CN111944287A - Preparation method of high-transparency easy-tearing polylactic acid blown film - Google Patents
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
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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
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- 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
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- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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Abstract
The invention provides a preparation method of a high-transparency easy-tearing polylactic acid blown film. The composite material consists of a mixture of polylactic acid (PLA), polybutylene terephthalate-adipate (PBAT), plasticizer acetyl tri-n-butyl citrate, lubricant ethylene bis stearamide, opening agent erucamide and nucleating agent white carbon black. Weighing PLA, PBAT, a plasticizer, a lubricant, a shedding agent and a nucleating agent in proportion, adding the weighed materials into a mixer, uniformly mixing the materials, adding the materials from a feed inlet of a double-screw extruder, performing melt extrusion, water cooling, granulating and drying to obtain the special resin for the modified polylactic acid blown film, and performing water cooling and blow molding on the special resin by a film blowing machine to obtain the high-transparency easily-torn polylactic acid blown film. The PBAT, the plasticizer, the lubricant, the opening agent and the nucleating agent have synergistic effect, can effectively improve the tensile elongation at break of the polylactic acid film, has higher transparency, obtains the flat, wrinkle-free, easy-to-tear, high-transparency and completely biodegradable film, has the tensile strength up to 54.6MPa, has the light transmittance of more than 94 percent and the haze of 5.3 percent when the thickness of the film is 0.025mm, has better mechanical property and excellent transparency, and can replace films such as PE, PP, PVC and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to a preparation method of a high-transparency easy-tearing polylactic acid blown film.
Background
Different from the traditional petroleum-based plastic, the polylactic acid is polymerized by lactic acid obtained by fermenting plant starch, is a renewable resource, has the biodegradation characteristic and has very important significance for protecting the environment. Under the situation that petroleum energy is increasingly tense, the development and research of polylactic resin are particularly important. The polylactic acid has the performance similar to that of common plastic polypropylene, such as high modulus, high tensile strength and good processability. However, polylactic acid is very brittle and has an impact strength of less than 5KJ/m2Severely limiting its widespread use.
Common film packaging material applications include food packaging, trash holding, goods packaging, heat shrink film, elastic film, and the like. Most applications require film materials with high clarity, tensile strength and tear strength. However, in general, formulations that improve the mechanical properties of polylactic acid-based films tend to reduce their clarity.
Polylactic acid films can replace polyethylene, polypropylene and polyvinyl chloride films in many occasions. The polylactic acid film is mainly divided into a high transparent film, a thermal shrinkage film and a pellet blending blow molding film bag. The main applications of the high-transparency film are as follows: packaging materials such as fresh flowers, vegetables, bread, fruits, candies, etc.; the laminating film is used for laminating and molding paper pulp tableware, portable paper bags, packaging folding boxes and toilet paper; making into household freshness protection packages.
Worasak Phytwarotai et al reported in Journal of Thermal Analysis and Calorimetric (2016,126: 1797. sup. 1808.) that PLA, PBAT, Talc as a nucleating agent (Talc) and diphenylmethane diisocyanate (MDI) as a compatibilizer were blended and blown into films at ratios of parts PLA/PBAT/Talc/MDI (phr/phr/phr/phr) of 100/0/0/0, 90/10/0/0, 90/10/1/0, 90/10/1/1, 90/10/1/3, 90/10/1/5, 90/10/1/7, respectively, and the results showed that Talc was a good nucleating agent for PLA, and the addition of Talc and PBAT greatly increased the nucleation rate for PLA, however, the addition of the compatibilizer MDI, and the formation of more long chain compounds, will hinder the crystallization behavior of PLA.
Stroc et al reported in journal plastics technology (2015,43 (10): 68-72.) that dibenzoyl peroxide (BOP) was used as an interfacial compatibilizer, and PLA and PBAT were blended, extruded and blown into films with ratios of PLA/PBAT/antioxidant 1010/BOP (phr/phr/phr/phr) of 55/45/0.5/1,45/55/0.5/1, and 35/65/0.5/1, respectively, and the results indicated that the film had strong tensile strength and tear strength, and that to some extent the PBAT increased, the film had good elongation at break.
The polylactic acid, glyceryl triacetate, lubricant and other components are blended to prepare the polylactic resin which is used for preparing the tear-resistant and high-transparency polylactic acid film (CN 1304471C).
The Chinese patent with application number 201611036012.5 discloses a high-content polylactic acid film and a preparation method thereof, and the film comprises, by weight, 50-65 parts of polylactic acid, 35-50 parts of a toughening agent, 1-10 parts of a plasticizer, 0.1-2 parts of a chain extender, 0.1-4 parts of an antioxidant, and 0.5-5 parts of an opening agent. The preparation method comprises the steps of carrying out reactive mixing extrusion on the components, selecting a method for combining plasticization and toughening to obtain PLA, and aiming at changing the performance defect of serious brittleness of polylactic acid by using a blending modification technology. The plasticizer is an environment-friendly plasticizer, the toughening agent PBAT is biodegradable, and the prepared film can be completely biodegradable, thereby being beneficial to environmental protection.
The modification research of the polylactic acid blown film at home and abroad adopts an up-blowing air-cooling film blowing method, and the main problems of the pure polylactic acid film, such as serious brittleness, tear resistance and poor flexibility, are that the wide application of the polylactic acid blown film is influenced. However, no report of preparing the high-transparency polylactic acid blown film by adopting a down-blowing water cooling method is found, the high transparency is maintained, the high tensile strength is realized, the easy tearing property is realized, and the prepared film can be used for packaging materials such as fresh flowers, vegetables, bread, fruits, candies and the like; the laminating film is used for laminating and molding paper pulp tableware, portable paper bags, packaging folding boxes and toilet paper; the film has the characteristic of complete biodegradation, expands the application field of the polylactic acid film, and has great economic benefit and environmental protection benefit.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a high-transparency easy-tearing polylactic acid blown film.
The invention provides a high-transparency easy-tearing polylactic acid blown film, which comprises the following components in parts by weight: 80-95 parts of polylactic acid, 4-19 parts of polybutylene terephthalate-adipate, 0.1-5 parts of plasticizer, 0.1-1 part of lubricant, 0.1-1 part of opening agent and 0.1-0.5 part of nucleating agent; the plasticizer is acetyl tri-n-butyl citrate, the lubricant is ethylene bis-stearamide, the opening agent is erucamide, and the nucleating agent is white carbon black.
The number average molecular weight of the polylactic acid is 60000-150000 g/mol;
the weight-average molecular weight of the poly (terephthalic acid-adipic acid-butanediol ester) is 60000-180000 g/mol;
the preparation method of the high-transparency easy-tearing polylactic acid blown film comprises the following steps:
weighing the components according to the formula, weighing PLA, PBAT, a plasticizer, a lubricant, a cracking agent and a nucleating agent in proportion, adding the weighed components into a mixer, uniformly mixing, adding the components from a feed inlet of a double-screw extruder, performing melt extrusion, water cooling, grain cutting and drying to obtain the special resin for the modified polylactic acid blown film, and performing water cooling and blow molding on the special resin by a film blowing machine downward blowing method to obtain the high-transparency easily-torn polylactic acid blown film. The conditions of extrusion granulation are as follows: the set temperature of the twin-screw extruder is as follows: a first area: 150 ℃ and 170 ℃, and the second zone: 170 ℃ and 190 ℃, and a three-zone: 180 ℃ and 200 ℃, four zones: 185 ℃ C., 205 ℃ C., five zones: 185 ℃ and 205 ℃, and six zones: 185 ℃ and 205 ℃, and a seventh zone: 185 ℃ and 205 ℃, eight zones: 185 ℃ and 205 ℃, head: 180 ℃ and 200 ℃, screw rotation speed: 100-. The set temperature of the film blowing machine is as follows: a first area: 175 ℃ and 185 ℃, and the second zone: 180 ℃ and 190 ℃, and a three region: 185 ℃ and 195 ℃, four zones: 185 ℃ and 195 ℃, five zones: 180 ℃ and 190 ℃, the rotating speed of the main machine screw: 50-300rpm, traction speed of 5-10 m/min and blow-up ratio of 2-5.
Has the advantages that: according to the preparation method of the high-transparency easy-tearing polylactic acid blown film, PBAT is used as a toughening agent of polylactic acid, acetyl tri-n-butyl citrate is used as a plasticizer, the tensile breaking elongation of the polylactic acid film can be effectively improved, the plasticizer is nontoxic and odorless, the environmental protection requirement is met, the defect of serious brittleness of the polylactic acid film is overcome, the transparency of the polylactic acid is maintained, the plasticizer can obviously improve the rheological behavior of the material, the processing performance of the polylactic acid film is improved, the lubricant can improve the surface smoothness of the blown film, the opening agent can improve the opening performance of the film, and the film is prevented from being bonded together; the white carbon black can be used as a polylactic acid nucleating agent, so that the number of polylactic acid crystal nuclei is increased, the crystal size is reduced, and the tensile strength and the tensile elongation at break of the film are improved; the blending modification method has simple equipment and advanced process. The high-transparency easy-tearing polylactic acid blown film product has wide application field, can replace PE, PP, PVC and the like, is compounded with a paperboard to be made into products such as a biscuit box and the like, and has wide market prospect in the field of food packaging films. The industrialization of polylactic acid is beneficial to the long-term development of energy and material resources, promotes the deep processing of agricultural products, reduces the dependence on petroleum, solves the white pollution, promotes the development of the novel environment-friendly material industry, and has great economic and social significance.
Detailed Description
In order to further understand the present invention, the following describes the preparation method of the high transparent easy tearing polylactic acid blown film provided by the present invention with reference to the examples. The polylactic acid in the following examples is prepared from Zhejiang Hainan biomaterial, Inc. under the model of EVODE110 (weight average molecular weight 35 ten thousand g/mol); PBAT is purchased from polyester Co., Ltd, blue mountain Tunghe, Xinjiang, and has a model number TH 801T. The tensile properties of the films in the following examples were tested according to the GB/T1010.3-2006 standard; the tear strength was tested according to QB/T1130-91; the light transmittance and haze were measured by selecting a thin film material having a thickness of 0.025mm from a WGT-S optical haze meter manufactured by Shanghai precision scientific instruments.
Example 1: the invention provides a high-transparency easy-tearing polylactic acid blown film, which comprises the following components in parts by weight:
weighing the components according to the formula, weighing PLA, PBAT, a plasticizer, a lubricant, a cracking agent and a nucleating agent in proportion, adding the weighed components into a mixer, uniformly mixing, adding the components from a feed inlet of a double-screw extruder, performing melt extrusion, water cooling, grain cutting and drying to obtain the special resin for the modified polylactic acid blown film, and performing water cooling and blow molding on the special resin by a film blowing machine downward blowing method to obtain the high-transparency easily-torn polylactic acid blown film. The conditions of extrusion granulation are as follows: the set temperature of the twin-screw extruder is as follows: a first area: 150 ℃ and 170 ℃, and the second zone: 170 ℃ and 190 ℃, and a three-zone: 180 ℃ and 200 ℃, four zones: 185 ℃ C., 205 ℃ C., five zones: 185 ℃ and 205 ℃, and six zones: 185 ℃ and 205 ℃, and a seventh zone: 185 ℃ and 205 ℃, eight zones: 185 ℃ and 205 ℃, head: 180 ℃ and 200 ℃, screw rotation speed: 100-. The set temperature of the film blowing machine is as follows: a first area: 175 ℃ and 185 ℃, and the second zone: 180 ℃ and 190 ℃, and a three region: 185 ℃ and 195 ℃, four zones: 185 ℃ and 195 ℃, five zones: 180 ℃ and 190 ℃, the rotating speed of the main machine screw: 50-300rpm, traction speed of 5-10 m/min and blow-up ratio of 2-5. The thickness of the film is controlled at 0.025mm, the mechanical properties and light transmittance of the film are tested, and the test results are shown in Table 1.
Example 2: the invention provides a high-transparency easy-tearing polylactic acid blown film, which comprises the following components in parts by weight:
the extrusion granulation and film blowing procedures in this step were the same as in example 1, the film thickness was controlled at 0.025mm, the mechanical properties and light transmittance of the film were measured, and the results are shown in table 1.
Example 3: the invention provides a high-transparency easy-tearing polylactic acid blown film, which comprises the following components in parts by weight:
the extrusion granulation and film blowing procedures in this step were the same as in example 1, the film thickness was controlled at 0.025mm, the mechanical properties and light transmittance of the film were measured, and the results are shown in table 1.
Example 4: the invention provides a high-transparency easy-tearing polylactic acid blown film, which is prepared by weighing the following components in parts by weight:
the extrusion granulation and film blowing procedures in this step were the same as in example 1, the film thickness was controlled at 0.025mm, the mechanical properties and light transmittance of the film were measured, and the results are shown in table 1.
TABLE 1 polylactic acid film mechanical property and transmittance test results
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. The high-transparency easy-tearing polylactic acid blown film is characterized by comprising the following components in parts by mass: 80-95 parts of polylactic acid, 4-19 parts of polybutylene terephthalate-adipate, 0.1-5 parts of plasticizer, 0.1-1 part of lubricant, 0.1-1 part of opening agent and 0.1-0.5 part of nucleating agent; the plasticizer is acetyl tri-n-butyl citrate, the lubricant is ethylene bis-stearamide, the opening agent is erucamide, and the nucleating agent is white carbon black.
2. The blown film of polylactic acid with high transparency and easy tearing as claimed in claim 1, wherein the number average molecular weight of the polylactic acid is 60000-150000 g/mol.
3. The blown film of polylactic acid with high transparency and easy tearing as claimed in claim 1, wherein the weight average molecular weight of the polybutylene terephthalate-adipate is 60000-180000 g/mol.
4. The preparation method of the high-transparency easy-tearing polylactic acid blown film according to claim 1, which is characterized by comprising the following steps and conditions; weighing the components according to the formula, weighing PLA, PBAT, a plasticizer, a lubricant, a shedding agent and a nucleating agent in proportion, adding the weighed components into a mixer, uniformly mixing, adding the components from a feed inlet of a double-screw extruder, performing melt extrusion, water cooling, grain cutting and drying to obtain the special resin for the modified polylactic acid blown film, and performing water cooling and blow molding on the special resin by a film blowing machine downward blowing method to obtain the high-transparency easily-torn polylactic acid blown film;
the conditions of extrusion granulation are as follows: the set temperature of the twin-screw extruder is as follows: a first area: 150-170oC, a second region: 170-190oC, three regions: 180-200oC, four regions: 185-205oC, five regions: 185-205oC, six areas: 185-205oC, seventh region: 185-205oC, eight region: 185-205oC, a machine head: 180-200oC, screw rotation speed: 100-;
the set temperature of the film blowing machine is as follows: a first area: 175-185oC, a second region: 180-190oC, three regions: 185-195oC, four regions: 185-195oC, five regions: 180-190oC, rotating speed of a main machine screw: 50-300rpm, traction speed of 5-10 m/min and blow-up ratio of 2-5.
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| CN112662147A (en) * | 2020-12-23 | 2021-04-16 | 青岛润兴塑料新材料有限公司 | High-performance ternary compound biodegradable film |
| CN113045881A (en) * | 2021-04-21 | 2021-06-29 | 珠海横琴辉泽丰包装科技有限公司 | Thermal-shrinkage degradable environment-friendly film material and preparation method and application method thereof |
| CN113789037A (en) * | 2021-10-10 | 2021-12-14 | 福建长泰万泰矿物制品有限公司 | Biodegradable plastic and express packaging bag made of biodegradable plastic |
| CN113845761A (en) * | 2021-08-18 | 2021-12-28 | 浙江中科应化生态新材料科技有限公司 | High-transparency completely degradable film and preparation method thereof |
| CN113956520A (en) * | 2021-12-09 | 2022-01-21 | 雄县恒通工贸有限责任公司 | Method for manufacturing biodegradable cast film paper |
| CN115521593A (en) * | 2021-12-29 | 2022-12-27 | 嘉兴高正新材料科技股份有限公司 | High-toughness environment-friendly transparent composite film material and preparation method thereof |
| CN118109026A (en) * | 2024-03-18 | 2024-05-31 | 安徽明讯新材料科技股份有限公司 | Recoverable transparent colored composite film and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112662147A (en) * | 2020-12-23 | 2021-04-16 | 青岛润兴塑料新材料有限公司 | High-performance ternary compound biodegradable film |
| CN113045881A (en) * | 2021-04-21 | 2021-06-29 | 珠海横琴辉泽丰包装科技有限公司 | Thermal-shrinkage degradable environment-friendly film material and preparation method and application method thereof |
| CN113845761A (en) * | 2021-08-18 | 2021-12-28 | 浙江中科应化生态新材料科技有限公司 | High-transparency completely degradable film and preparation method thereof |
| CN113789037A (en) * | 2021-10-10 | 2021-12-14 | 福建长泰万泰矿物制品有限公司 | Biodegradable plastic and express packaging bag made of biodegradable plastic |
| CN113789037B (en) * | 2021-10-10 | 2022-12-02 | 福建长泰万泰矿物制品有限公司 | Biodegradable plastic and express packaging bag made of biodegradable plastic |
| CN113956520A (en) * | 2021-12-09 | 2022-01-21 | 雄县恒通工贸有限责任公司 | Method for manufacturing biodegradable cast film paper |
| CN115521593A (en) * | 2021-12-29 | 2022-12-27 | 嘉兴高正新材料科技股份有限公司 | High-toughness environment-friendly transparent composite film material and preparation method thereof |
| CN115521593B (en) * | 2021-12-29 | 2024-04-12 | 嘉兴高正新材料科技股份有限公司 | High-toughness environment-friendly transparent composite film material and preparation method thereof |
| CN118109026A (en) * | 2024-03-18 | 2024-05-31 | 安徽明讯新材料科技股份有限公司 | Recoverable transparent colored composite film and preparation method thereof |
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