙 | A kind of preparation method of bending-resistant type bamboo-plastic composite material |
| CN111825845A (en) * | 2020-06-23 | 2020-10-27 | 东华大学 | Polylactic acid graft modified natural fiber and PLA composite material and preparation method thereof |
| CN111825845B (en) * | 2020-06-23 | 2022-06-14 | 东华大学 | Polylactic acid graft modified natural fiber and PLA composite material and preparation method thereof |
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Application publication date: 20130501 |