阅读说明：本技术 一种以乳酸菌和聚酯类为主料的生物降解薄膜及其制造方法 (Biodegradable film with lactic acid bacteria and polyesters as main materials and manufacturing method thereof ) 是由 陈可夏 陈通达 陈通庆 陈通子 于 2021-11-11 设计创作，主要内容包括：本发明涉及生物降解薄膜技术领域,且公开了一种以乳酸菌和聚酯类为主料的生物降解薄膜及其制造方法,包括以下按重量份称取的成分：淀粉45-55份,乳酸菌20-35份,聚酯类42-50份,聚碳酸丁二酯13-21份,聚酯纤维30-35份,乙酰柠檬酸三丁酯6-9份,无机填料10-20份。该以乳酸菌和聚酯类为主料的生物降解薄膜及其制造方法,具有优良的使用性能,废弃后可被由自然界存在的微生物和藻类完全分解,最终被无机化成为自然界中碳素循环,并且完全没有有害物质残留的产品,进而不会造成环境污染,提高了生物降解薄膜的环保性能,以及能够有效提高生物降解薄膜的拉伸强度和抗冲击强度,并提高了生物降解薄膜使用的可靠性,而且制造方法简便高效。(The invention relates to the technical field of biodegradable films, and discloses a biodegradable film taking lactic acid bacteria and polyesters as main materials and a manufacturing method thereof, wherein the biodegradable film comprises the following components in parts by weight: 45-55 parts of starch, 20-35 parts of lactic acid bacteria, 42-50 parts of polyesters, 13-21 parts of polybutylene carbonate, 30-35 parts of polyester fiber, 6-9 parts of acetyl tributyl citrate and 10-20 parts of inorganic filler. The biodegradable film taking the lactic acid bacteria and the polyesters as the main materials and the manufacturing method thereof have excellent service performance, can be completely decomposed by microorganisms and algae existing in the nature after being discarded, and finally become a product with carbon circulation in the nature by inorganic treatment, and completely has no harmful substance residue, thereby not causing environmental pollution, improving the environmental protection performance of the biodegradable film, effectively improving the tensile strength and the impact strength of the biodegradable film, and improving the reliability of the use of the biodegradable film, and the manufacturing method is simple, convenient and efficient.)

1. The biodegradable film taking lactic acid bacteria and polyesters as main materials is characterized by comprising the following components in parts by weight: 45-55 parts of starch, 20-35 parts of lactic acid bacteria, 42-50 parts of polyesters, 13-21 parts of polybutylene carbonate, 30-35 parts of polyester fiber, 6-9 parts of acetyl tributyl citrate and 10-20 parts of inorganic filler.

2. The biodegradable film taking lactic acid bacteria and polyesters as main materials according to claim 1, wherein the polyesters comprise the following components in parts by weight: 70-85 parts of branched polyester, 11-13 parts of a chain extender, 8-12 parts of an antioxidant, 6-9 parts of a stabilizer and 10-15 parts of a nucleating agent.

3. The biodegradable film using lactic acid bacteria and polyesters as main materials according to claim 1, wherein the polyester fiber is any one of polytrimethylene terephthalate fiber and polybutylene terephthalate fiber; the diameter of the polyester fiber is 0.9-2.6 microns.

4. The biodegradable film based on lactic acid bacteria and polyesters according to claim 2, wherein said long-chain branched polyester is prepared by uniformly mixing a long-chain branched aliphatic polyester and a long-chain branched aliphatic-aromatic copolyester in a ratio of 3: 2.

5. The biodegradable film based on lactic acid bacteria and polyesters according to claim 2, wherein the chain extender is at least one of toluene diisocyanate, bischloroformate, hexamethylene diisocyanate and isophorone diisocyanate, the antioxidant is any two of bisphenol A phosphite, octadecyl propionate and dodecyl thiopropyl phosphite, the stabilizer is at least one of calcium stearate, zinc oxide, kaolin and montmorillonite, and the nucleating agent is at least one of aluminum carbonate, terephthalic acid and aluminum oxide.

6. The biodegradable film using lactic acid bacteria and polyesters as main materials according to claim 1, wherein said inorganic filler is any two of nano-hydroxyapatite, nano-halloysite and nano-white carbon black.

7. The method for manufacturing the biodegradable film mainly comprising lactic acid bacteria and polyesters according to claim 1, comprising the steps of:

s1, preparing raw materials, namely weighing starch, lactic acid bacteria, polyesters, polybutylene carbonate, polyester fibers, acetyl tributyl citrate and inorganic filler according to parts by weight;

s2, preparing polylactic acid, namely preparing unrefined glucose from starch, adding the glucose into a fermentation tank, adding lactic acid bacteria into the fermentation tank, fermenting the glucose into lactic acid, concentrating the lactic acid to prepare lactide, performing vacuum purification on lactide monomers, and completing ring opening by a solvent-free dissolving process to polymerize the monomers into the polylactic acid;

s3, drying, namely drying the polylactic acid processed and prepared in the step S2 for 4 to 5 hours at the temperature of between 80 and 85 ℃ in a vacuum environment;

s4, mixing, namely pouring polylactic acid, polyesters, polybutylene carbonate, polyester fibers, acetyl tributyl citrate and inorganic filler into mixing equipment, and fully mixing for 1-1.5 hours;

s5, granulating, namely adding the raw materials mixed in the step S4 into a double-screw extruder to be extruded to form resin particles, wherein the melting temperature of the double-screw extruder is 175-225 ℃;

s6, blowing the film, namely conveying the semi-finished product resin granulated in the step S5 to a single-screw extruder for high-temperature melting, wherein the melting temperature is 195-230 ℃, conveying the melted resin to a film blowing machine through the screw extruder for film blowing, and cooling and shaping the biodegradable film blown out of the film blowing machine through cooling equipment;

s7, printing, namely conveying the biodegradable film produced by the film blowing in the step S6 to printing equipment for printing;

and S8, sealing, packaging and storing, namely winding the biodegradable film produced in the step S7 into a product, conveying the wound biodegradable film product into a sealing bag for drying, sealing and storing, and finally registering and warehousing the sealed biodegradable film product.

Technical Field

The invention relates to the technical field of biodegradable films, in particular to a biodegradable film taking lactic acid bacteria and polyesters as main materials and a manufacturing method thereof.

Background

Petroleum resources are used as raw materials to produce a large amount of polyolefins such as polyvinyl chloride, polyethylene, polypropylene and the like, polyesters such as polystyrene, polyethylene terephthalate, polybutylene terephthalate and the like, polyamides such as polyamide 6 and other various plastics, and the plastics are generally stable and not easily decomposed in natural environment, so that a part of products containing the plastics are recycled after use, but most of the products are incinerated, carbon dioxide generated by incineration becomes one of causes of global warming, and halogen-containing plastics such as polyvinyl chloride and plastics containing different atoms such as nitrogen, phosphorus, sulfur and the like are easily incinerated to generate harmful gases, thereby causing great environmental pollution.

The traditional plastic film has the conditions of long decomposition time and incomplete decomposition in a natural environment after being used, so that the environmental pollution is easily caused, the environmental protection performance of the plastic film is further influenced, and the plastic film also has the characteristics of weak tensile strength and weak impact strength in the using process and influences the use reliability of the plastic film.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a biodegradable film taking lactic acid bacteria and polyesters as main materials and a manufacturing method thereof, the biodegradable film has excellent service performance, can be completely decomposed by microorganisms and algae existing in the nature after being discarded, is finally inorganized into a product with carbon circulation in the nature, has no harmful substance residue at all, further does not cause environmental pollution, improves the environmental protection performance of the biodegradable film, can effectively improve the tensile strength and the impact strength of the biodegradable film, improves the reliability of the biodegradable film in use and the like, solves the problems of long decomposition time and incomplete decomposition after the use of the existing plastic film, and solves the problems of weak tensile strength and weak impact strength of the plastic film in the use process.

(II) technical scheme

In order to realize the purposes that the biodegradable film has excellent use performance, can be completely decomposed by microorganisms and algae existing in the nature after being discarded, is finally inorganized into a product which has carbon circulation in the nature and has no harmful substance residue, further causes no environmental pollution, improves the environmental protection performance of the biodegradable film, can effectively improve the tensile strength and the impact strength of the biodegradable film, and improves the use reliability of the biodegradable film, the invention provides the following technical scheme: a biodegradable film taking lactic acid bacteria and polyesters as main materials comprises the following components in parts by weight: 45-55 parts of starch, 20-35 parts of lactic acid bacteria, 42-50 parts of polyesters, 13-21 parts of polybutylene carbonate, 30-35 parts of polyester fiber, 6-9 parts of acetyl tributyl citrate and 10-20 parts of inorganic filler.

Preferably, the polyester comprises the following components in parts by weight: 70-85 parts of branched polyester, 11-13 parts of a chain extender, 8-12 parts of an antioxidant, 6-9 parts of a stabilizer and 10-15 parts of a nucleating agent.

Preferably, the polyester fiber is any one of polytrimethylene terephthalate fiber and polybutylene terephthalate fiber; the diameter of the polyester fiber is 0.9-2.6 microns.

Preferably, the long-chain branched polyester is prepared by uniformly mixing long-chain branched aliphatic polyester and long-chain branched aliphatic-aromatic copolyester according to the proportion of 3: 2.

Preferably, the chain extender is at least one of toluene diisocyanate, bischloroformate, hexamethylene diisocyanate and isophorone diisocyanate, the antioxidant is any two of bisphenol A phosphite, octadecyl propionate and dodecyl thiopropyl propionate, the stabilizer is at least one of calcium stearate, zinc oxide, kaolin and montmorillonite, and the nucleating agent is at least one of aluminum carbonate, terephthalic acid and aluminum oxide.

Preferably, the inorganic filler is any two of nano hydroxyapatite, nano halloysite and nano white carbon black.

The preparation method of the biodegradable film taking the lactic acid bacteria and the polyesters as the main materials comprises the following steps:

s1, preparing raw materials, namely weighing starch, lactic acid bacteria, polyesters, polybutylene carbonate, polyester fibers, acetyl tributyl citrate and inorganic filler according to parts by weight;

s2, preparing polylactic acid, namely preparing unrefined glucose from starch, adding the glucose into a fermentation tank, adding lactic acid bacteria into the fermentation tank, fermenting the glucose into lactic acid, concentrating the lactic acid to prepare lactide, performing vacuum purification on lactide monomers, and completing ring opening by a solvent-free dissolving process to polymerize the monomers into the polylactic acid;

s3, drying, namely drying the polylactic acid processed and prepared in the step S2 for 4 to 5 hours at the temperature of between 80 and 85 ℃ in a vacuum environment;

s4, mixing, namely pouring polylactic acid, polyesters, polybutylene carbonate, polyester fibers, acetyl tributyl citrate and inorganic filler into mixing equipment, and fully mixing for 1-1.5 hours;

s5, granulating, namely adding the raw materials mixed in the step S4 into a double-screw extruder to be extruded to form resin particles, wherein the melting temperature of the double-screw extruder is 175-225 ℃;

s6, blowing the film, namely conveying the semi-finished product resin granulated in the step S5 to a single-screw extruder for high-temperature melting, wherein the melting temperature is 195-230 ℃, conveying the melted resin to a film blowing machine through the screw extruder for film blowing, and cooling and shaping the biodegradable film blown out of the film blowing machine through cooling equipment;

s7, printing, namely conveying the biodegradable film produced by the film blowing in the step S6 to printing equipment for printing;

and S8, sealing, packaging and storing, namely winding the biodegradable film produced in the step S7 into a product, conveying the wound biodegradable film product into a sealing bag for drying, sealing and storing, and finally registering and warehousing the sealed biodegradable film product.

(III) advantageous effects

Compared with the prior art, the invention provides a biodegradable film taking lactic acid bacteria and polyesters as main materials and a manufacturing method thereof, and the biodegradable film has the following beneficial effects:

the biodegradable film with lactic acid bacteria and polyesters as main materials and the manufacturing method thereof are characterized in that the polyesters, starch and lactic acid bacteria are arranged, polylactic acid prepared from starch and lactic acid bacteria is blended with organic high molecular compounds with different components, so that the tensile strength of the biodegradable film can be ensured, the breaking elongation rate is improved, meanwhile, inorganic filler is added, hydroxyl groups contained in the inorganic filler can form strong hydrogen bonds with polylactic acid molecules, the mechanical strength of a filling system is high, the mechanical property is improved, the polylactic acid is attached to straightened polyester fibers in a tensile flow field to directly form a semi-crystalline structure, meanwhile, the selected polyester fibers are degradable fibers, the excellent degradable performance of the biodegradable film is kept, the biodegradable film is mainly prepared from the polyesters and the polylactic acid, and the polyesters and the polylactic acid can ensure that the biodegradable film can be completely decomposed by the lactic acid bacteria after being used, the biodegradable film is completely biodegradable plastic, has excellent use performance, can be completely decomposed by microorganisms and algae existing in the nature after being discarded, is finally inorganized into carbon circulation in the nature, has no product with harmful substance residue, further cannot cause environmental pollution, improves the environmental protection performance of the biodegradable film, can effectively improve the tensile strength and the impact strength of the biodegradable film, and improves the use reliability of the biodegradable film.

Detailed Description

The technical solutions in the embodiments of the present invention will be 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.

A biodegradable film taking lactic acid bacteria and polyesters as main materials comprises the following components in parts by weight: 48 parts of starch, 30 parts of lactic acid bacteria, 45 parts of polyester, 15 parts of polybutylene carbonate, 33 parts of polyester fiber, 8 parts of acetyl tributyl citrate and 16 parts of inorganic filler.

The polyester comprises the following components in parts by weight: 77 parts of branched polyester, 12 parts of chain extender, 11 parts of antioxidant, 8 parts of stabilizer and 135 parts of nucleating agent, wherein the polyester can increase the tensile strength of the film and ensure the use reliability of the film.

The polyester fiber is any one of polytrimethylene terephthalate fiber and polybutylene terephthalate fiber; the diameter of the polyester fiber is 1 micron, and the polyester fiber is also degradable fiber, so that the excellent degradable performance of the poly film is maintained.

The long branched polyester is prepared by uniformly mixing long branched aliphatic polyester and long branched aliphatic-aromatic copolyester according to the proportion of 3:2, wherein the long branched chain is in a branched polymer, the branched chain is divided into a long branched chain and a short branched chain according to the length of the branched chain, the length of the long branched chain is equivalent to that of a main chain, and the length of the short branched chain is similar to that of a longer side group, so that the mechanical property of the film can be ensured.

The chain extender is at least one of toluene diisocyanate, bischloroformate, hexamethylene diisocyanate and isophorone diisocyanate, the chain extender can ensure the reliable molding of resin, the antioxidant is any two of bisphenol A phosphite, octadecyl propionate and dodecyl thiopropyl propionate, the antioxidant is a substance capable of removing damage of free radicals to human bodies and ensures the use safety of the film, the stabilizer is at least one of calcium stearate, zinc oxide, kaolin and montmorillonite, the stabilizer can ensure the stable structure of the film and further ensures the reliable use of the film, the nucleating agent is at least one of aluminum carbonate, terephthalic acid and aluminum oxide, and the nucleating agent enables the film to have reliable mechanical properties.

The inorganic filler is any two of nano hydroxyapatite, nano halloysite and nano white carbon black.

The preparation method of the biodegradable film taking the lactic acid bacteria and the polyesters as the main materials comprises the following steps:

s1, preparing raw materials, namely weighing starch, lactic acid bacteria, polyesters, polybutylene carbonate, polyester fibers, acetyl tributyl citrate and inorganic filler according to parts by weight;

s2, preparing polylactic acid, namely preparing unrefined glucose from starch, adding the glucose into a fermentation tank, adding lactic acid bacteria into the fermentation tank, fermenting the glucose into lactic acid, concentrating the lactic acid to prepare lactide, performing vacuum purification on lactide monomers, and completing ring opening by a solvent-free dissolving process to polymerize the monomers into the polylactic acid;

s3, drying, namely drying the polylactic acid processed and prepared in the step S2 for 4.5 hours at 82 ℃ in a vacuum environment;

s4, mixing, namely pouring polylactic acid, polyesters, polybutylene carbonate, polyester fibers, acetyl tributyl citrate and inorganic filler into mixing equipment, and fully mixing for 1.3 hours;

s5, granulating, namely adding the raw materials mixed in the step S4 into a double-screw extruder to be extruded to form resin particles, wherein the melting temperature of the double-screw extruder is 200 ℃;

s6, blowing the film, namely conveying the semi-finished product resin granulated in the step S5 to a single-screw extruder for high-temperature melting, wherein the melting temperature is within 210 ℃, conveying the melted resin to a film blowing machine through the screw extruder for film blowing, and cooling and shaping the biodegradable film blown out of the film blowing machine through cooling equipment;

s7, printing, namely conveying the biodegradable film produced by the film blowing in the step S6 to printing equipment for printing;

s8, sealing, packaging and storing, namely winding the biodegradable film produced in the step S7 into a product, sending the wound biodegradable film product into a sealing bag for drying, sealing and storing, and finally registering and warehousing the sealed biodegradable film product.

In summary, the biodegradable film using lactic acid bacteria and polyesters as main materials and the manufacturing method thereof, when manufacturing the biodegradable film, firstly, weighing starch, lactic acid bacteria, polyesters, polybutylene carbonate, polyester fiber, acetyl tributyl citrate and inorganic filler according to the weight parts, then, preparing starch into unrefined glucose, then, adding glucose into a fermentation tank, adding lactic acid bacteria into the fermentation tank, fermenting the glucose into lactic acid, then, concentrating the lactic acid and processing the lactic acid into lactide, performing vacuum purification on lactide monomer, completing the ring opening action by a dissolving process without using a solvent to polymerize the monomer into polylactic acid, then, drying the polylactic acid in a vacuum environment at 82 ℃ for 4.5 hours, then, mixing and granulating the raw materials, and improving the high-temperature melting of semi-finished resin prepared by a single-screw extruder after the granulation is completed, then conveying the melted resin to a film blowing machine through a screw extruder for film blowing, simultaneously cooling and shaping the biodegradable film blown out of the film blowing machine through cooling equipment, blending polylactic acid prepared from starch and lactic acid bacteria and organic high molecular compounds matched with different components, ensuring the tensile strength of the biodegradable film and improving the elongation at break, simultaneously adding inorganic filler, wherein hydroxyl groups contained in the inorganic filler can form strong hydrogen bonds with polylactic acid molecules, the mechanical strength of a filling system is high, the mechanical property is also improved, the polylactic acid attached to the straightened polyester fiber in a stretching flow field directly forms a semi-crystalline structure, simultaneously the selected polyester fiber is also degradable fiber, the excellent degradable performance of the biodegradable film is kept, and the biodegradable film is mainly prepared from polyester and polylactic acid, the polyester and the polylactic acid can ensure that the biodegradable film can be completely decomposed by lactic acid bacteria after being used, the biodegradable film is completely biodegradable plastic and has excellent use performance, can be completely decomposed by microorganisms and algae existing in the nature after being discarded, and finally is inorganized into carbon circulation in the nature, and no harmful substance is remained, so that the environment pollution can not be caused, the environmental protection performance of the biodegradable film is improved, the tensile strength and the impact strength of the biodegradable film can be effectively improved, and the use reliability of the biodegradable film is improved.

It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.