CN101381468A - Preparation method of linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material - Google Patents
Preparation method of linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material Download PDFInfo
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- CN101381468A CN101381468A CNA2008102316431A CN200810231643A CN101381468A CN 101381468 A CN101381468 A CN 101381468A CN A2008102316431 A CNA2008102316431 A CN A2008102316431A CN 200810231643 A CN200810231643 A CN 200810231643A CN 101381468 A CN101381468 A CN 101381468A
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Abstract
The invention discloses a method for preparing a composite material of fibrilia enhanced lactic acid/polyethylene glycol alloy. The method comprises the following steps: firstly, preparing lactic acid/polyethylene glycol alloy; secondly, taking fibrilia and carrying out preliminary treatment on the fibrilia; preparing vulcabond/acetone solvent; adding the lactic acid/polyethylene glycol alloy into the vulcabond/acetone solution, adding the fibrilia subjected to the preliminary treatment and a plasticizing agent for mixing and drying; placing the mixture in a mould for hot pressing; and taking out the mould with the mixture, demoulding and annealing the mixture to produce the composite material of fibrilia enhanced lactic acid/polyethylene glycol alloy. The method ensures that fibrilia and the lactic acid/polyethylene glycol alloy are crossly linked through the vulcabond to form a net structure, thereby obtaining the composite material of fibrilia enhanced lactic acid/polyethylene glycol alloy with firm interface, improving the fibrilia enhanced effect, obviously improving the interface bonding strength of the composite material, expanding the application field of the fibrilia composite material, and having environmental benefits.
Description
Technical field
The invention belongs to the manufacture technology of composite material field, relate to a kind of preparation method of matrix material, particularly a kind of preparation method of linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material.
Background technology
At present, the technology that known preparation flaxen fiber strengthens lactic acid composite material has: 1) patent " polymer composites that the natural plant fibre enhanced can be degraded fully and preparation method thereof " (patent No. ZL02149613.7, publication number CN1422899, open day 2003.06.11); 2) patent " preparation method of natural composite material " (patent No. ZL99116291.9, publication number CN1242396, open day 2000.01.26); 3) " a kind of preparation method of composite material of poly lacltic acid enhanced by ramie fiber " (application number 200510110181.4, publication number CN1760266, open day 2006.04.19); 4) " a kind of preparation method of reinforced polylactic acid composite material for ramie-fabric " (application number 200610027821.X, publication number CN1869107, open day 2006.11.29); 5) chemistry and biotechnology [J], " ramee strengthens the process and performance research of poly (propylene carbonate) matrix material " of 2006.8,23 (8): 18～20 publications; 6) mechanical engineering material [J], 2001.8,25 (8): 15～18 " the room temperature alkaline purification is to the influences of ramee and composite property thereof " of publishing; 7) matrix material journal [J], " research of ramie/LLDPE composite materials property " of 2001.11,18 (4): 23～28 publications; 8) Shanghai plastics [J], 2005.2, (2): " ramie strengthens the research of UP resin composite materials " of 25～27 publications; 9. polymer material science and engineering [J], " graft polymerization reactions of ramee and toluene-2,4-vulcabond " of 2007.1,23 (1): 45～48 publications; 10) " a kind of preparation method of grafted fibrilia modified and reinforced composite " (application number 200710017359.X, publication number CN101012622, open day 2007.08.08).
Natural fiber strengthens the forward position that the degradable resin based composites is present environmental effect matrix material research, but the flame resistivity of ubiquity matrix resin is apparently higher than natural fiber at present, make the composite material forming difficulty, the crystal face of matrix material and mechanical property deficiency, therefore, study low temperature moulding and improve the focus that interface performance becomes present research.More than disclosed technology also effectively do not overcome the above problems, and mainly adopt alkaline purification, coupling agent surface modification or vulcabond graft modification that flaxen fiber is handled, again with to have thermoplasticity, thermoset and degradable resin poly(lactic acid) compound, the preparation matrix material, do not relate to vulcabond as linking agent directly and lactic acid/polyethyleneglycol be cross-linked to form alloy, this alloy again with the crosslinked method for preparing matrix material of flaxen fiber, thereby solve environmental effect natural-fiber composite material difficult forming and interface performance defect of insufficient.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material, utilize vulcabond to prepare matrix material as the linking agent of flaxen fiber and lactic acid/polyethyleneglycol alloy, this matrix material has low temperature moulding, interface in conjunction with firm characteristics.
The technical solution adopted in the present invention is, a kind of preparation method of linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material carries out according to the following steps:
Step 1: preparation lactic acid/polyethyleneglycol alloy
Get concentrated lactic acid and polyoxyethylene glycol respectively, mix, add 1g～5g polyoxyethylene glycol in control 1ml～3ml lactic acid, in the mixture of above-mentioned lactic acid and polyoxyethylene glycol, add the tin protochloride and the vitriol oil, mix, obtain mixing solutions, control 100ml lactic acid adds the tin protochloride of 0.1g～0.5g, the quality of the vitriol oil accounts for 0.01%～0.5% of mixing solutions total mass, it is in 105 ℃～170 ℃ the vacuum drying oven that this mixing solutions is placed temperature, heating 10h～50h makes lactic acid/polyethyleneglycol alloy;
Step 2: flaxen fiber is carried out pre-treatment
Get flaxen fiber, come unstuck, after the alkaline purification, drying, degreasing, immerse Toluene-2,4-diisocyanate .6-vulcabond/acetone soln, dipping 0.5h～2h puts into 3g～6g flaxen fiber in control 1ml～2ml Toluene-2,4-diisocyanate .6-vulcabond;
Or, get flaxen fiber, carry out alkaline purification, drying and degreasing,
Or, get flaxen fiber, carry out drying and degreasing;
Step 3: preparation vulcabond/acetone soln
Get vulcabond and acetone respectively, mix, make vulcabond/acetone soln, the volume ratio of vulcabond and acetone is 1～2:0～2 in this solution;
Step 4: mixing
The lactic acid/polyethyleneglycol alloy that step 1 is made adds vulcabond acetone/solution that step 3 makes, add softening agent and the flaxen fiber after step 2 is handled again, form mixture, add 1ml～3ml lactic acid/polyethyleneglycol alloy and 1g～5g flaxen fiber in control 1ml～2ml vulcabond acetone/solution, the quality of softening agent accounts for 1%～5% of mixture total mass, this mixture is carried out mixing, dry, make raw material;
Step 5: preparation linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material
The raw material that step 4 is made, put into mould, placing temperature is that 85 ℃～130 ℃, pressure are the environment of 1.5MPa～5MPa, hot pressing 1h～4h, take out, the demoulding, placing temperature then is 75 ℃～120 ℃ vacuum drying oven, annealing 4h～40h promptly makes linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material.
Feature of the present invention also is,
Coming unstuck in the step 2 wherein adopts existing conventional weaving to use retting technology, and flaxen fiber is come unstuck fully or not exclusively.
Alkaline purification in the step 2 wherein, it is that the NaOH aqueous solution of 5wt%～25wt% soaks 10h～30h that flaxen fiber is placed concentration, is washed with water to neutral pH=7 again.
Drying in the step 2 wherein, it is 60 ℃～105 ℃ environment that flaxen fiber is put into temperature, heating 4h～5h.
Degreasing in the step 2 wherein places acetone soln to soak 10h～25h in flaxen fiber, oven dry.
Toluene-2,4-diisocyanate .6-vulcabond/acetone soln in the step 2 is wherein got Toluene-2,4-diisocyanate .6-vulcabond and acetone respectively, mixes to obtain this solution, and wherein, the volume ratio of Toluene-2,4-diisocyanate .6-vulcabond and acetone is 2:5～20.
Flaxen fiber is selected raw ramie, degummed ramie, yarn or the fabric of ramee, flax fiber, hemp fibre or sisal fibers for use.
Vulcabond in the step 3 is wherein selected a kind of in Toluene-2,4-diisocyanate .4-vulcabond, Toluene-2,4-diisocyanate .6-vulcabond or the lysinediisocyanate for use.
Softening agent in the step 4 is wherein selected a kind of in dibutyl phthalate, dioctyl phthalate (DOP) or the tributyl citrate for use.
The inventive method adopts vulcabond with lactic acid/polyethyleneglycol and the crosslinked preparation matrix material of flaxen fiber, has following characteristics:
1. adopt vulcabond as linking agent, spissated lactic acid and polyoxyethylene glycol are prepared into polymer alloy.
2. utilize alkaline purification and vulcabond crosslinked, make flaxen fiber and lactic acid/polyethyleneglycol alloy coupling change flaxen fiber and combine with the interface of lactic acid/polyethyleneglycol alloy.
3. utilize the low temperature and pressure moulding process to prepare linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material.
4. the matrix material reinforced effects that makes significantly improves, and interface bond strength obviously improves, and makes the natural degradable linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material have more wide application prospect.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
The inventive method is applicable to raw ramie, degummed ramie, yarn or the fabric of ramee, flax fiber, hemp fibre or sisal fibers.At first prepare lactic acid/polyethyleneglycol alloy, flaxen fiber is comprised come unstuck, pre-treatment that degreasing, alkaline purification and vulcabond are handled; Then, flaxen fiber and vulcabond and lactic acid/polyethyleneglycol alloy is mixing; Afterwards, the low temperature and pressure moulding obtains matrix material.This method is specifically carried out according to the following steps:
Step 1: preparation lactic acid/polyethyleneglycol alloy
Get concentrated lactic acid and polyoxyethylene glycol respectively, mix, add 1～5g polyoxyethylene glycol in control 1～3ml lactic acid, add the tin protochloride and the vitriol oil again, obtain mixing solutions, add 0.1～0.5g tin protochloride in the control 100ml lactic acid, the quality of the vitriol oil accounts for 0.01%～0.5% of mixing solutions total mass, mix, then, placing temperature is in 105 ℃～170 ℃ the vacuum drying oven, heating 10h～50h, the dehydration polycondensation makes lactic acid/polyethyleneglycol alloy;
Step 2: flaxen fiber is carried out pre-treatment
Get natural flaxen fiber, adopt existing conventional weaving retting technology, flaxen fiber is come unstuck fully or not exclusively, then, placing concentration is that the NaOH aqueous solution of 5wt%～25wt% soaks 10h～30h, carries out alkaline purification, is washed with water to neutral pH=7 again, put into temperature and be 60 ℃～105 ℃ environment, behind dry 4h～5h, in acetone soln, soak 10h～25h, after the degreasing, oven dry, afterwards, immerse Toluene-2,4-diisocyanate .6-vulcabond/acetone soln, dipping 0.5h～2h, the volume ratio of Toluene-2,4-diisocyanate .6-vulcabond and acetone is to put into 3～6g flaxen fiber in 2:5～20,1～2ml Toluene-2,4-diisocyanate .6-vulcabond in this solution;
Or, get natural flaxen fiber, placing concentration is that the NaOH aqueous solution of 5wt%～25wt% soaks 10h～30h, is washed with water to neutral pH=7 again, put into temperature and be 60 ℃～105 ℃ environment, behind dry 4h～5h, in acetone soln, soak 10h～25h, after the degreasing, oven dry
Or, get natural flaxen fiber, put into temperature and be 60 ℃～105 ℃ environment, behind dry 4h～5h, in acetone soln, soak 10h～25h, after the degreasing, oven dry;
Step 3: preparation vulcabond/acetone soln
Get vulcabond and acetone respectively, mix, make vulcabond acetone/solution, the volume ratio of vulcabond and acetone is 1～2:0～2 in this solution;
Step 4: mixing
The lactic acid/polyethyleneglycol alloy that step 1 is made adds vulcabond acetone/solution that step 3 makes, add softening agent and the flaxen fiber after step 2 is handled again, form mixture, add 1～3ml lactic acid/polyethyleneglycol alloy and 1～5g flaxen fiber in control 1～2ml vulcabond acetone/solution, the quality of softening agent accounts for 1%～5% of mixture total mass, this mixture is carried out mixing, dry, make raw material;
Step 5: preparation linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material
The raw material that step 4 is made, put into mould, placing temperature is that 85 ℃～130 ℃, pressure are the environment of 1.5MPa～5MPa, hot pressing 1h～4h, take out, the demoulding, placing temperature then is 75 ℃～120 ℃ vacuum drying oven, annealing 4h～40h promptly makes linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material.
In the inventive method,
Flaxen fiber is selected raw ramie, degummed ramie, yarn or the fabric of ramee, flax fiber, hemp fibre or sisal fibers for use.
Vulcabond is selected a kind of in Toluene-2,4-diisocyanate .4-vulcabond, Toluene-2,4-diisocyanate .6-vulcabond or the lysinediisocyanate for use.
Softening agent is selected a kind of in dibutyl phthalate, dioctyl phthalate (DOP) or the tributyl citrate for use.
Embodiment 1
Get spissated lactic acid and polyoxyethylene glycol respectively, mix, add the 1g polyoxyethylene glycol in the control 1ml lactic acid, add the tin protochloride and the vitriol oil again, add the 0.1g tin protochloride in the 100ml lactic acid, the quality of the vitriol oil is 0.01% of a total mass, mix, placing temperature is in 105 ℃ the vacuum drying oven, heating 50h, the dehydration polycondensation makes lactic acid/polyethyleneglycol alloy.With ramee come unstuck fully the back (degummed ramie), the NaOH aqueous solution of putting into concentration and be 5wt% soaks 30h, be washed to pH and be neutral (pH=7), in temperature is dry 5h in 60 ℃ the vacuum environment, puts into acetone soln then and soaks 25h, takes out oven dry, immerse Toluene-2,4-diisocyanate .6-vulcabond/acetone soln, the volume ratio of Toluene-2,4-diisocyanate .6-vulcabond and acetone is 2:5 in this solution, puts into the 3g flaxen fiber, dipping 0.5h in the control 1ml Toluene-2,4-diisocyanate .6-vulcabond.Get Toluene-2,4-diisocyanate .4-vulcabond.Lactic acid/polyethyleneglycol alloy is added Toluene-2,4-diisocyanate .4-vulcabond solution, add flaxen fiber and the dibutyl phthalate that accounts for total mass 1% after handling again, add 1ml lactic acid/polyethyleneglycol and 1g flaxen fiber in the control 1ml Toluene-2,4-diisocyanate .4-vulcabond, mixing, drying makes raw material; This raw material is put into mould, and placing temperature is that 85 ℃, pressure are the environment of 1.5MPa, and hot pressing 4h takes out, and the demoulding then, is put into temperature and be 75 ℃ vacuum drying oven, and annealing 40h makes ramee and strengthens the lactic acid/polyethyleneglycol alloy compound material plate.
Embodiment 2
Get spissated lactic acid and polyoxyethylene glycol respectively, mix, add the 5g polyoxyethylene glycol in the control 3ml lactic acid, add the tin protochloride and the vitriol oil again, add the 0.5g tin protochloride in the control 100ml lactic acid, the quality of the vitriol oil is 0.5% of a total mass, mix, placing temperature is in 170 ℃ the vacuum drying oven, heating 10h, the dehydration polycondensation makes lactic acid/polyethyleneglycol alloy.After the sisal hemp raw ramie come unstuck fully, the NaOH aqueous solution of putting into concentration and be 25wt% soaked 10h, and be washed to pH and be neutral (pH=7), be dry 4h in 105 ℃ the vacuum environment in temperature, put into acetone soln then and soak 10h, take out oven dry.Immerse Toluene-2,4-diisocyanate .6-vulcabond/acetone soln, the volume ratio of Toluene-2,4-diisocyanate .6-vulcabond and acetone is 2:20 in this solution, puts into the 6g flaxen fiber, dipping 2h in the control 2ml Toluene-2,4-diisocyanate .6-vulcabond; Get Toluene-2,4-diisocyanate .6-vulcabond and acetone respectively, the mixed Toluene-2,4-diisocyanate .6-vulcabond/acetone soln that gets, the volume ratio of Toluene-2,4-diisocyanate .6-vulcabond and acetone is 2:2 in this solution.Lactic acid/polyethyleneglycol alloy is added Toluene-2,4-diisocyanate .6-vulcabond/acetone soln, add flaxen fiber and the dibutyl phthalate that accounts for total mass 5% after handling again, add 3ml lactic acid/polyethyleneglycol and 5g flaxen fiber in the control 2ml Toluene-2,4-diisocyanate .6-vulcabond, mixing, drying makes raw material; This raw material is put into mould, and placing temperature is that 130 ℃, pressure are the environment of 5MPa, and hot pressing 1h takes out, and the demoulding then, is put into temperature and be 120 ℃ vacuum drying oven, and annealing 4h makes sisal fibers and strengthens the lactic acid/polyethyleneglycol alloy compound material plate.
Embodiment 3
Get spissated lactic acid and polyoxyethylene glycol respectively, mix, add the 3g polyoxyethylene glycol in the control 2ml lactic acid, add the tin protochloride and the vitriol oil again, add the 0.3g tin protochloride in the control 100ml lactic acid, the quality of the vitriol oil is 0.3% of a total mass, mix, placing temperature is in 140 ℃ the vacuum drying oven, heating 30h, the dehydration polycondensation makes lactic acid/polyethyleneglycol alloy.After hempen original ramie come unstuck fully, the NaOH aqueous solution of putting into concentration and be 15wt% soaked 20h, and be washed to pH and be neutral (pH=7), be dry 4.5h in 85 ℃ the vacuum environment in temperature, put into acetone soln then and soak 18h, take out oven dry.Get hexamethylene diisocyanate and acetone respectively, the mixed vulcabond/acetone soln that gets, the volume ratio of hexamethylene diisocyanate and acetone is 1.5:1 in this solution.Lactic acid/polyethyleneglycol alloy is added hexamethylene diisocyanate/acetone soln, add the tributyl citrate of handling the back flaxen fiber and accounting for total mass 3% again, add 2ml lactic acid/polyethyleneglycol alloy and 3g flaxen fiber in the control 1.5ml hexamethylene diisocyanate, mixing, drying makes raw material; This raw material is put into model, and placing temperature is that 108 ℃, pressure are the environment of 3MPa, and hot pressing 3h takes out, and the demoulding then, is put into temperature and be 95 ℃ vacuum drying oven, and annealing 20h makes hemp fibre and strengthens the lactic acid/polyethyleneglycol alloy compound material plate.
Embodiment 4
Getting spissated lactic acid respectively mixes with polyoxyethylene glycol, add the 1g polyoxyethylene glycol in the control 1ml lactic acid, add the tin protochloride and the vitriol oil again, mix, add the 0.1g tin protochloride in the control 100ml lactic acid, the quality of the vitriol oil is 0.01% of a total mass, placing temperature is in 125 ℃ the vacuum drying oven, heating 20h, the dehydration polycondensation makes lactic acid and polyethyleneglycol alloy.The sisal hemp raw ramie that does not come unstuck is put into the %NaOH aqueous solution that concentration is 15wt, soak 15h, be washed to pH and be neutral (pH=7), placing temperature is 75 ℃ vacuum drying oven, adds 4.5h, then, soaks 15h in acetone soln, takes out oven dry.Get Toluene-2,4-diisocyanate .4-vulcabond and acetone respectively, mix, make Toluene-2,4-diisocyanate .4-vulcabond/acetone soln, the volume ratio of Toluene-2,4-diisocyanate .4-vulcabond and acetone is 4:1 in this solution.Lactic acid/polyethyleneglycol alloy is added in Toluene-2,4-diisocyanate .4-vulcabond/acetone soln, add flaxen fiber and the dioctyl phthalate (DOP) that accounts for total mass 2% after handling again, add 1ml lactic acid/polyethyleneglycol alloy and 1g flaxen fiber in the control 1ml Toluene-2,4-diisocyanate .4-vulcabond, mixing, dry, make raw material, this raw material is put into mould, placing temperature is that 95 ℃, pressure are the environment of 2MPa, and hot pressing 4h takes out, the demoulding, placing temperature is 85 ℃ environment, and annealing 20h obtains sisal fibers and strengthens the lactic acid/polyethyleneglycol alloy compound material plate.
Embodiment 5
Getting spissated lactic acid respectively mixes with polyoxyethylene glycol, add the 5g polyoxyethylene glycol in the control 3ml lactic acid, add the tin protochloride and the vitriol oil again, mix, add 0.5g lactic acid in the control 100ml tin protochloride, the quality of the vitriol oil is 0.5% of a total mass, then, placing temperature is in 160 ℃ the vacuum drying oven, heating 15h, the dehydration polycondensation makes lactic acid/polyethyleneglycol alloy.Flax shive after will coming unstuck, weaving, putting into concentration is the NaOH aqueous solution of 20wt%, soak 25h after, be washed to pH and be neutral (pH=7), placing temperature is that dry 4h soaks 20h in acetone soln, take out oven dry in 95 ℃ the vacuum drying oven.Get Toluene-2,4-diisocyanate .4-vulcabond and acetone respectively, mix, make Toluene-2,4-diisocyanate .4-vulcabond/acetone soln, the volume ratio of Toluene-2,4-diisocyanate .4-vulcabond and acetone is 1:0.5 in this solution.Lactic acid/polyethyleneglycol alloy is added in Toluene-2,4-diisocyanate .4-vulcabond/acetone soln, add flaxen fiber and the tributyl citrate that accounts for total mass 4% after handling again, add 3ml lactic acid/polyethyleneglycol alloy and 4g flaxen fiber in the control 2ml Toluene-2,4-diisocyanate .4-vulcabond, mixing, dry, make raw material, it is that 115 ℃, pressure are the environment of 4.5MPa that this raw material is placed temperature, behind the hot pressing 3h, take out, 110 ℃ environment is put into temperature and is in the demoulding, annealing 15h makes flax fiber and strengthens the lactic acid/polyethyleneglycol alloy compound material plate.
Embodiment 6
Getting spissated lactic acid respectively mixes with polyoxyethylene glycol, add the 3g polyoxyethylene glycol in the control 2ml lactic acid, add the tin protochloride and the vitriol oil again, mix, add the 0.3g tin protochloride in the control 100ml lactic acid, the quality of the vitriol oil is 0.3% of a total mass, then, placing temperature is in 160 ℃ the vacuum drying oven, heating 15h, the dehydration polycondensation makes lactic acid/polyethyleneglycol alloy.To be the ramie raw ramie that comes unstuck, putting into concentration is the NaOH aqueous solution of 20wt%, soak 25h after, be washed to pH and be neutral (pH=7), placing temperature is that dry 4h soaks 20h in acetone soln, take out oven dry in 95 ℃ the vacuum drying oven.Get Toluene-2,4-diisocyanate .4-vulcabond and acetone respectively, mix, make Toluene-2,4-diisocyanate .4-vulcabond/acetone soln, the volume ratio of Toluene-2,4-diisocyanate .4-vulcabond and acetone is 1:1 in this solution.Lactic acid/polyethyleneglycol alloy is added in Toluene-2,4-diisocyanate .4-vulcabond/acetone soln, add flaxen fiber and the tributyl citrate that accounts for total mass 4% after handling again, add 3ml lactic acid/polyethyleneglycol alloy and 4g flaxen fiber in the control 2ml Toluene-2,4-diisocyanate .4-vulcabond, mixing, dry, make raw material, it is that 115 ℃, pressure are the environment of 4.5MPa that this raw material is placed temperature, behind the hot pressing 3h, take out, 110 ℃ environment is put into temperature and is in the demoulding, annealing 20h makes ramee and strengthens the lactic acid/polyethyleneglycol alloy compound material plate.
Embodiment 7
Get spissated lactic acid and polyoxyethylene glycol respectively, mix, add the 3g polyoxyethylene glycol in the control 2ml lactic acid, add the tin protochloride and the vitriol oil again, mix, add the 0.3g tin protochloride in the control 100ml lactic acid, the quality of the vitriol oil is 0.3% of a total mass, mixes, placing temperature is in 140 ℃ the vacuum drying oven, heating 30h, the dehydration polycondensation makes lactic acid/polyethyleneglycol alloy.Ramee cloth after will coming unstuck, weaving is dry 4.5h in 85 ℃ the vacuum environment in temperature, puts into acetone soln then and soaks 18h, takes out oven dry.Get hexamethylene diisocyanate and acetone respectively, the mixed vulcabond/acetone soln that gets, the volume ratio of hexamethylene diisocyanate and acetone is 1.5:1 in this solution.Lactic acid/polyethyleneglycol alloy is added hexamethylene diisocyanate/acetone soln, add the tributyl citrate of handling the back flaxen fiber and accounting for total mass 3% again, add 2ml lactic acid/polyethyleneglycol and 3g flaxen fiber in the control 1.5ml hexamethylene diisocyanate, mixing, drying makes raw material; This raw material is put into model, and placing temperature is that 108 ℃, pressure are the environment of 3MPa, and hot pressing 4h takes out, and the demoulding then, is put into temperature and be 95 ℃ vacuum drying oven, and annealing 30h makes ramee and strengthens the lactic acid/polyethyleneglycol alloy compound material plate.
The inventive method is cross-linked to form flaxen fiber and lactic acid/polyethyleneglycol alloy by vulcabond Network structure obtains firmly linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material of interface, improves The enhancing effect of flaxen fiber, the composite material interface bond strength that obtains is obviously improved, and has expanded flaxen fiber The application of composite has environmental benefit.
Claims (9)
1. the preparation method of a linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material is characterized in that, carries out according to the following steps:
Step 1: preparation lactic acid/polyethyleneglycol alloy
Get concentrated lactic acid and polyoxyethylene glycol respectively, mix, add 1g～5g polyoxyethylene glycol in control 1ml～3ml lactic acid, in the mixture of above-mentioned lactic acid and polyoxyethylene glycol, add the tin protochloride and the vitriol oil, mix, obtain mixing solutions, control 100ml lactic acid adds the tin protochloride of 0.1g～0.5g, the quality of the vitriol oil accounts for 0.01%～0.5% of mixing solutions total mass, it is in 105 ℃～170 ℃ the vacuum drying oven that this mixing solutions is placed temperature, heating 10h～50h makes lactic acid/polyethyleneglycol alloy;
Step 2: flaxen fiber is carried out pre-treatment
Get flaxen fiber, come unstuck, after the alkaline purification, drying, degreasing, immerse Toluene-2,4-diisocyanate .6-vulcabond/acetone soln, dipping 0.5h～2h puts into 3g～6g flaxen fiber in control 1ml～2ml Toluene-2,4-diisocyanate .6-vulcabond;
Or, get flaxen fiber, carry out alkaline purification, drying and degreasing,
Or, get flaxen fiber, carry out drying and degreasing;
Step 3: preparation vulcabond/acetone soln
Get vulcabond and acetone respectively, mix, make vulcabond/acetone soln, the volume ratio of vulcabond and acetone is 1～2:0～2 in this solution;
Step 4: mixing
The lactic acid/polyethyleneglycol alloy that step 1 is made adds vulcabond acetone/solution that step 3 makes, add softening agent and the flaxen fiber after step 2 is handled again, form mixture, add 1ml～3ml lactic acid/polyethyleneglycol alloy and 1g～5g flaxen fiber in control 1ml～2ml vulcabond acetone/solution, the quality of softening agent accounts for 1%～5% of mixture total mass, this mixture is carried out mixing, dry, make raw material;
Step 5: preparation linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material
The raw material that step 4 is made, put into mould, placing temperature is that 85 ℃～130 ℃, pressure are the environment of 1.5MPa～5MPa, hot pressing 1h～4h, take out, the demoulding, placing temperature then is 75 ℃～120 ℃ vacuum drying oven, annealing 4h～40h promptly makes linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material.
2. preparation method according to claim 1 is characterized in that, coming unstuck in the described step 2 adopts existing conventional weaving to use retting technology, and flaxen fiber is come unstuck fully or not exclusively.
3. preparation method according to claim 1 is characterized in that, the alkaline purification in the described step 2, and it is that the NaOH aqueous solution of 5wt%～25wt% soaks 10h～30h that flaxen fiber is placed concentration, is washed with water to neutral pH=7 again.
4. preparation method according to claim 1 is characterized in that, the drying in the described step 2, and it is 60 ℃～105 ℃ environment that flaxen fiber is put into temperature, heating 4h～5h.
5. preparation method according to claim 1 is characterized in that, the degreasing in the described step 2 places acetone soln to soak 10h～25h in flaxen fiber, oven dry.
6. preparation method according to claim 1, it is characterized in that, Toluene-2,4-diisocyanate .6-vulcabond/acetone soln in the described step 2, get Toluene-2,4-diisocyanate .6-vulcabond and acetone respectively, mix and obtain this solution, wherein, the volume ratio of Toluene-2,4-diisocyanate .6-vulcabond and acetone is 2:5～20.
7. according to claim 1,2,3,4,5 or 6 described preparation methods, it is characterized in that described flaxen fiber is selected raw ramie, degummed ramie, yarn or the fabric of ramee, flax fiber, hemp fibre or sisal fibers for use.
8. according to the preparation method that claim 1 was, it is characterized in that in the described step 3, vulcabond is selected a kind of in Toluene-2,4-diisocyanate .4-vulcabond, Toluene-2,4-diisocyanate .6-vulcabond or the lysinediisocyanate for use.
9. preparation method according to claim 1 is characterized in that, in the described step 4, softening agent is selected a kind of in dibutyl phthalate, dioctyl phthalate (DOP) or the tributyl citrate for use.
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| CN2008102316431A CN101381468B (en) | 2008-10-09 | 2008-10-09 | Preparation method of linen fiber enhanced lactic acid/polyethyleneglycol alloy compound material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103261264A (en) * | 2010-12-17 | 2013-08-21 | Sk化学株式会社 | Polylactic acid resin composition and packaging film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261264A (en) * | 2010-12-17 | 2013-08-21 | Sk化学株式会社 | Polylactic acid resin composition and packaging film |
| CN103261264B (en) * | 2010-12-17 | 2015-04-01 | Sk化学株式会社 | Polylactic acid resin composition and packaging film |
| US9567428B2 (en) | 2010-12-17 | 2017-02-14 | Young-Man Yoo | Polylactic acid resin composition and a packaging film |
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