CN111016230A - Method for preparing bio-plastic film by post-inflation stretch blow molding - Google Patents
Method for preparing bio-plastic film by post-inflation stretch blow molding Download PDFInfo
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- CN111016230A CN111016230A CN201911273469.1A CN201911273469A CN111016230A CN 111016230 A CN111016230 A CN 111016230A CN 201911273469 A CN201911273469 A CN 201911273469A CN 111016230 A CN111016230 A CN 111016230A
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The invention relates to the technical field of bioplastic preparation, and discloses a method for preparing a bioplastic film by post-inflation stretch blow molding. The preparation method comprises the following preparation processes: (1) uniformly dispersing micronized starch, inorganic filler, biomass polymer, white oil, coupling agent, stearic acid, paraffin and compatilizer to prepare a mixed material; (2) adding the mixed material into a co-rotating double-screw extruder, mixing, reacting, extruding and granulating to obtain bioplastic granules; (3) extruding the bioplastic granules by a double-layer sheet extruder to obtain two layers of sheets, respectively hot-pressing and compacting, and then inflating, thermally sealing edges and stretching; (4) and flattening and shaping the stretched film by using a hot roller, cutting edges, and coiling to obtain the bioplastic film. The invention can effectively prevent the film from being uneven in thickness and broken by tightly compacting the prefabricated sheet, has easily controlled preparation process and simple equipment, and has positive significance for promoting the large-scale production and application of the biological plastic film.
Description
Technical Field
The invention relates to the technical field of bioplastic preparation, and discloses a method for preparing a bioplastic film by post-inflation stretch blow molding.
Background
The plastic film is a plastic product widely applied at present, the development and application of plastic film packaging materials bring great convenience to our lives, and the plastic film packaging materials are widely applied to the fields of food, medicine, chemical industry and the like besides the application on food packaging. With the increasing requirements of food, vegetables, fruits and the like on plastic film packaging, the high performance requirements of agricultural mulching films and greenhouse films, the increasing application of industrial films and the application of computers and automation technologies, plastic films are continuously innovated.
The production methods of plastic films mainly include calendering and extrusion methods, wherein the extrusion methods are divided into extrusion blow molding, extrusion stretching and extrusion casting. The most widely used production processes today are extrusion blow molding, extrusion stretching and extrusion casting, especially polyolefin films, while calendering is mainly used for the production of some polyvinyl chloride films. In extrusion blow molding, extrusion stretching and extrusion casting, applications are increasing due to the increasing overall manufacturing technology of extrusion blow molding equipment and the much lower costs with respect to stretching and casting equipment. However, extrusion stretching equipment is still widely used in the production of high quality biaxially oriented films.
Compared with calendering and casting, the equipment for preparing the film by extrusion blow molding has less investment, small occupied area and more balanced longitudinal and transverse performances of the film. The common blown film mainly comprises a polyethylene film, a polyvinyl chloride film, an EVA film, a polyamide film and the like. However, many polymers are currently difficult to blow mold into films due to their low melt strength. For example, the PP film is mainly formed by extrusion casting and biaxial stretching, and the melt strength of the PP resin is low, so that the extrusion blow molding is difficult, and the casting and biaxial stretching directly cause the cost to rise. In addition, with the development of functional films, various additives such as inorganic fillers, metal fillers, fibers and the like are added into plastics, which directly results in difficulty in film blowing processing. Especially, the application of the bioplastic is gradually popularized and applied in recent years, and the popularization of the bioplastic is limited due to the difficulty in molding and processing the bioplastic and the difficulty in stably blowing the film.
Chinese patent application No. 201410634910.5 discloses a starch nano composite film and a preparation method thereof, wherein the starch nano composite film is a mixture formed by adding auxiliary materials into a film-forming base material; the starch-based nano composite film with excellent mechanical strength, water resistance, heat sealing performance, light transmittance and ageing resistance is prepared by mixing modified starch and polyvinyl alcohol as film forming base materials and glycerol, epoxidized soybean oil, epoxy methyl ester, citric acid ester, organic modified montmorillonite, stearic acid, glyceryl monostearate and liquid paraffin through high-speed stirring, double-screw extrusion granulation and single-screw extrusion film blowing.
Chinese invention patent application No. 201710352464.2 discloses a lignin modified starch-based PBAT biodegradable film material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) drying PBAT and lignin in vacuum; (2) adding the dried PBAT, the lignin, the chain extender, the antioxidant, the plasticizer, the lubricant and the heat stabilizer into a high-speed mixer, and uniformly mixing; (3) extruding and granulating the obtained mixed material by a double-screw extruder to obtain lignin-starch-based PBAT composite plastic granules; (4) and blowing the composite plastic granules at a certain temperature to prepare the lignin modified starch-based PBAT biodegradable film material.
According to the above, the film blowing process for plastic films in the existing scheme usually adopts closed film tube air-filling to achieve longitudinal traction stretching and transverse blowing. Because of the influence of the thermal property of the polymer, the melt strength is low when the polymer is overheated, the film bubble can be unstably vibrated and even collapsed, and the thickness of the film is not uniform; whereas a too low temperature may result in a reduced lateral blow-up ratio. When the film blowing machine is used for degrading plastics by biomass, direct film blowing is difficult, more importantly, the film blowing with the added filler is easy to break, and the continuous and stable film blowing is difficult.
Disclosure of Invention
When the existing film blowing process for widely applied plastic films is used for preparing the biomass degradation plastic films, the problems of easy film breaking, difficult continuous and stable film blowing and uneven film thickness exist, and the application of the film blowing process in the preparation of the biomass degradation plastic films is restricted. Therefore, the invention provides a method for preparing a bio-plastic film by post-inflation stretch blow molding, which realizes stable film blowing of biomass degradable plastic and effectively prevents film breaking.
The invention achieves the above purpose by the following technical scheme:
a method for preparing a bio-plastic film by post-inflation stretch blow molding comprises the following specific steps:
(1) adding micronized starch and inorganic filler into a high-speed mixer, stirring and drying, then adding a biomass polymer, white oil, a coupling agent, stearic acid, paraffin and a compatilizer, and uniformly dispersing to obtain a mixed material;
(2) adding the mixed material obtained in the step (1) into a co-rotating double-screw extruder, carrying out further mixing reaction through the double-screw extruder, simultaneously fully mixing the mixed biomass polymer with starch and inorganic filler through a compatilizer, discharging moisture and volatile substances through a vacuum port, and finishing extrusion granulation to obtain bioplastic granules;
(3) feeding the bioplastic granules obtained in the step (2) into a double-layer sheet extruder, respectively feeding two layers of sheets obtained by extrusion into an upper laminating roller set and a lower laminating roller set for hot pressing to densify the sheets, supplying air between the sheets by using an air pump after rolling, then performing heat-sealing pressing on two sides of the sheets while the sheets are hot to form a closed cylinder, and then performing traction and stretching by using a traction roller;
(4) flattening and shaping the stretched film in the step (3) through a hot roller, cutting edges, and coiling to obtain the bio-plastic film.
Starch is used as a natural high molecular compound, has wide sources, various varieties and low cost, is completely degraded into carbon dioxide and water in a natural environment, and does not cause any pollution to the environment, so the starch-based degradable plastic becomes a biodegradable plastic which is researched and developed most at home and abroad. The main component of the starch-based biodegradable material is biodegradable natural high molecular starch, which is decomposed into glucose and then into water and carbon dioxide under the action of microorganisms, so that the starch is used as a functional filler for degrading plastics. In the present invention, the micronized starch preferably has a particle size of 1000 mesh, and is preferably at least one of pea starch and corn starch;
preferably, the inorganic filler has a particle size of 1250 mesh, and is preferably at least one of calcium carbonate and talc;
preferably, the biomass polymer is one of polylactic acid, polycaprolactone and polybutylene succinate;
preferably, the white oil is industrial heavy white oil;
preferably, the coupling agent is an aluminate coupling agent and can be at least one of DL-411, DL-411AF and DL-411D, DL-411 DF;
preferably, the paraffin wax is 56# or 58# granular paraffin wax;
preferably, the compatibilizer is at least one of EMB4210 and 900E.
Preferably, in the mixed material in the step (1), by weight, 10-20 parts of micronized starch, 5-15 parts of inorganic filler, 60-70 parts of biomass polymer, 1-2 parts of white oil, 0.5-1 part of coupling agent, 0.3-1 part of stearic acid, 0.2 part of paraffin and 3-5 parts of compatilizer are added.
Preferably, the heating temperature of the high-speed mixer in the step (1) is 100-120 ℃, the stirring speed is 120-150 r/min, and the mixing time is 20-60 min.
Preferably, the screw rotating speed of the twin-screw extruder in the step (2) is 120-130 r/min, and the heating temperature is 160-180 ℃.
The invention selects a double-layer sheet extruder to extrude the bioplastic granules into the double-layer sheet, the press roller group is close to the die head as much as possible, the phenomenon of poor surface finish caused by the sagging and wrinkling of the product can be prevented, the linear velocity of the press roller is slightly higher than the extrusion velocity, and the sheet can be effectively compacted without damage. Preferably, the distance between the press roller group in the step (3) and the die head is preferably 50-100 mm; the linear speed of the compression roller is 1.1-1.25 times of the sheet extrusion linear speed; the roller temperature of the pressing roller group is 100-110 ℃.
According to the invention, the extruded sheet is subjected to hot edge sealing and inflation stretching after being compacted by the compression roller, the sheet can be tightly attached to the wall of a subsequently pressed cavity after inflation, and meanwhile, the compressed air also has a cooling effect and is kept for a certain time under a certain inflation pressure for applying pressure, so that the sheet can be fully cooled and shaped, and the smoothness of the appearance and the uniformity of the wall thickness of a product are improved; in addition, the larger the blow-up ratio is, the larger the product size is, the wall thickness is reduced, and the too small blow-up ratio easily causes the cost of raw materials to be increased, and the wall thickness of the product is, so that the larger blow-up ratio is selected; and (3) inflating and stretching after hot-pressing edge sealing, and controlling the longitudinal stretching ratio to realize uniform thickness under the condition of effectively avoiding film rupture, and further shaping under a hot roller to obtain the biodegradable plastic film with excellent performance. Preferably, the pressure of the heat-sealing pressing in the step (3) is 0.2-0.4 MPa; the longitudinal stretching ratio of the traction roller is 5-8 times; the transverse inflation ratio of the inflator pump is 4-5 times.
The bioplastic film prepared by the method not only avoids the film rupture phenomenon in blow molding, but also has good thickness uniformity. Through the test, the deviation value of the thickness of the prepared film with the thickness of 30 μm is only +/-1.0 μm.
The invention provides a method for preparing a bioplastic film by post-inflation stretch blow molding, which comprises the steps of firstly preparing a mixed material consisting of micronized starch, inorganic filler, a biomass polymer, white oil, a coupling agent, stearic acid, paraffin and a compatilizer by using a high-speed mixer, then mixing the mixed material in a co-rotating double-screw extruder for reaction, fully mixing the mixed biomass polymer with the starch and the inorganic filler by the compatilizer, and extruding and granulating to obtain bioplastic granules; extruding the plastic granules into two layers of sheets with the same thickness through a double-layer sheet extruder, respectively carrying out hot-pressing compaction by using an upper laminating roller set and a lower laminating roller set, then carrying out hot edge sealing, inflation and stretching, and finally carrying out flattening and shaping, edge cutting and coiling through a hot roller to obtain the bio-plastic film.
The invention provides a method for preparing a bio-plastic film by post-inflation stretch blow molding, which has the outstanding characteristics and excellent effects compared with the prior art:
1. a method for preparing a biological plastic film by a post-inflation stretching technology is provided.
2. The method comprises the steps of firstly preparing a sheet, enabling the sheet to be compact and not damaged by a press roll, then further performing edge sealing and inflation stretching, and sizing the stretched film under a hot roll to obtain the bio-plastic film.
3. The prefabricated sheet is tightly compacted, so that the uneven thickness of the film is prevented, and the film rupture is effectively prevented, and the prefabricated sheet has positive significance for promoting the large-scale production and application of the biological plastic film.
4. The preparation process is easy to control, the equipment is simple, and the defects of complexity, easy membrane rupture and uneven thickness of the direct sheet biaxial stretching equipment are overcome.
Drawings
FIG. 1 is a schematic view of the preparation process of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding micronized starch and inorganic filler into a high-speed mixer, stirring and drying, then adding a biomass polymer, white oil, a coupling agent, stearic acid, paraffin and a compatilizer, and uniformly dispersing to obtain a mixed material; pea starch with the grain size of 1000 meshes of micronized starch; calcium carbonate having a particle size of 1250 mesh as an inorganic filler; the biomass polymer is polylactic acid; the white oil is industrial heavy white oil; the coupling agent is an aluminate coupling agent DL-411; the paraffin is 56# granular paraffin; the compatilizer is 900E;
in the mixed material, by weight, 18 parts of micronized starch, 13 parts of inorganic filler, 68 parts of biomass polymer, 1 part of white oil, 0.5 part of coupling agent, 0.5 part of stearic acid, 0.2 part of paraffin and 4.5 parts of compatilizer;
(2) adding the mixed material obtained in the step (1) into a co-rotating double-screw extruder, carrying out further mixing reaction through the double-screw extruder, simultaneously fully mixing the mixed biomass polymer with starch and inorganic filler through a compatilizer, discharging moisture and volatile substances through a vacuum port, and finishing extrusion granulation to obtain bioplastic granules; the heating temperature of the high-speed mixer is 100 ℃, the stirring speed is 150r/min, and the mixing time is 20 min; the screw rotating speed of the double-screw extruder is 130r/min, and the heating temperature is 180 ℃;
(3) feeding the bioplastic granules obtained in the step (2) into a double-layer sheet extruder, respectively feeding two layers of sheets obtained by extrusion into an upper laminating roller set and a lower laminating roller set for hot pressing to densify the sheets, supplying air between the sheets by using an air pump after rolling, then performing heat-sealing pressing on two sides of the sheets while the sheets are hot to form a closed cylinder, and then performing traction and stretching by using a traction roller; the thickness of the upper layer sheet and the lower layer sheet is 1 mm; the distance between the press roll group and the die head is 100 mm; the linear speed of the compression roller is 1.25 times of the linear speed of sheet extrusion; the roller temperature of the compression roller group is 100 ℃; the pressure of heat sealing and pressing is 0.2 MPa; the longitudinal stretching ratio of the drawing roll is 8 times; the transverse blow-up ratio of the inflator pump is 4 times;
(4) flattening and shaping the stretched film in the step (3) through a hot roller, cutting edges, and coiling to obtain the bio-plastic film.
Example 2
(1) Adding micronized starch and inorganic filler into a high-speed mixer, stirring and drying, then adding a biomass polymer, white oil, a coupling agent, stearic acid, paraffin and a compatilizer, and uniformly dispersing to obtain a mixed material; corn starch with grain size of 1000 mesh; the particle size of the inorganic filler is 1250-mesh talcum powder; the biomass polymer is polycaprolactone; the white oil is industrial heavy white oil; the coupling agent is an aluminate coupling agent DL-411 AF; the paraffin is No. 58 granular paraffin; the compatilizer is EMB 4210;
in the mixed material, by weight, 15 parts of micronized starch, 11 parts of inorganic filler, 65 parts of biomass polymer, 1.5 parts of white oil, 0.8 part of coupling agent, 0.6 part of stearic acid, 0.2 part of paraffin and 4 parts of compatilizer;
(2) adding the mixed material obtained in the step (1) into a co-rotating double-screw extruder, carrying out further mixing reaction through the double-screw extruder, simultaneously fully mixing the mixed biomass polymer with starch and inorganic filler through a compatilizer, discharging moisture and volatile substances through a vacuum port, and finishing extrusion granulation to obtain bioplastic granules; the heating temperature of the high-speed mixer is 120 ℃, the stirring speed is 120r/min, and the mixing time is 60 min; the screw rotating speed of the double-screw extruder is 120r/min, and the heating temperature is 165 ℃;
(3) feeding the bioplastic granules obtained in the step (2) into a double-layer sheet extruder, respectively feeding two layers of sheets obtained by extrusion into an upper laminating roller set and a lower laminating roller set for hot pressing to densify the sheets, supplying air between the sheets by using an air pump after rolling, then performing heat-sealing pressing on two sides of the sheets while the sheets are hot to form a closed cylinder, and then performing traction and stretching by using a traction roller; the thickness of the upper layer sheet and the lower layer sheet is 2 mm; the distance between the press roll group and the die head is 50 mm; the linear speed of the compression roller is 1.1 times of the linear speed of sheet extrusion; the roll temperature of the compression roll group is 110 ℃; the pressure of heat sealing and pressing is 0.2 MPa; the longitudinal stretching ratio of the drawing roll is 5 times; the transverse blow-up ratio of the inflator pump is 5 times;
(4) flattening and shaping the stretched film in the step (3) through a hot roller, cutting edges, and coiling to obtain the bio-plastic film.
Example 3
(1) Adding micronized starch and inorganic filler into a high-speed mixer, stirring and drying, then adding a biomass polymer, white oil, a coupling agent, stearic acid, paraffin and a compatilizer, and uniformly dispersing to obtain a mixed material; pea starch with the grain size of 1000 meshes of micronized starch; calcium carbonate having a particle size of 1250 mesh as an inorganic filler; the biomass polymer is poly butylene succinate; the white oil is industrial heavy white oil; the coupling agent is an aluminate coupling agent DL-411D; the paraffin is 56# granular paraffin; the compatilizer is 900E;
in the mixed material, 20 parts of micronized starch, 15 parts of inorganic filler, 60 parts of biomass polymer, 2 parts of white oil, 1 part of coupling agent, 1 part of stearic acid, 0.2 part of paraffin and 5 parts of compatilizer by weight;
(2) adding the mixed material obtained in the step (1) into a co-rotating double-screw extruder, carrying out further mixing reaction through the double-screw extruder, simultaneously fully mixing the mixed biomass polymer with starch and inorganic filler through a compatilizer, discharging moisture and volatile substances through a vacuum port, and finishing extrusion granulation to obtain bioplastic granules; the heating temperature of the high-speed mixer is 110 ℃, the stirring speed is 130r/min, and the mixing time is 40 min; the screw rotating speed of the double-screw extruder is 125r/min, and the heating temperature is 160 ℃;
(3) feeding the bioplastic granules obtained in the step (2) into a double-layer sheet extruder, respectively feeding two layers of sheets obtained by extrusion into an upper laminating roller set and a lower laminating roller set for hot pressing to densify the sheets, supplying air between the sheets by using an air pump after rolling, then performing heat-sealing pressing on two sides of the sheets while the sheets are hot to form a closed cylinder, and then performing traction and stretching by using a traction roller; the thickness of the upper layer sheet and the lower layer sheet is 1.5 mm; the distance between the press roll group and the die head is 80 mm; the linear speed of the compression roller is 1.15 times of the linear speed of sheet extrusion; the roll temperature of the compression roll group is 105 ℃; the pressure of heat sealing and pressing is 0.3 MPa; the longitudinal stretching ratio of the drawing roll is 6 times; the transverse blow-up ratio of the inflator pump is 4 times;
(4) flattening and shaping the stretched film in the step (3) through a hot roller, cutting edges, and coiling to obtain the bio-plastic film.
Example 4
(1) Adding micronized starch and inorganic filler into a high-speed mixer, stirring and drying, then adding a biomass polymer, white oil, a coupling agent, stearic acid, paraffin and a compatilizer, and uniformly dispersing to obtain a mixed material; corn starch with grain size of 1000 mesh; the particle size of the inorganic filler is 1250-mesh talcum powder; the biomass polymer is polylactic acid; the white oil is industrial heavy white oil; the coupling agent is an aluminate coupling agent DL-411 DF; the paraffin is No. 58 granular paraffin; the compatilizer is EMB 4210;
in the mixed material, by weight, 10 parts of micronized starch, 5 parts of inorganic filler, 70 parts of biomass polymer, 1 part of white oil, 0.5 part of coupling agent, 0.3-1 part of stearic acid, 0.2 part of paraffin and 3 parts of compatilizer;
(2) adding the mixed material obtained in the step (1) into a co-rotating double-screw extruder, carrying out further mixing reaction through the double-screw extruder, simultaneously fully mixing the mixed biomass polymer with starch and inorganic filler through a compatilizer, discharging moisture and volatile substances through a vacuum port, and finishing extrusion granulation to obtain bioplastic granules; the heating temperature of the high-speed mixer is 105 ℃, the stirring speed is 140r/min, and the mixing time is 50 min; the screw rotating speed of the double-screw extruder is 125r/min, and the heating temperature is 175 ℃;
(3) feeding the bioplastic granules obtained in the step (2) into a double-layer sheet extruder, respectively feeding two layers of sheets obtained by extrusion into an upper laminating roller set and a lower laminating roller set for hot pressing to densify the sheets, supplying air between the sheets by using an air pump after rolling, then performing heat-sealing pressing on two sides of the sheets while the sheets are hot to form a closed cylinder, and then performing traction and stretching by using a traction roller; the thickness of the upper layer sheet and the lower layer sheet is 2 mm; the distance between the press roll group and the die head is 70 mm; the linear speed of the compression roller is 1.2 times of the linear speed of sheet extrusion; the roll temperature of the compression roll group is 108 ℃; the pressure of heat sealing and pressing is 0.25 MPa; the longitudinal stretching ratio of the drawing roll is 7 times; the transverse blow-up ratio of the inflator pump is 5 times;
(4) flattening and shaping the stretched film in the step (3) through a hot roller, cutting edges, and coiling to obtain the bio-plastic film.
Example 5
(1) Adding micronized starch and inorganic filler into a high-speed mixer, stirring and drying, then adding a biomass polymer, white oil, a coupling agent, stearic acid, paraffin and a compatilizer, and uniformly dispersing to obtain a mixed material; pea starch with the grain size of 1000 meshes of micronized starch; calcium carbonate having a particle size of 1250 mesh as an inorganic filler; the biomass polymer is polycaprolactone; the white oil is industrial heavy white oil; the coupling agent is an aluminate coupling agent DL-411; the paraffin is 56# granular paraffin; the compatilizer is EMB 4210;
in the mixed material, by weight, 12 parts of micronized starch, 12 parts of inorganic filler, 68 parts of biomass polymer, 1 part of white oil, 0.5 part of coupling agent, 1 part of stearic acid, 0.2 part of paraffin and 3 parts of compatilizer;
(2) adding the mixed material obtained in the step (1) into a co-rotating double-screw extruder, carrying out further mixing reaction through the double-screw extruder, simultaneously fully mixing the mixed biomass polymer with starch and inorganic filler through a compatilizer, discharging moisture and volatile substances through a vacuum port, and finishing extrusion granulation to obtain bioplastic granules; the heating temperature of the high-speed mixer is 115 ℃, the stirring speed is 135r/min, and the mixing time is 40 min; the screw rotating speed of the double-screw extruder is 25r/min, and the heating temperature is 170 ℃;
(3) feeding the bioplastic granules obtained in the step (2) into a double-layer sheet extruder, respectively feeding two layers of sheets obtained by extrusion into an upper laminating roller set and a lower laminating roller set for hot pressing to densify the sheets, supplying air between the sheets by using an air pump after rolling, then performing heat-sealing pressing on two sides of the sheets while the sheets are hot to form a closed cylinder, and then performing traction and stretching by using a traction roller; the thickness of the upper layer sheet and the lower layer sheet is 1 mm; the distance between the press roll group and the die head is 60 mm; the linear speed of the compression roller is 1.1 times of the linear speed of sheet extrusion; the roll temperature of the compression roll group is 110 ℃; the pressure of heat sealing and pressing is 0.4 MPa; the longitudinal stretching ratio of the drawing roll is 8 times; the transverse blow-up ratio of the inflator pump is 5 times;
(4) flattening and shaping the stretched film in the step (3) through a hot roller, cutting edges, and coiling to obtain the bio-plastic film.
Comparative example 1
Comparative example 1 the bioplastic pellets obtained in example 1 were blown directly on a conventional type 45 film blowing machine without post-inflation stretching.
The stability of the prepared films of example 1 and comparative example 1 was evaluated. For qualitative comparative analysis, the films prepared by both methods were controlled to have a width of 800mm and a thickness of about 30 μm.
And (3) film breaking condition: the stability of the films prepared by the methods of example 1 and comparative example 1 was followed, and the number of membrane rupture times per 10 rolls (15 kg/roll) of the film produced was mainly counted.
Thickness deviation value: the thickness was measured using a thickness gauge at both sides and the middle of the film, and the measurement was performed every 50 meters for measuring the uniformity of the film, as shown in table 1.
Table 1:
as can be seen from table 1: the preparation method has the advantages that the film breaking rate is low, and the thickness uniformity of the obtained film is good; in contrast, in comparative example 1, direct film blowing was used, and the obtained film had poor uniformity of thickness, and the bubble vibration was unstable, resulting in easy film rupture, and even if film formation was possible, the film thickness was very uneven.
Claims (9)
1. A method for preparing a bio-plastic film by post-inflation stretch blow molding is characterized by comprising the following specific steps:
(1) adding micronized starch and inorganic filler into a high-speed mixer, stirring and drying, then adding a biomass polymer, white oil, a coupling agent, stearic acid, paraffin and a compatilizer, and uniformly dispersing to obtain a mixed material;
(2) adding the mixed material obtained in the step (1) into a co-rotating double-screw extruder, carrying out further mixing reaction through the double-screw extruder, simultaneously fully mixing the mixed biomass polymer with starch and inorganic filler through a compatilizer, discharging moisture and volatile substances through a vacuum port, and finishing extrusion granulation to obtain bioplastic granules;
(3) feeding the bioplastic granules obtained in the step (2) into a double-layer sheet extruder, respectively feeding two layers of sheets obtained by extrusion into an upper laminating roller set and a lower laminating roller set for hot pressing to densify the sheets, supplying air between the sheets by using an air pump after rolling, then performing heat-sealing pressing on two sides of the sheets while the sheets are hot to form a closed cylinder, and then performing traction and stretching by using a traction roller;
(4) flattening and shaping the stretched film in the step (3) through a hot roller, cutting edges, and coiling to obtain the bio-plastic film.
2. The method for preparing a bio-plastic film according to claim 1, wherein the post-inflation stretch blow molding comprises the following steps:
the grain size of the micronized starch is 1000 meshes, and the micronized starch is preferably at least one of pea starch and corn starch;
the particle size of the inorganic filler is 1250 meshes, and the inorganic filler is preferably at least one of calcium carbonate and talcum powder;
the biomass polymer is one of polylactic acid, polycaprolactone and polybutylene succinate;
the white oil is industrial heavy white oil;
the coupling agent is an aluminate coupling agent and can be at least one of DL-411, DL-411AF and DL-411D, DL-411 DF;
the paraffin is 56# or 58# granular paraffin;
the compatilizer is at least one of EMB4210 and 900E.
3. The method for preparing a bio-plastic film according to claim 1, wherein the post-inflation stretch blow molding comprises the following steps: in the mixed material in the step (1), 10-20 parts of micronized starch, 5-15 parts of inorganic filler, 60-70 parts of biomass polymer, 1-2 parts of white oil, 0.5-1 part of coupling agent, 0.3-1 part of stearic acid, 0.2 part of paraffin and 3-5 parts of compatilizer by weight.
4. The method for preparing a bio-plastic film according to claim 1, wherein the post-inflation stretch blow molding comprises the following steps: the heating temperature of the high-speed mixer in the step (1) is 100-120 ℃, the stirring speed is 120-150 r/min, and the mixing time is 20-60 min.
5. The method for preparing a bio-plastic film according to claim 1, wherein the post-inflation stretch blow molding comprises the following steps: the screw rotating speed of the double-screw extruder in the step (2) is 120-130 r/min, and the heating temperature is 160-180 ℃.
6. The method for preparing a bio-plastic film according to claim 1, wherein the post-inflation stretch blow molding comprises the following steps: and (3) the thickness ratio of the upper layer sheet to the lower layer sheet in the step (3) is 1:1, and the thicknesses of the upper layer sheet and the lower layer sheet are 1-2 mm.
7. The method for preparing a bio-plastic film according to claim 1, wherein the post-inflation stretch blow molding comprises the following steps: the compression roller group in the step (3) should be as close to the die head as possible, and the distance is preferably 50-100 mm; the linear speed of the compression roller is 1.1-1.25 times of the sheet extrusion linear speed; the roller temperature of the pressing roller group is 100-110 ℃.
8. The method for preparing a bio-plastic film according to claim 1, wherein the post-inflation stretch blow molding comprises the following steps: and (4) the pressure of the heat sealing pressing in the step (3) is 0.2-0.4 MPa.
9. The method for preparing a bio-plastic film according to claim 1, wherein the post-inflation stretch blow molding comprises the following steps: the longitudinal stretching ratio of the traction roller in the step (3) is 5-8 times; the transverse inflation ratio of the inflator pump is 4-5 times.
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