CN101891941A - Biodegradable composite foamed plastic and preparation method - Google Patents
Biodegradable composite foamed plastic and preparation method Download PDFInfo
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- CN101891941A CN101891941A CN 201010235181 CN201010235181A CN101891941A CN 101891941 A CN101891941 A CN 101891941A CN 201010235181 CN201010235181 CN 201010235181 CN 201010235181 A CN201010235181 A CN 201010235181A CN 101891941 A CN101891941 A CN 101891941A
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Abstract
The invention discloses a biodegradable composite foamed plastic. The biodegradable composite foamed plastic consists of the following components in percentage by mass: 2 to 30 percent of fibrilia, 0.2 to 2 percent of foaming agent, 0.02 to 0.5 percent of blowing promoter, 0.3 to 1.0 percent of mold releasing agent, 1 to 2 percent of surface conditioning agent, and the balance of polylactic acid master batches, wherein the summation of the mass percentage of each component is 100 percent. The invention also discloses a preparation method of the biodegradable composite foamed plastic, which comprises the following steps of: firstly, weighing raw materials according to the proportions; secondly, performing surface treatment on the fibrilia; thirdly, mixing the treated fibrilia, the polylactic acid master batches, the foaming agent, the blowing promoter and the mold releasing agent; and finally, putting the mixture into a baking oven at the temperature of between 168 and 190 DEG C to perform die pressing and foaming forming to obtain the biodegradable composite foamed plastic, wherein the time is 10 to 30 minutes and the pressure is 5 to 20 MPa. The foamed plastic prepared by the method is biodegradable and environment-friendly, has high chemical properties and excellent overall properties, and can be widely used in the material field of building and common facilities components, automotive components and computer components, various packages, shock resistance, heat insulation and the like.
Description
Technical field
The invention belongs to environmentally friendly porous plastics technical field, be specifically related to a kind of biodegradable syntactic foam, the invention still further relates to the preparation method of these plastics.
Background technology
Traditional porous plastics is the plastics of polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), urethane materials such as (PU), in aspect excellences such as light weight, thermal insulation, sound insulation property, resiliency, specific tenacitys, be widely used in aspects such as insulation, buffering, absorption and load larrying member.But all be nondegradable plastics, use to be placed in the physical environment and almost can not decompose, produce again after the burning disposal and contain carbonic acid gas (CO in a large number
2), toxic compounds and obnoxious flavoures such as nitrogen, sulphur, phosphorus, halogen, severe contamination human physical environment of depending on for existence.So the porous plastics that the complete biology of a kind of energy of people's active demand falls replaces traditional porous plastics.
Poly(lactic acid) (PLA) is the glucose that the starch that extracts from some plants such as corn, field potato obtains after acid is decomposed, and generates lactic acid through lactobacillus-fermented again, and carboxyl in the lactic acid molecules and hydroxyl be the synthetic superpolymer under proper condition.Be that PLA is to be raw material with Biological resources, the biodegradable polymer through chemosynthesis obtains is broken down into carbonic acid gas and water after the use, finish natural circulation, does not pollute the environment, and is the novel degradable polymer of a kind of important environmental friendliness; PLA is the desirable equivalent material of petroleum-based plastics, can reduce to the dependence of petroleum resources with to the pollution of environment; Simultaneously can improve additional value of farm products, have a good application prospect in fields such as packing and consumer goods.
Current, degradable PLA porous plastics is the PLA foaming product of single raw material mostly, its preparation method mainly contains: adopt thermotolerance PLA sodium nano composite material technology 1., carry out the molecular designing of nanometer level, chemical decoration technique and special melting mixing technology, improve the melt strength of PLA, use supercritical CO
2Develop powerful PLA extrusion foaming sheet material, but cost is higher.2. adopt the method for sneaking into pneumatogen in PLA to prepare the PLA expanded plastic, this enforcement working method is difficulty comparatively, does not promote.3. be raw material with PLA, non-filler adopts chemistry and physical foaming method, hot-forming preparation PLA porous plastics, and the aforesaid method performance difficulty, even use, melt strength is relatively poor, cost performance is higher, does not therefore apply.4. be raw material with PLA, non-filler adopts chemical foaming, and hot-forming preparation PLA foam can replace polystyrene foamed plastics, but the cost performance height.
Summary of the invention
The purpose of this invention is to provide a kind of biodegradable syntactic foam, solved existingly with single PLA be that the melt strength of porous plastics of main raw material is not high, working method comparatively difficulty, cost is higher and the problem of interface compatibility difference.
Another object of the present invention provides a kind of preparation method of above-mentioned plastics.
The technical solution adopted in the present invention is, a kind of biodegradable syntactic foam, according to mass percent, composed of the following components: flaxen fiber 2%～30%, whipping agent 0.2%～2%, frothing aid 0.02%～0.5%, releasing agent 0.3%～1.0%, surface treatment agent 1%～2%, surplus is the poly(lactic acid) master batch, and the mass percent sum of each component is 100%.
Another technical scheme of the present invention is, a kind of preparation method of biodegradable syntactic foam specifically implements according to following steps:
Step 1: take by weighing 2%～30% flaxen fiber, 0.2%～2% whipping agent, 0.02%～0.5% frothing aid according to mass percent, 0.3%～1.0% releasing agent, 1%～2% surface treatment agent, surplus are the poly(lactic acid) master batch, and the mass percent sum of each component is 100%;
Step 2: flaxen fiber surface treatment, with flaxen fiber dry 6h in 105 ℃ loft drier that the last step takes by weighing, put into the surface treatment agent that the step takes by weighing then, the treatment time is 1h～4h, flaxen fiber after will handling is subsequently put into 105 ℃ the dry 6h of loft drier, takes out to be cooled to room temperature;
Step 3: the flaxen fiber that will go up after the processing that obtains of step mixes with poly(lactic acid) master batch, whipping agent, frothing aid, the releasing agent that step 1 takes by weighing, place 168 ℃～190 ℃ baking oven moulded from foam moulding, time is 10～30min, pressure is 5～20Mpa, obtains the biodegradable syntactic foam of the present invention.
Characteristics of the present invention also are,
The mixture of one or more in flaxen fiber employing Chinese fiber crops wherein, ramie, flax, jute, bluish dogbane, sisal hemp, abaca, the kendir, flaxen fiber length is 1～5mm.
It is one or more mixture in 8%～20%NaOH solution, maleic anhydride, stearic acid, the silane coupling agent that wherein surface treatment agent adopts concentration.
Whipping agent wherein adopts Cellmic C 121, and frothing aid adopts zinc oxide.
Wherein releasing agent adopts a kind of in dimethyl silicone oil, MAXI type silicone grease or the liquid paraffin.
The invention has the beneficial effects as follows, cost is low, simple for process, interface compatibility is better, biodegradable, the environmentally safe of the porous plastics of gained, mechanical property is better, excellent combination property can be widely used in building and communal facility parts, automobile component and computer components, various packing, the material field such as shockproof, heat insulation.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
The biodegradable syntactic foam of the present invention, according to mass percent, it consists of: flaxen fiber 2%～30%, whipping agent 0.2%～2%, frothing aid 0.02%～0.5%, releasing agent 0.3%～1.0%, surface treatment agent 1%～2%, surplus is the poly(lactic acid) master batch, and the mass percent sum of each component is 100%.
The preparation method of the biodegradable syntactic foam of the present invention, specifically implement according to following steps:
Step 1: take by weighing 2%～30% flaxen fiber, 0.2%～2% whipping agent, 0.02%～0.5% frothing aid according to mass percent, 0.3%～1.0% releasing agent, 1%～2% surface treatment agent, surplus are the poly(lactic acid) master batch, and the mass percent sum of each component is 100%;
Step 2: flaxen fiber surface treatment, with flaxen fiber dry 6h in 105 ℃ loft drier that the last step takes by weighing, put into the surface treatment agent that the step takes by weighing after the taking-up, treatment time 1h～4h, flaxen fiber after will handling is subsequently put into 105 ℃ the dry 6h of loft drier, takes out to be cooled to room temperature;
Step 3: the flaxen fiber after the processing that step 2 is obtained mixes with poly(lactic acid) master batch, whipping agent, frothing aid, releasing agent, place 168 ℃～190 ℃ baking oven moulded from foam moulding, time is 10～30min, pressure is 5～20MPa, obtains the biodegradable syntactic foam of the present invention.
The mixture of one or more in flaxen fiber employing Chinese fiber crops wherein, ramie, flax, jute, bluish dogbane, sisal hemp, abaca, the kendir, flaxen fiber length is 1～5mm.
It is one or more mixture in 8%～20%NaOH solution, maleic anhydride, stearic acid, the silane coupling agent that wherein surface treatment agent adopts concentration.
Whipping agent wherein adopts Cellmic C 121 (AC), and frothing aid adopts zinc oxide.
Wherein releasing agent adopts a kind of in dimethyl silicone oil, MAXI type silicone grease, the liquid paraffin.
Embodiment 1
Earlier dimethyl silicone oil or MAXI type silicone grease are evenly spread upon the foaming molding mold internal surface, be as the criterion to form film, consumption does not account for the total share of syntactic foam.With 2 parts of china-hemp fibers be immersed in that concentration is 8%, temperature is 60min in 120 ℃ the NaOH solution, takes out the back with the warm water washing for several times, put into 105 ℃ oven drying and handle 6h.The china-hemp fibers of 1mm after will handling then and 0.2 part of AC whipping agent, 0.06 part of zinc oxide, 97.74 parts of PLA carry out uniform mixing in mixing roll.Last moulded from foam moulding in 168 ℃ baking oven, the time is 10min, pressure is 5MPa, makes Biodegradable foam plastic.The density that obtains porous plastics is: 0.71g/cm
3, mechanical property is characterized by: flexural strength 18.97MPa, tensile strength 4.76MPa, elongation at break 6.71%.The biological degradation experiment can be degraded fully.
Embodiment 2
Earlier dimethyl silicone oil or MAXI type silicone grease are evenly spread upon the foaming molding mold internal surface, be as the criterion to form film, consumption does not account for the total share of syntactic foam.With 8 parts of ramees be immersed in that concentration is 8%, temperature is 60min in 120 ℃ the stearic acid solution, takes out the back with the warm water washing for several times, put into 105 ℃ oven drying and handle 6h.The ramee of 2mm after will handling then and 0.4 part of AC whipping agent, 0.12 part of zinc oxide, 91.48 parts of PLA carry out uniform mixing in mixing roll.Last moulded from foam moulding in 168 ℃ baking oven, the time is 15min, pressure is 5MPa, makes Biodegradable foam plastic.The density that obtains porous plastics is: 0.64g/cm
3, mechanical property is characterized by: flexural strength 11.56MPa, tensile strength 3.46MPa, elongation at break 10.92%.The biological degradation experiment can be degraded fully.
Embodiment 3
Earlier liquid paraffin is evenly spread upon the foaming molding mold internal surface, be as the criterion to form film, consumption does not account for the total share of syntactic foam.With 15 parts of flax fibers be immersed in that concentration is 15%, temperature is 60min in 120 ℃ the NaOH solution, takes out the back with the warm water washing for several times, put into 105 ℃ oven drying and handle 6h.The flax fiber of 2mm after will handling then and 0.6 part of AC whipping agent, 0.12 part of zinc oxide, 84.28 parts of PLA carry out uniform mixing in mixing roll.Last moulded from foam moulding in 175 ℃ baking oven, the time is 15min, pressure is 20MPa, makes Biodegradable foam plastic.The density that obtains porous plastics is: 0.66g/cm
3, mechanical property is characterized by: flexural strength 10.94MPa, tensile strength 4.27MPa, elongation at break 20.16%.The biological degradation experiment can be degraded fully.
Embodiment 4
Earlier liquid paraffin or MAXI type silicone grease are evenly spread upon the foaming molding mold internal surface, be as the criterion to form film, consumption does not account for the total share of syntactic foam.With the mixture of 20 parts of jute fibres and bastose be immersed in that concentration is 1%, temperature is 60min in 120 ℃ the maleic anhydride solution, takes out the back with the warm water washing for several times, put into 105 ℃ oven drying and handle 6h.The jute fibre of 4mm after will handling then and the mixture of bastose and 0.6 part of AC whipping agent, 0.12 part of zinc oxide, 79.28 parts of PLA carry out uniform mixing in mixing roll.Last moulded from foam moulding in 175 ℃ baking oven, the time is 20min, pressure is 10MPa, makes Biodegradable foam plastic.The density that obtains porous plastics is: 0.57g/cm
3, mechanical property is characterized by: flexural strength 11.42MPa, tensile strength 4.47MPa, elongation at break 21.48%.The biological degradation experiment can be degraded fully.
Embodiment 5
Earlier dimethyl silicone oil or liquid paraffin are evenly spread upon the foaming molding mold internal surface, be as the criterion to form film, consumption does not account for the total share of syntactic foam.With the mixture of 25 parts of sisal fiberss, abaca fibre and apocynum fibres be immersed in that concentration is 1%, temperature is 60min in 120 ℃ the silane coupler solution, takes out the back with the warm water washing for several times, put into 105 ℃ oven drying and handle 6h.The mixture of sisal fibers, abaca fibre and the apocynum fibre of the 4mm after will handling then and 0.8 part of AC whipping agent, 0.095 part of zinc oxide, 74.005 parts of PLA carry out uniform mixing in mixing roll.Last moulded from foam moulding in 180 ℃ baking oven, the time is 25min, pressure is 15MPa, makes Biodegradable foam plastic.The density that obtains porous plastics is: 0.49g/cm
3, mechanical property is characterized by: flexural strength 11.82MPa, tensile strength 4.85MPa, elongation at break 22.58%.The biological degradation experiment can be degraded fully.
Embodiment 6
Earlier dimethyl silicone oil is evenly spread upon the foaming molding mold internal surface, be as the criterion to form film, consumption does not account for the total share of syntactic foam.With 30 parts of china-hemp fibers be immersed in that concentration is 1%, temperature is 120 ℃ silane coupling agent and stearic acid coupling agent mixing solutions in 60min, take out the back for several times with the warm water washing, put into 105 ℃ oven drying and handle 6h.The china-hemp fibers of 5mm after will handling then and 2.0 parts of AC whipping agents, 0.5 part of zinc oxide, 67.5 parts of PLA carry out uniform mixing in mixing roll.Last moulded from foam moulding in 190 ℃ baking oven, the time is 30min, pressure is 20MPa, makes Biodegradable foam plastic.The density that obtains porous plastics is: 0.43g/cm
3, mechanical property is characterized by: flexural strength 9.84MPa, tensile strength 4.02MPa, elongation at break 18.75%.The biological degradation experiment can be degraded fully.
Useful effect of the present invention place is described from the principle aspect:
For overcome PLA foaming body self melt strength lower cause in the foaming process bubble to break and the independent bubbles porosity low, the defective that stretching intensity is lower, fragility is bigger, the flaxen fiber that adopts raw material to come from nature strengthens mechanical intensity and melt intensity, the toughness that increases pure polylactic acid foam, the reduction PLA cost that poly-lactic acid improves foaming body, thereby overcome the defective of poly-lactic acid itself, reach and not only reduce material cost but also can put forward high performance purpose.
When the quality percentage of flaxen fiber was 2%～30%, stretching intensity, the crooked intensity of foaming body increased along with the increase of fiber content; Fragility also will be improved greatly. When flaxen fiber content was lower than 2%, the stretching intensity of foaming body was suitable with the intensity of crooked intensity and pure polylactic acid foam, and fragility is bigger. When flaxen fiber content was higher than 30%, poly-lactic acid content reduced, and flaxen fiber can not all be bondd, and caused the stretching intensity of foaming body, crooked intensity to begin to descend.
2. the azo diformamide is widely used efficient aerating powder, and gas forming amount is big, and price is cheap, 190～205 ℃ of decomposition temperatures, its catabolite nontoxic, no smelly, do not pollute. Can make even, fine and close, the pure white foam body in bubble hole. Nonflammable, room temperature storage is very stable. Adding zinc oxide blowing promotor can reduce the decomposition temperature of blowing agent.
When the quality percentage of blowing agent was 0.2%～2%, foaming body bubble hole was even, fine and close, and did not have the bubble hole and subside and merging. When foaming agents content is lower than 0.2%, foaming agents content very little, the less and skewness in bubble hole of foaming body; When foaming agents content was higher than 2%, the bubble hole caused more greatly steeping the hole and subsides and merging, and its stretching intensity and crooked intensity reduce.
When the quality percentage of blowing promotor was 0.02%～0.5%, the decomposition temperature of blowing agent was between 168 ℃～190 ℃. When the quality percentage of blowing promotor was lower than 0.02%, the decomposition temperature of blowing agent was higher than 190 ℃, and the poly-melt viscosity of lactic acid under this temperature is littler, thereby caused steeping the less even foaming failure in hole. When the quality percentage of blowing promotor was higher than 0.5%, the decomposition temperature of blowing agent was lower than 168 ℃ of the melt temperatures of poly-lactic acid, thereby causes the foaming failure.
3. when surface conditioning agent quality percentage was 1%～2%, the flaxen fiber that obtains and the interface compatibility of poly-lactic acid were better, and pull-off intensity obviously improves. When surface conditioning agent was lower than 1%, flaxen fiber hydrophilic radical still part exists, and was relatively poor with the hydrophobic grouping compatibility of poly-lactic acid, do not have desirable increase-volume effect, so interface mechanical characteristic is relatively poor; When surface conditioning agent quality percentage is higher than 2%, the flaxen fiber surface can cover too much inorganic agent, form polymolecular layer, easily cause the inhomogeneities of interface structure between filler and the resin, and unreacted other groups also can produce ill-effect in the surface conditioning agent, thereby reduce the mechanics performance of composite.
But the present invention's biodegradation syntactic foam and its preparation method, cost is greatly lower, simple for process, interface compatibility is better, but the foamed plastics biodegradation of gained, environmentally safe, the mechanics better performances, comprehensive excellent performance can be widely used in building and communal facility parts, auto parts and components and computer components, various packing, the Material Field such as shockproof, heat insulation.
Claims (10)
1. biodegradable syntactic foam, it is characterized in that, according to mass percent, composed of the following components: flaxen fiber 2%～30%, whipping agent 0.2%～2%, frothing aid 0.02%～0.5%, releasing agent 0.3%～1.0%, surface treatment agent 1%～2%, surplus is the poly(lactic acid) master batch, and the mass percent sum of each component is 100%.
2. biodegradable syntactic foam according to claim 1, it is characterized in that, the mixture of one or more in described flaxen fiber employing Chinese fiber crops, ramie, flax, jute, bluish dogbane, sisal hemp, abaca, the kendir, flaxen fiber length is 1～5mm.
3. biodegradable syntactic foam according to claim 1 is characterized in that, it is one or more mixture in 8%～20%NaOH solution, maleic anhydride, stearic acid, the silane coupling agent that described surface treatment agent adopts concentration.
4. biodegradable syntactic foam according to claim 1 is characterized in that, described whipping agent adopts Cellmic C 121, and frothing aid adopts zinc oxide.
5. biodegradable syntactic foam according to claim 1 is characterized in that, described releasing agent adopts a kind of in dimethyl silicone oil, MAXI type silicone grease or the liquid paraffin.
6. the preparation method of a biodegradable syntactic foam is characterized in that, specifically implements according to following steps:
Step 1: take by weighing 2%～30% flaxen fiber, 0.2%～2% whipping agent, 0.02%～0.5% frothing aid according to mass percent, 0.3%～1.0% releasing agent, 1%～2% surface treatment agent, surplus are the poly(lactic acid) master batch, and the mass percent sum of each component is 100%;
Step 2: flaxen fiber surface treatment, with flaxen fiber dry 6h in 105 ℃ loft drier that the last step takes by weighing, put into the surface treatment agent that the step takes by weighing then, the treatment time is 1h～4h, flaxen fiber after will handling is subsequently put into 105 ℃ the dry 6h of loft drier, takes out to be cooled to room temperature;
Step 3: the flaxen fiber that will go up after the processing that obtains of step mixes with poly(lactic acid) master batch, whipping agent, frothing aid, the releasing agent that step 1 takes by weighing, place 168 ℃～190 ℃ baking oven moulded from foam moulding, time is 10～30min, pressure is 5～20Mpa, obtains the biodegradable syntactic foam of the present invention.
7. the preparation method of biodegradable syntactic foam according to claim 6, it is characterized in that, the mixture of one or more in described flaxen fiber employing Chinese fiber crops, ramie, flax, jute, bluish dogbane, sisal hemp, abaca, the kendir, flaxen fiber length is 1～5mm.
8. the preparation method of biodegradable syntactic foam according to claim 6, it is characterized in that it is one or more mixture in 8%～20%NaOH solution, maleic anhydride, stearic acid, the silane coupling agent that described surface treatment agent adopts concentration.
9. the preparation method of biodegradable syntactic foam according to claim 6 is characterized in that, described whipping agent adopts Cellmic C 121, and frothing aid adopts zinc oxide.
10. the preparation method of biodegradable syntactic foam according to claim 6 is characterized in that, described releasing agent adopts a kind of in dimethyl silicone oil, MAXI type silicone grease or the liquid paraffin.
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| CN101891941B (en) | 2012-07-18 |
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