CN100516349C - Preparation method of grafted fibrilia modified and reinforced composite material - Google Patents
Preparation method of grafted fibrilia modified and reinforced composite material Download PDFInfo
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- CN100516349C CN100516349C CNB200710017359XA CN200710017359A CN100516349C CN 100516349 C CN100516349 C CN 100516349C CN B200710017359X A CNB200710017359X A CN B200710017359XA CN 200710017359 A CN200710017359 A CN 200710017359A CN 100516349 C CN100516349 C CN 100516349C
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Abstract
The invention discloses a manufacturing method for modification to graft apocynum fiber and the reinforced composite. At first, pre-treatment is carried out to apocynum fiber; then it is grafted with diisocyanate; and then after the grafted apocynum fiber is weaved into fiber beam or fabric, it is compounded with resin; finally reinforced resin matrix composite of apocynum fiber is produced. The method of invention makes short apocynum fiber beam form into continuous long fiber beam. The continuous long fiber beam reinforces resin matrix composite so as to improve the dispersion to structure and performance of short apocynum fiber, improve reinforced effect of apocynum fiber and obtain the composite. The intensity of composite can achieve 200MPa or so. The apocynum fiber takes the place of the glass fiber and enters into the high strength composite area. The application prospect is wide and it is provided with environmental benefit.
Description
Technical field
The invention belongs to fibrilia modified and the reinforced composite technical field, relate to the preparation method that a kind of flax fibre strengthens polymer matrix composites, particularly, prepare the method that strengthens polymer matrix composites after flax fibre and the vulcabond grafting.
Background technology
At present, the technology that known flax fibre strengthens polymer matrix composites has: 1. number of patent application 02149613.7 " polymer composites that can degrade fully that natural plant fibre strengthens and preparation method thereof " (publication number CN1422899, open day on June 11st, 2003); 2. number of patent application 99116291.9 " preparation method of natural composite material " (publication number CN1242396, open day on January 26th, 2000); 3. number of patent application 200510110181.4 " a kind of preparation method of composite material of poly lacltic acid enhanced by ramie fiber " (publication number CN1760266, open day on April 19th, 2006); 4. number of patent application 200610027821.X " a kind of preparation method of reinforced polylactic acid composite material for ramie-fabric " (publication number CN1869107, open day on November 29th, 2006); 5. article " ramee strengthens the process and performance research of poly (propylene carbonate) composite " (chemistry and bioengineering [J], 2006.8,23 (8): 18～20); 6. article " the room temperature alkali treatment is to the influence of ramee and composite property thereof " (mechanical engineering material [J], 2001.8,25 (8): 15～18); 7. article " research of ramie/LLDPE composite materials property " (composite journal [J], 2001.11,18 (4): 23～28); 8. article " ramie strengthens the research of UP resin composite materials " (Shanghai plastics [J], 2005.2, (2): 25～27).
More than disclosed technology mainly be after ramie is adopted alkali treatment or coupling agent surface modification, with the compound preparation composite of thermoplasticity, thermosetting and degradable resin, and to lack ramee structure reinforced composite.The composite material interface weakness of these method preparations, the fiber reinforcement effect is not remarkable.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of grafted fibrilia modified and reinforced composite, adopt vulcabond and fibrilia grafting, make cast tow fiber bunchy form the continuous fiber bundle in conjunction with weaving technology, with continuous fiber bundle structure reinforced composite, the composite fiber that has solved existing method preparation strengthens the inapparent defective of effect.
The technical solution adopted in the present invention is, a kind of preparation method of grafted fibrilia modified and reinforced composite specifically may further comprise the steps,
A) flax fibre is carried out pre-treatment: come unstuck, degreasing and alkali treatment;
B) behind the flax fibre and vulcabond grafting with pre-treatment, be woven into fibre bundle or fabric, or after the flax fibre of pre-treatment is woven into fibre bundle or fabric, again with the vulcabond grafting;
C) with the fibre bundle or fabric and the resin compounded that are woven into;
Promptly make flax fibre and strengthen polymer matrix composites.
Characteristics of the present invention also are:
Among the step a, ungrease treatment is that flax fibre is soaked 10h～25h with acetone.
Among the step a, alkali treatment is that flax fibre is soaked 10h～30h in concentration is the NaOH aqueous solution of 5wt%～25wt%, is washed with water to neutrality again.
Step b, flax fibre and vulcabond grafting are to adopt: with the flax fibre of pre-treatment, add acetone soln by bath raio 1: 25～35, add vulcabond again, the amount ratio of vulcabond and flax fibre is 1～4: 1～4, make catalyst with inorganic acid, make reaction pH between 2～3,50～70 ℃ of ultrasonic heating, behind reaction 4～15h, be adsorbed on vulcabond on the fiber with the acetone flush away, drying promptly obtains grafted fibrilia.
Step b weaves or weaves earlier the back grafting after the grafting of the existing textile technology of application elder generation, obtains continuous fiber bundle or fabric construction and strengthens body.
Step c adopts the heat pressing process moulding to prepare continuous fiber and strengthens polymer matrix composites.
Flax fibre is raw ramie, degummed ramie, yarn or the fabric of ramee, linen fibre or sisal fiber.
Vulcabond is selected from Toluene-2,4-diisocyanate .4-vulcabond, Toluene-2,4-diisocyanate .6-vulcabond, hexamethylene diisocyanate or lysinediisocyanate.
The present invention adopts vulcabond and fibrilia grafting, makes cast tow fiber bunchy form the continuous fiber bundle in conjunction with weaving technology, makes its change as the enhancing structure generation matter of composite, with continuous fiber bundle structure reinforced composite.
1. utilize alkali treatment and ultrasonic heating to improve the vulcabond percent grafting, change flax fibre by grafting and combine with the interface of matrix resin with fiber, fiber.
2. utilize weaving technology that the cast tow fiber weaving is become the continuous fiber bundle, improve the dispersiveness of cast tow fibre structure and performance, obtain the continuous fiber structural composite material and strengthen body, improve the flax fibre reinforced composite and strengthen effect.
3. utilize continuous fiber reinforced composite materials such as conventional processing of polymer matrix composites prepared such as hot-forming grade.
Composite that the inventive method prepares strengthens effect and significantly improves, and intensity reaches about 200MPa, make flax fibre replace glass fibre and enter the high-strength composite material field, application prospect extensively, have an environmental benefit.
The specific embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Flax fibre of the present invention strengthens the preparation method of polymer matrix composites, is applicable to raw ramie, degummed ramie, yarn or the fabric of ramee, linen fibre or sisal fiber.At first flax fibre is carried out pre-treatment, comprise come unstuck, degreasing and alkali treatment; The fiber that to handle and vulcabond grafting again; Use weaving technology then flax fibre is woven into fibre bundle or fabric, or earlier flax fibre is woven into fibre bundle or fabric, again with the vulcabond grafting; Last and resin compounded prepares composite.
Come unstuck in the pre-treatment to adopt and come unstuck fully or not exclusively come unstuck, all adopt existing conventional weaving retting technology; Ungrease treatment is that natural flax fibre is soaked 10h～25h with acetone; Alkali treatment is that natural flax fibre is soaked 10h～30h in concentration is the NaOH aqueous solution of 5wt%～25wt%, is washed with water to neutrality (pH=7) again.
Flax fibre and vulcabond grafting are to adopt: with the flax fibre of pre-treatment, add acetone soln by bath raio 1: 25～35, add vulcabond again, vulcabond (ml) is 1～4: 1～4 with the amount ratio of flax fibre (g), make catalyst with inorganic acid, make reaction pH between 2～3,50～70 ℃ of ultrasonic heating, behind reaction 4～15h, be adsorbed on vulcabond on the fiber with the acetone flush away, drying promptly obtains grafted fibrilia, and vulcabond wherein can be selected Toluene-2,4-diisocyanate .4-vulcabond for use, Toluene-2,4-diisocyanate .6-vulcabond, hexamethylene diisocyanate or lysinediisocyanate.
Weave or weave earlier the back grafting after using the first grafting of existing textile technology, obtain continuous fiber bundle or fabric construction and strengthen body.
Conventional composite material process plannings such as employing hot pressing prepare continuous fiber and strengthen polymer matrix composites, promptly make natural flax fibre and strengthen polymer matrix composites.
Embodiment 1
Ramee through coming unstuck fully (degummed ramie), 15wt%NaOH aqueous solution soaking 24h is washed to pH and is neutral (pH=7), 60 ℃ of vacuumize 4～5h, after immersion 24h carries out degreasing in acetone soln, be put in the reactor, add acetone soln, bath raio is 1: 30, add Toluene-2,4-diisocyanate .4-vulcabond again, Toluene-2,4-diisocyanate .4-vulcabond (ml) is 2: 1 with the amount ratio of flax fibre (g), drips the concentrated sulfuric acid, makes pH between 2～3; The ultrasonic water bath heating keeps 50 ℃ of reaction temperatures, and reaction time 10h, percent grafting are 45%, takes out ramee, and acetone cleans removes unreacted Toluene-2,4-diisocyanate .4-vulcabond, washing, 80 ℃ of dryings; Weave resultant yarn or textile structural and strengthen body, with the unidirectional laying of 0.06mm polyethylene (PE) film interlayer; 125 ℃, 1.5MPa is hot-forming, and 105 ℃ of annealing 2h obtain ramee and strengthen the PE composite panel, and after testing, its intensity is 190MPa.
Embodiment 2
Come unstuck, flax shive after weaving, 10wt%NaOH aqueous solution soaking 25h, be washed to pH and be neutral (pH=7), 60 ℃ of vacuumize 4～5h, after immersion 25h carries out degreasing in acetone soln, be put in the reactor, add acetone soln; bath raio is 1: 25; add Toluene-2,4-diisocyanate .6-vulcabond again, Toluene-2,4-diisocyanate .6-vulcabond (ml) is 1: 1 with the amount ratio of flax fibre (g), drips the concentrated sulfuric acid; make between pH=2～3; the ultrasonic water bath heating, and 65 ℃ of maintenance reaction temperatures, reaction time 6h; percent grafting is 39%; take out linen fibre, acetone clean and remove unreacted Toluene-2,4-diisocyanate .6-vulcabond, and washing; 80 ℃ of dryings is with the unidirectional laying of 0.06mm polyethylene (PE) film interlayer; 125 ℃, 1.5MPa is hot-forming; 105 ℃ of annealing 2h obtain linen fibre and strengthen the PE composite panel, and after testing, its intensity is 185MPa.
Embodiment 3
The sisal hemp raw ramie that does not come unstuck, 20wt%NaOH aqueous solution soaking 10h, be washed to pH and be neutral (pH=7), 60 ℃ of vacuumize 4～5h are after immersion 10h carries out degreasing in acetone soln, be put in the reactor, adding the acetone soln bath raio is 1: 35, adds hexamethylene diisocyanate again, and hexamethylene diisocyanate (ml) is 1: 4 with the amount ratio of flax fibre (g), drip the concentrated sulfuric acid, make between pH=2～3; The ultrasonic water bath heating keeps 55 ℃ of reaction temperatures, and reaction time 15h, percent grafting are 26%; Take out sisal fiber, acetone cleans removes unreacted hexamethylene diisocyanate, washing, and 80 ℃ of dryings are weaved resultant yarn or textile structural and are strengthened body, with the unidirectional laying of 0.06mm polyethylene (PE) film interlayer; 125 ℃, 1.5MPa is hot-forming; 105 ℃ of annealing 2h obtain sisal fiber and strengthen the PE composite panel, and after testing, its intensity is 195MPa.
Embodiment 4
The ramie raw ramie that does not come unstuck, 25wt%NaOH aqueous solution soaking 15h, be washed to pH and be neutral (pH=7), 60 ℃ of vacuumize 4～5h are after immersion 24h carries out degreasing in acetone soln, be put in the reactor, adding the acetone soln bath raio is 1: 30, adds lysinediisocyanate again, and lysinediisocyanate (ml) is 1: 2 with the amount ratio of flax fibre (g), drip the concentrated sulfuric acid, make between pH=2～3; The ultrasonic water bath heating keeps 50 ℃ of reaction temperatures, and reaction time 8h, percent grafting are 23%; Take out ramee, acetone cleans removes unreacted lysinediisocyanate, washing, and 80 ℃ of dryings are weaved resultant yarn or textile structural and are strengthened body, with the unidirectional laying of 0.06mm polyethylene (PE) film interlayer; 125 ℃, 1.5MPa is hot-forming; 105 ℃ of annealing 2h obtain ramee and strengthen the PE composite panel, and after testing, its intensity is 210MPa.
Embodiment 5
Come unstuck, ramee bundle after weaving, 5wt%NaOH aqueous solution soaking 30h, be washed to pH and be neutral (pH=7), 60 ℃ of vacuumize 4～5h, after immersion 15h carries out degreasing in acetone soln, be put in the reactor, add acetone soln; bath raio is 1: 25; add Toluene-2,4-diisocyanate .4-vulcabond again, Toluene-2,4-diisocyanate .4-vulcabond (ml) is 1: 1 with the amount ratio of flax fibre (g), drips the concentrated sulfuric acid; make between pH=2～3; the ultrasonic water bath heating, and 70 ℃ of maintenance reaction temperatures, reaction time 4h; percent grafting is 41%; take out ramee, acetone clean and remove unreacted Toluene-2,4-diisocyanate .4-vulcabond, and washing; 80 ℃ of dryings is with the unidirectional laying of 0.06mm polyethylene (PE) film interlayer; 125 ℃, 1.5MPa is hot-forming; 105 ℃ of annealing 2h obtain ramee and strengthen the PE composite panel, and after testing, its intensity is 187MPa.
Claims (6)
1. the preparation method of a grafted fibrilia modified and reinforced composite is characterized in that, specifically may further comprise the steps:
A) flax fibre is carried out pre-treatment: come unstuck, degreasing and alkali treatment;
B) use existing textile technology, behind the flax fibre and vulcabond grafting with pre-treatment, be woven into fibre bundle or fabric, or after the flax fibre of pre-treatment is woven into fibre bundle or fabric, with the vulcabond grafting, obtain continuous fiber bundle or fabric construction and strengthen body again
Described flax fibre and vulcabond grafting are to adopt: with the flax fibre of pre-treatment, add acetone soln by bath raio 1: 25～35, add vulcabond again, the amount ratio of vulcabond and flax fibre is 1～4: 1～4, makes catalyst with inorganic acid, make reaction pH between 2～3,50～70 ℃ of ultrasonic heating, reaction 4～15h is adsorbed on vulcabond on the fiber with the acetone flush away, drying obtains grafted fibrilia;
C) with the fibre bundle or fabric and the resin compounded that are woven into;
Promptly make flax fibre and strengthen polymer matrix composites.
2. according to the described preparation method of claim 1, it is characterized in that among the step a, described ungrease treatment is that flax fibre is soaked 10h～25h with acetone.
3. according to the described preparation method of claim 1, it is characterized in that among the step a, described alkali treatment is that flax fibre is soaked 10h～30h in concentration is the NaOH aqueous solution of 5wt%～25wt%, is washed with water to neutrality again.
4. according to the described preparation method of claim 1, it is characterized in that described step c adopts the hot pressing composite material process planning to prepare continuous fiber and strengthens polymer matrix composites.
5. according to the described preparation method of claim 1, it is characterized in that described flax fibre is raw ramie, degummed ramie, yarn or the fabric of ramee, linen fibre or sisal fiber.
6. according to the described preparation method of claim 1, it is characterized in that described vulcabond is selected from Toluene-2,4-diisocyanate .4-vulcabond, Toluene-2,4-diisocyanate .6-vulcabond, hexamethylene diisocyanate or lysinediisocyanate.
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| CN101891941B (en) * | 2010-07-23 | 2012-07-18 | 西安工程大学 | Biodegradable composite foamed plastic and preparation method |
| CN103408910A (en) * | 2013-07-31 | 2013-11-27 | 宁夏青林盛华科技有限公司 | Fully-degraded natural fiber/carbon dioxide polymer composite material and preparation method thereof |
| CN104711850B (en) * | 2015-03-10 | 2017-03-01 | 哈尔滨工业大学 | Method flax shive being surface-treated using nano hydrated zirconium oxide |
| CN105504708A (en) * | 2015-12-03 | 2016-04-20 | 丁玉琴 | Preparation method of ramie fiber/ basalt fiber/ polylactic acid ternary composite |
| CN107012587A (en) * | 2017-05-15 | 2017-08-04 | 吉林大学 | A kind of natural environmental-protective type flaxen fiber enhancing degradable polyalcohol group felt material and its composite board and preparation method |
| CN112273116B (en) * | 2020-10-19 | 2023-02-14 | 西安工程大学 | Preparation method of morph-genetic structure carbon-modified sunshade net film material |
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