CN111073232A - Reinforced filling type full-biodegradable plastic film and preparation method thereof - Google Patents
Reinforced filling type full-biodegradable plastic film and preparation method thereof Download PDFInfo
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to an enhanced filling type full-biodegradable plastic film which comprises the following components in parts by weight: 100 parts of full biodegradable resin, 350 parts of solvent 300-350 parts, 4-8 parts of chain extender, 50-65 parts of filler, 1-3 parts of lubricant and 1-3 parts of compatibilizer; the preparation method comprises the following steps: adding full-biodegradable resin into a solvent, adding a chain extender in a dissolved state, stirring and reacting completely, and evaporating the solvent to dryness; and (2) putting the obtained crosslinked full-biodegradable resin into an internal mixer, adding a filler, a lubricant and a compatibilizer for internal mixing, putting the blend obtained after internal mixing into a double-screw extruder for extrusion granulation, and blowing the prepared reinforced filling full-biodegradable resin particles by using a film blowing device to obtain the reinforced filling full-biodegradable plastic film. The invention can obviously improve the mechanical property of the full-biodegradable plastic film, improve the addition of biomass and further reduce the material cost.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an enhanced filling type full-biodegradable plastic film and a preparation method thereof.
Background
At present, plastic films are widely developed in many fields due to the advantages of light weight, high strength, stable chemical performance, low price and the like, but used plastic films are not processed properly and are mostly treated as solid waste, while common plastic wastes are difficult to naturally degrade in the environment, so that the pollution to the natural environment is more and more serious, and serious harm is caused to the life of people, and therefore, in order to solve the problem, biodegradable plastic films are paid more and more attention.
Most of the existing biodegradable plastic films are prepared by adopting powder fillers and the like and biodegradable resin through twin screws, but the performance of the full-biodegradable material can be greatly reduced after the powder fillers are added, and the conventional blending modification can not achieve the purpose of obviously improving the performance of the material; and the main body in the film material is biodegradable resin, so that the performance of the biodegradable resin is enhanced to become a means for effectively improving the performance of the material, but the effect of enhancing the chain extension of the resin by adding the chain extender is not ideal and the chain extension rate is not high only by processing the resin with double screws.
Therefore, there is a need to design a new reinforced filled type fully biodegradable plastic film and a preparation method thereof to overcome the above problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an enhanced filling type fully biodegradable plastic film and a preparation method thereof, which can obviously improve the mechanical property of the fully biodegradable plastic film, improve the addition of biomass and further reduce the material cost.
In order to achieve the purpose, the technical scheme of the invention is that the reinforced filling type full-biodegradable plastic film comprises the following components in parts by mass: 100 parts of full-biodegradable resin, 300 parts of solvent, 350 parts of chain extender, 4-8 parts of filler, 1-3 parts of lubricant and 1-3 parts of compatibilizer.
Further, the fully biodegradable resin comprises at least one of polylactic acid, polybutylene terephthalate-adipate-butylene glycol, polybutylene terephthalate-butylene succinate, polybutylene succinate-adipate-butylene glycol, polybutylene adipate, polycaprolactone and polyhydroxyalkanoate.
The solvent is any one of chloroalkanes and phenols such as dichloromethane, tetrahydrofuran, chloroform, acetone, phenol, tetrachloroethane, and the like.
Further, the chain extender is any one of bifunctional acid derivatives, isocyanate compounds, anhydride compounds and epoxides. The bifunctional acid derivative comprises 2, 2-dimethylolbutyric acid, 2-dimethylolpropionic acid and the like; the isocyanate compound comprises diisocyanate, p-phenylene diisocyanate and the like; the acid anhydride compound includes phthalic anhydride, maleic anhydride, trimellitic acid glycoside, methyl benzene diluted acid glycoside, benzoic anhydride, etc.; the epoxides include 1, 2-epoxy-4-vinylcyclohexane, ethyl 2, 3-epoxypropionate, glycidyl methacrylate, and the like.
Further, the filler comprises at least one of calcium carbonate, calcite, kaolin, talcum powder, barium sulfate, magnesium sulfate and silicon dioxide.
Further, the lubricant comprises any one of monoglyceride, white oil, polyethylene wax, silicone oil, calcium stearate, stearic acid, zinc stearate, and liquid paraffin.
Further, the compatibilizer comprises at least one of aluminate and titanate.
The invention also provides a preparation method of the reinforced filling type full-biodegradable plastic film, which comprises the following steps:
1) adding the full-biodegradable resin into a solvent, adding a chain extender in a dissolved state, stirring and reacting completely, and evaporating the solvent to obtain the crosslinked full-biodegradable resin;
2) putting the prepared crosslinked fully biodegradable resin into an internal mixer, adding a filler, a lubricant and a compatibilizer, and internally mixing for 25-30 min;
3) putting the blend obtained after banburying into a double-screw extruder for extrusion and granulation to obtain reinforced filling type full-biodegradable resin particles;
4) and blowing the manufactured reinforced filling type full-biodegradable resin particles by using a film blowing device to obtain the reinforced filling type full-biodegradable plastic film.
Further, the step 1) is specifically as follows: putting the full-biodegradable resin into a reaction kettle which is filled with a solvent and is provided with a condensing system, heating to 45 ℃, adding a chain extender while stirring after the full-biodegradable resin is completely dissolved, continuously stirring for reaction for 30min, closing the condensing system, evaporating the solvent to dryness to obtain the crosslinked full-biodegradable resin, and recovering the solvent.
Further, the processing temperature for extruding and granulating by using a double-screw extruder in the step 3) is 130-220 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention can obviously improve the mechanical property of the full-biodegradable plastic after being filled with the filler, improve the addition of the filler and further reduce the material cost;
(2) according to the invention, the fully biodegradable resin is firstly dissolved in the solvent, the chain extender is added and stirred, so that the chain extender is fully contacted and reacted with the resin, the obtained chain-extended resin is blended with the filler, the lubricant and the compatibilizer, and the performance of the obtained fully biodegradable plastic film is greatly improved.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an enhanced filling type full-biodegradable plastic film which comprises the following components in parts by mass: 100 parts of full-biodegradable resin, 300 parts of solvent, 350 parts of chain extender, 4-8 parts of filler, 1-3 parts of lubricant and 1-3 parts of compatibilizer.
The invention also provides a preparation method of the reinforced filling type full-biodegradable plastic film, which comprises the following steps:
1) adding the full-biodegradable resin into a solvent, adding a chain extender in a dissolved state, stirring and reacting completely, and evaporating the solvent to obtain the crosslinked full-biodegradable resin;
2) putting the prepared crosslinked fully biodegradable resin into an internal mixer, adding a filler, a lubricant and a compatibilizer, and internally mixing for 25-30 min;
3) putting the blend obtained after banburying into a double-screw extruder for extrusion and granulation to obtain reinforced filling type full-biodegradable resin particles;
4) and blowing the manufactured reinforced filling type full-biodegradable resin particles by using a film blowing device to obtain the reinforced filling type full-biodegradable plastic film.
The method of the invention is adopted to dissolve the full-biodegradable resin in the solvent, the chain extender is added and stirred, the chain extender is fully contacted and reacted with the resin, the obtained chain-extended resin is blended with the filler, the lubricant and the compatibilizer, and the performance of the obtained full-biodegradable plastic film is greatly improved.
Example 1
The embodiment provides an enhanced filling type full-biodegradable plastic film which comprises the following components in parts by mass: 100 parts of poly (terephthalic acid) -butanediol adipate, 350 parts of dichloromethane, 5 parts of diisocyanate, 55 parts of calcium carbonate, 2 parts of white oil and 2 parts of aluminate.
The embodiment also provides a preparation method of the reinforced filling type full-biodegradable plastic film, which comprises the following steps:
1) putting the poly (terephthalic acid) -adipic acid-butanediol ester into a reaction kettle which is provided with dichloromethane and is provided with a condensation system, heating to 45 ℃, adding diisocyanate while stirring after the poly (terephthalic acid) -adipic acid-butanediol ester is completely dissolved, continuously stirring for reaction for 30min, closing the condensation system, evaporating dichloromethane to dryness to obtain cross-linked fully biodegradable resin, and recovering the solvent to a recovery bottle for secondary utilization;
2) putting the prepared crosslinked fully biodegradable resin into an internal mixer, adding calcium carbonate, white oil and aluminate, and internally mixing for 25 min;
3) putting the blend obtained after banburying into a double-screw extruder for extrusion granulation, wherein the processing temperature is 130 ℃, and obtaining reinforced filling type fully biodegradable resin particles;
4) and blowing the manufactured reinforced filling type full-biodegradable resin particles by using a film blowing device to obtain the reinforced filling type full-biodegradable plastic film.
Comparative example 1
Comparative example 1 provides a biodegradable plastic film comprising the following components in parts by mass: 100 parts of poly (terephthalic acid) -butanediol adipate, 5 parts of diisocyanate, 55 parts of calcium carbonate, 2 parts of white oil and 2 parts of aluminate; the preparation method adopts conventional blending, and comprises the following specific steps: putting the poly (terephthalic acid) -adipate-butylene glycol ester, diisocyanate, calcium carbonate, white oil and aluminate into an internal mixer, and internally mixing for 25min to obtain a uniformly mixed material; then extruding and granulating by a double-screw extruder, wherein the processing temperature is 130 ℃; finally, blowing the film by using film blowing equipment to prepare the biodegradable plastic film.
Example 2
The embodiment provides an enhanced filling type full-biodegradable plastic film which comprises the following components in parts by mass: 100 parts of polybutylene succinate, 300 parts of dichloromethane, 5 parts of p-phenylene diisocyanate, 60 parts of barium sulfate, 1 part of polyethylene wax and 1.5 parts of titanate.
The embodiment also provides a preparation method of the reinforced filling type full-biodegradable plastic film, which comprises the following steps:
1) putting poly (butylene succinate) into a reaction kettle which is filled with dichloromethane and provided with a condensation system, heating to 45 ℃, adding p-phenylene diisocyanate while stirring after the poly (butylene succinate) is completely dissolved, continuing stirring for reaction for 30min, closing the condensation system, evaporating the dichloromethane to dryness to obtain crosslinked fully biodegradable resin, and recovering the solvent to a recovery bottle for secondary utilization;
2) putting the prepared crosslinked fully biodegradable resin into an internal mixer, adding barium sulfate, polyethylene wax and titanate, and internally mixing for 25 min;
3) putting the blend obtained after banburying into a double-screw extruder for extrusion granulation, wherein the processing temperature is 220 ℃, and obtaining reinforced filling type fully biodegradable resin particles;
4) and blowing the manufactured reinforced filling type full-biodegradable resin particles by using a film blowing device to obtain the reinforced filling type full-biodegradable plastic film.
Comparative example 2
Comparative example 1 provides a biodegradable plastic film comprising the following components in parts by mass: 100 parts of polybutylene succinate, 5 parts of p-phenylene diisocyanate, 60 parts of barium sulfate, 1 part of polyethylene wax and 1.5 parts of titanate; the preparation method adopts conventional blending, and comprises the following specific steps: putting polybutylene succinate, p-phenylene diisocyanate, barium sulfate, polyethylene wax and titanate into an internal mixer, and carrying out internal mixing for 25min to obtain a uniformly mixed material; then extruding and granulating by a double-screw extruder, wherein the processing temperature is 220 ℃; finally, blowing the film by using film blowing equipment to prepare the biodegradable plastic film.
Example 3
The embodiment provides an enhanced filling type full-biodegradable plastic film which comprises the following components in parts by mass: 50 parts of polybutylene succinate, 50 parts of polybutylene adipate, 320 parts of trichloromethane, 4 parts of phthalic anhydride, 50 parts of talcum powder, 3 parts of liquid paraffin and 1 part of aluminate.
The preparation method of the reinforced filled type full-biodegradable plastic film of the embodiment is the same as that of the embodiment 1, and only the formulation is different.
Example 4
The embodiment provides an enhanced filling type full-biodegradable plastic film which comprises the following components in parts by mass: 30 parts of poly (terephthalic acid) -butanediol adipate, 70 parts of poly (terephthalic acid) -butanediol succinate, 350 parts of trichloromethane, 8 parts of 1, 2-epoxy-4-vinylcyclohexane, 30 parts of calcium carbonate, 35 parts of talcum powder, 1 part of white oil, 3 parts of aluminate and 1 part of titanate.
The preparation method of the reinforced filled type full-biodegradable plastic film of the embodiment is the same as that of the embodiment 1, and only the formulation is different.
The mechanical properties of the films obtained in example 1, example 2, comparative example 1 and comparative example 2 were measured, and the results are shown in table 1.
As can be seen from Table 1, the film prepared by the preparation method provided by the invention has more excellent mechanical properties under the same filler addition; on the premise of ensuring the product performance, the addition amount of the filler can be increased, thereby reducing the material cost.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The reinforced filling type full-biodegradable plastic film is characterized by comprising the following components in parts by mass: 100 parts of full-biodegradable resin, 300 parts of solvent, 350 parts of chain extender, 4-8 parts of filler, 1-3 parts of lubricant and 1-3 parts of compatibilizer.
2. The reinforced filled type full biodegradable plastic film according to claim 1, wherein: the full-biodegradable resin comprises at least one of polylactic acid, poly (terephthalic acid) -butanediol adipate, poly (terephthalic acid) -butanediol succinate, poly (butylene succinate), poly (succinic acid) -butanediol adipate, poly (butylene adipate), polycaprolactone and polyhydroxyalkanoate.
3. The reinforced filled type full biodegradable plastic film according to claim 1, wherein: the solvent is any one of dichloromethane, tetrahydrofuran, trichloromethane, acetone, phenol and tetrachloroethane.
4. The reinforced filled type full biodegradable plastic film according to claim 1, wherein: the chain extender is any one of bifunctional acid derivatives, isocyanate compounds, anhydride compounds and epoxides.
5. The reinforced filled type full biodegradable plastic film according to claim 1, wherein: the filler comprises at least one of calcium carbonate, calcite, kaolin, talcum powder, barium sulfate, magnesium sulfate and silicon dioxide.
6. The reinforced filled type full biodegradable plastic film according to claim 1, wherein: the lubricant comprises any one of monoglyceride, white oil, polyethylene wax, silicone oil, calcium stearate, stearic acid, zinc stearate and liquid paraffin.
7. The reinforced filled type full biodegradable plastic film according to claim 1, wherein: the compatibilizer comprises at least one of aluminate and titanate.
8. A method for preparing the reinforced filled type full biodegradable plastic film according to any one of claims 1 to 7, comprising the steps of:
1) adding the full-biodegradable resin into a solvent, adding a chain extender in a dissolved state, stirring and reacting completely, and evaporating the solvent to obtain the crosslinked full-biodegradable resin;
2) putting the prepared crosslinked fully biodegradable resin into an internal mixer, adding a filler, a lubricant and a compatibilizer, and internally mixing for 25-30 min;
3) putting the blend obtained after banburying into a double-screw extruder for extrusion and granulation to obtain reinforced filling type full-biodegradable resin particles;
4) and blowing the manufactured reinforced filling type full-biodegradable resin particles by using a film blowing device to obtain the reinforced filling type full-biodegradable plastic film.
9. The method for preparing the reinforced filled type full biodegradable plastic film according to claim 8, wherein the method comprises the following steps: the step 1) is specifically as follows: putting the full-biodegradable resin into a reaction kettle which is filled with a solvent and is provided with a condensing system, heating to 45 ℃, adding a chain extender while stirring after the full-biodegradable resin is completely dissolved, continuously stirring for reaction for 30min, closing the condensing system, evaporating the solvent to dryness to obtain the crosslinked full-biodegradable resin, and recovering the solvent.
10. The method for preparing the reinforced filled type full biodegradable plastic film according to claim 8, wherein the method comprises the following steps: the processing temperature for extruding and granulating by adopting a double-screw extruder in the step 3) is 130-220 ℃.
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