WO2011079492A1

WO2011079492A1 - Fully biodegradable multi-component film material and preparing method thereof

Info

Publication number: WO2011079492A1
Application number: PCT/CN2010/001055
Authority: WO
Inventors: 董丽松; 吕渭川; 韩常玉; 冉祥海; 边俊甲
Original assignee: 天津国韵生物材料有限公司; 中国科学院长春应用化学研究所
Priority date: 2009-12-28
Filing date: 2010-07-14
Publication date: 2011-07-07
Also published as: CN101824210A

Abstract

A fully biodegradable multi-component film material and a preparing method thereof are disclosed. The fully biodegradable multi-component film material comprises polylactic acid (PLA), 3-hydroxybutyric acid-4-hydroxybutyric acid copolymer (P3, 4HB), plasticizer, heat-resisting stabilizer, antioxidant agent, lubricating agent, nucleating agent, and anti-electrostatic agent, wherein, the mass ratio of polylactic acid (PLA), 3-hydroxybutyric acid-4-hydroxybutyric acid copolymer (P3, 4HB), plasticizer, heat-resisting stabilizer, antioxidant agent, lubricating agent, nucleating agent, and anti-electrostatic agent is 100: 5-40: 2-15: 0.1-2: 0.1-2: 0.1-2: 0.1-2: 0.1-2.

Description

Multi-component thin film material capable of complete biodegradation and preparation method thereof

The present invention is in the field of polymer modification and processing, and more particularly, the present invention discloses a fully biodegradable multicomponent film material and a process for its preparation. Background technique

The negative impact of the post-consumer waste of polymer materials on the environment has caused widespread concern. The best way to solve this serious "white pollution" problem is to select a biodegradable solution. The polymer material enables the corresponding product to enter the garbage disposal system after consumption, and finally decomposes into carbon dioxide and water without causing any harm to the environment. Therefore, the development, development and industrialization of biodegradable polymer materials are very active and the development is quite rapid.

Polyhydroxydecanoate (PHA), which is a storage material for carbon sources and energy sources enriched in the metabolism of certain microorganisms, is highly valued in biodegradable polymer materials. From the molecular chain structure, PHA is an aliphatic polyester with a very rich molecular chain structure. Compared with biodegradable polymer materials such as polylactic acid and polyglycolic acid obtained by chemical synthesis, the diversified performance of PHA structural diversity makes it a distinct advantage in applications.

The first discovered in PHA is the homopolymer, poly-3-hydroxybutyrate (PHB). However, due to its high brittleness, high melting point and low thermal decomposition temperature, it has severely restricted the wide application of PHB.

In PHA, a good combination of properties is its copolymer, such as 3-hydroxybutyric acid-3-hydroxyvaleric acid copolymer (PHBV), 3-hydroxybutyric acid-4-hydroxybutyric acid copolymer (P3, 4HB) . Since the copolymerization destroys the regularity of the molecular chain, the melting point of the polymer and the defects caused by crystallization are lowered, and the mechanical properties and processability of the copolymer are improved. BIOPOL and ENMAT are PHBV special resins introduced by ICI and Ningbo Tianan, respectively. SOGREEN is Tianjin Guoyun Company Introduced P3, 4HB special resin.

These copolymers can improve their mechanical properties and processability by adjusting the content of comonomers. Therefore, they are beneficial to the wide application of PHA completely biodegradable polymer materials. For example, in various green packaging films and containers, paper coating, heat and water resistant oil resistant products, bacterial beds for sewage treatment, telecommunications device casings, and cutting-edge technologies such as medicine and tissue engineering materials, such as Chinese patent CN1556836A, CN1501992A and It is described in CN1784467A.

Polylactic acid (PLA) is another fully biodegradable polymer material obtained by fermenting lactic acid as a monomer from plant polysaccharides, and lactic acid is subjected to polycondensation or ring-opening polymerization of lactide to obtain PLA. It can be seen that PLA and PHA are different from other general polymer materials in that they utilize renewable plant resources and have biodegradable properties. The development of PHA and PLA is one of the effective ways to alleviate the depleting oil resources and protect the ecological environment.

PLA is the largest biodegradable polymer material currently produced at the largest scale, and has a high cost performance compared to other biodegradable polymer materials. NatureWorks USA has an annual production capacity of 140,000 tons of PLA. In China, Zhejiang Hisun Biomaterials Co., Ltd. has built a demonstration production line with an annual output of 5,000 tons of PLA, and is able to provide PLA products at home and abroad.

The multi-component composition such as PHA or PLA is blended and modified to form a biodegradable polymer material, which can obviously improve the thermoplastic processing performance of the single component, and can be prepared into a film material by using the existing polymer processing equipment. Used in packaging, catering, agriculture and other fields, it has a very broad application prospect.

Representative patents include: 1) US Patent 7,208,535, "PHA compositions and methods for their use in the production of PHA films", the patent discloses The composition and technique of the blown film formation of PHBV; 2) U.S. Patent 5,763,513, "L-lactic acid polymer composition, molded product and film,," A two-way stretch film forming technique for PLA is disclosed; 3) US Patent No. 6,808,795, "Polyhydroxyalkanoate copolymer and poly lactic acid polymer compositions for laminates and films", the patent discloses PHA And PLA multilayer composite thin Membrane. Due to the stage of development, the films disclosed in the above patents have more or less deficiencies in terms of transparency, flexibility, dimensional stability, tear resistance, etc., which cannot meet the needs of practical applications, in order to meet practical application requirements. , extensive and in-depth research and development has been ongoing.

SUMMARY OF THE INVENTION The object of the present invention is to provide a novel fully biodegradable multicomponent film material and a process for the preparation thereof, in view of the deficiencies of the prior art. The multi-component composite modification technology can significantly improve the melt viscosity and strength of the system to meet the needs of the blow molding process. At the same time, it can effectively improve the mechanical properties, dimensional stability and other properties of the film product. In addition, due to the small investment in the blow molding process and the simple equipment, the combination of such multi-component composite modification technology and blow molding processing technology can effectively reduce the cost of the obtained film, which will facilitate the packaging of film materials, catering and There are a wide range of applications in agriculture and other fields. Description of the invention

In view of the deficiencies of the prior art, the present invention provides a novel fully biodegradable multicomponent film material and a preparation method thereof. The multi-component composite modification technology can reduce the processing temperature and significantly improve the melt viscosity and strength of the system, thereby meeting the processing needs of the blown film formation process. At the same time, it can effectively improve the mechanical properties, dimensional stability and other properties of the film product. In addition, the combination of such multi-component composite modification technology and blow molding technology can effectively reduce the cost of the resulting film, and will facilitate the wide application of film materials in packaging, catering and agriculture.

In one aspect, the fully biodegradable multicomponent film material disclosed herein comprises polylactic acid

PLA (its number average molecular weight 30,000-200,000, hereinafter abbreviated as "PLA"), 3-hydroxybutyric acid-4-hydroxybutyric acid copolymer P3, 4HB (the copolymer P3, 4HB 4-hydroxybutyric acid ( The content of 4HB) is 5-40 mol%, hereinafter referred to as "P3, 4HB"), plasticizer, wherein the mass ratio of PLA, P3, 4HB, and plasticizer is 100: 5-40: 2-15 .

If the copolymer P3, 4HB is absent, or although P3, 4HB is contained but the content of 4-hydroxybutyric acid 4HB is less than 5 mol%, the obtained film has poor toughness and tear resistance, and the obtained film is poor. The flatness is also poor. However, if the content of 4-hydroxybutyric acid 4HB in the copolymer P3, 4HB exceeds 40 mol%, the copolymer does not exist in the form of pellets or powder, but exists in the form of a bulk material, which causes blow molding. Processing cannot be implemented smoothly.

The addition of a plasticizer allows the PLA and the copolymer P3, 4HB to be blown into a film, but if the amount of the plasticizer exceeds 15 parts by mass (relative to 100 parts by mass of PLA), it may occur upon twin-screw granulation. The granule phenomenon and the openness of the obtained film are lowered, failing to meet the quality requirements.

The above fully biodegradable multicomponent film material preferably further contains a heat resistant stabilizer. The heat resistant stabilizer is used in an amount of 0.1 to 2 parts by mass based on 100 parts by mass of the PLA. Heat resistant stabilizers, high material processing temperatures. If the amount of the heat-resistant stabilizer added is less than 0.1 part by mass, the effect of increasing the processing temperature of the material cannot be effectively achieved, but if the amount of the heat-resistant stabilizer exceeds 2 parts by mass (relative to 100 parts by mass of PLA), the result The film may have more gel points and cannot meet the quality requirements.

In order to improve the fluidity of the processed material, the above fully biodegradable multicomponent film material preferably further contains a lubricant. The lubricant is used in an amount of 0.1 to 2 parts by mass based on 100 parts by mass of the PLA. The lubricant can improve the processing fluidity. If there is no lubricant, the material viscosity is higher under the same processed cake, so the phase increase is required: 03⁄43⁄4, which will increase the energy.

Further, PLA and P3, 4HB are not highly crystalline, and in the preparation of the fully biodegradable multicomponent film material of the present invention, it is preferred to further add a nucleating agent to the material. The nucleating agent is used in an amount of 0.1 to 2 parts by mass based on 100 parts by mass of the PLA. The addition of a nucleating agent helps the material to crystallize rapidly after being blow molded, so that the molten material is rapidly converted into a solid state to prevent the film from sticking. However, if the amount of the nucleating agent exceeds 2 parts by mass (relative to 100 parts by mass of PLA), the resulting film may lose transparency and the performance at the hem may be deteriorated, failing to meet the quality requirements.

On the other hand, not only the feasibility and convenience of processing, but also the appearance and stability of the finished film material and the antistatic property, a more fully biodegradable multi-component film material disclosed in the present invention is considered. Containing polylactic acid PLA, 3-hydroxybutyric acid-4-hydroxybutyric acid copolymer P3, 4HB, plasticizer, heat stabilizer, antioxidant, lubricant, nucleating agent, antistatic agent, The mass ratio of PLA, P3, 4HB, plasticizer, heat stabilizer, antioxidant, lubricant, nucleating agent, antistatic agent is 100: 5-40: 2-15: 0.1-2: 0.1-2: 0.1-2: 0.1-2: 0.1-2.

Further, the above plasticizers are: dioctyl phthalate, diethyl phthalate, diisooctyl phthalate, tributyl citrate, acetyl citrate tris(2-ethylhexyl) Ester), butyl hexanoyl citrate, di(2-ethylhexyl) adipate, polyethylene glycol, polypropylene glycol oxalate, epoxidized soybean oil, etc., one or two, If you choose two, you should keep the total number of copies unchanged;

The above heat-resistant stabilizer is: montmorillonite, silica, kaolin, zinc oxide, magnesium oxide, calcium stearate, succinic anhydride, cis-diol dianhydride, and one or more of butylene oxide. If two or more are selected, the total number of copies should be kept unchanged;

The above antioxidant is one of triphenyl phosphite, ethyl phosphite or bisphenol A phosphite; the above lubricant is stearic acid amide, oleic acid amide, erucic acid amide, zinc stearate, ethylene double One of stearyl amide (a sulfhydryl difatty amide);

The nucleating agent is one of dibenzylidene sorbitol, terephthalic acid, aluminum hydroxide, aluminum oxide, talc, and boron nitride;

The above antistatic agent is one of a fatty amine (e.g., laurylamine), decyl sulfonate, glycerol monolaurate, and glycerol dilaurate.

The invention also discloses a method for preparing the above fully biodegradable multi-component film material, in particular, the above components are stirred in a high-speed mixer for 3-10 minutes, then subjected to twin-screw extrusion granulation, and then single The screw extrusion blown film unit blows into a film, and the thickness of the film product can be controlled at 15-100 μm.

The twin screw extrusion system temperature is set to:

One zone: 70-80 °C

Zone 2: 120-160 °C

Three zones: 120-160 °C

Four zones: 140-180 °C

Five districts: 150-200 °C

Six districts: 150-180 °C Seven districts: 150-170 °C

Die: 140-160 °C

The single screw extrusion blow filming temperature is set to:

One area: 140-180 °C

Zone 2: 150-200. C

Three zones: 150-200 °C

Processing parameters are as follows:

Blowing ratio: 1 : 2.5-1 : 4

Traction speed: 3-6 m/mino

Main engine speed: 50-110 rpm.

Under the above processing conditions, a stable bubble can be formed to achieve blown film formation, and the obtained film material has the following mechanical properties: longitudinal tensile strength 30-50 MPa, transverse tensile strength 25-40 MPa, longitudinal elongation at break 50-300%, transverse elongation at break 40-250%, right angle tear strength 80-130MPa.

The obtained film was tested by the National Quality Supervision and Inspection Center for Plastic Products, and the biodegradation characteristics reached the requirements of GB/T 19277-2003, and it has complete biodegradability. Example

The invention will be further described in detail below by way of examples showing the invention. However, the invention is not limited to these examples.

The TE-35 twin-screw extruder of Nanjing Keya Plastic Equipment Co., Ltd. was selected, with a length to diameter ratio of 48. The Dalian JJ Huayang Plastic Machinery Co., Ltd. SJM-Z30X30 blown film unit was selected, with a length to diameter ratio of 30.

The tensile performance test was carried out in accordance with GB/T 1040.3-2006. Example 1

Weigh each component in the following parts by mass: PLA 100 parts (number average molecular weight is 30,000), P3, 4HB 5 parts (4HB content 5 mol%), 2 parts of diethyl phthalate, 0.1 part of silicon, 0.1 part of triphenyl phosphite, 0.1 part of stearamide, 0.1 part of dibenzylidene sorbitol, laurel 0.1 part of the amine, the above components were stirred in a high-speed mixer for 3 minutes, and after twin-screw granulation, the film was blown by single-screw extrusion to obtain a film product of ΙΟΟμπι.

The twin screw extrusion system temperature is set to:

Zone 1: 70 V

Zone 2: 120 °C

Three zones: 120 °C

Four zones: 140 °C

Five zones: 150 °C

Six districts: 150 °C

Seven districts: 150 V

Die: 140 °C

The single screw extrusion blow filming temperature is set to:

One zone: 140 °C

Zone 2: 150 °C

Three zones: 150 °C

Processing parameters are as follows:

Blowing ratio: 1 : 2.5

Bowing I speed: 3 m/miri.

Main engine speed: 50 rpm.

Mechanical properties of the obtained film material: longitudinal tensile strength 30 MPa, transverse tensile strength 25 MPa, longitudinal elongation at break 50%, transverse elongation at break 40%, and right angle tear strength 80 MPa. Example 2

Weigh each component in the following parts by mass: PLA 100 parts (number average molecular weight is 200,000), P3, 4HB 40 parts (4HB content 40 mol%), 15 parts of dioctyl phthalate, 2 parts of montmorillonite, 2 parts of oleic acid amide, 2 parts of terephthalic acid, 2 parts of decyl sulfonate, After the above components were stirred in a high-speed mixer for 10 minutes, the film was subjected to twin-screw granulation, and the film was blown by single-screw extrusion to obtain a film of 15 μm.

The twin screw extrusion system temperature is set to:

Zone 1: 80 V

Zone 2: 160 V

Three districts: 160 "C

Four zones: 180 V

Five districts: 200 V

Six districts: 180. C

Seven districts: 170. C

Die - 160 °C

The single screw extrusion blow filming temperature is set to:

One zone: 180 °C

Zone 2: 200 °C

Three zones: 190 °C

Processing parameters are as follows:

Blowing ratio: 1 : 4

Bowing I speed: 6 m/miri.

Main engine speed: 110 rpm.

The mechanical properties of the obtained film material are as follows: longitudinal tensile strength 50 MPa, transverse tensile strength 40 MPa, longitudinal elongation at break 300%, transverse elongation at break 250%, right angle tear strength 130 MPa _o Example 3 Weigh the components in the following parts by mass: PLA 100 parts (number average molecular weight 100,000), P3, 4HB 10 parts (4HB content 10 mol%), diisooctyl phthalate 10 parts, kaolin 1 part 1 part of ethyl phosphite, 1 part of erucic acid amide, 2 parts of aluminum hydroxide, 0.5 parts of glycerol monolaurate, the above components were stirred in a high-speed mixer for 5 minutes, after twin-screw granulation, A single screw extrusion blown film can obtain a film of 60 μm.

The temperature range of the twin-screw extrusion system is:

One zone: 75 V

Zone 2: 150 °C

Three districts: 150. C

Four zones: 170 V

Five districts: 190. C

Six districts: 170 °C

Seven districts: 170. C

Die: 160. C

The single screw extrusion blown film temperature range is:

One zone: 170 °C

Zone 2: 190 V

Three zones: 190 °C

Processing parameters are as follows:

Blowing ratio: 1 : 3

Bowing I speed: 4 m/miii.

Main engine speed: 80 rpm.

The mechanical properties of the obtained film material are as follows: longitudinal tensile strength 45 MPa,

35MPa, longitudinal elongation at break 150%, transverse elongation at break 130%,

HOMPao Example 4

Weigh the components in the following parts by mass: PLA 100 parts (number average molecular weight 80,000), P3, 4HB 20 parts (4HB content 15 mol%), tributyl citrate 10 parts, zinc oxide 0.5 parts, sub 1 part of bisphenol A phosphate, 0.2 parts of zinc stearate, 1 part of alumina, 0.3 parts of glycerol dilaurate, and the above components were stirred in a high-speed mixer for 5 minutes, and then subjected to twin-screw granulation. A single-screw extrusion blown film can obtain a film of 40 μm.

The temperature range of the twin-screw extrusion system is:

One district: 75 "C

Zone 2: 155 V

Zone 3: 155 V

Four districts: 175. C

Five zones: 195 °C

Six districts: 175 °C

Seven Districts: 175 "C

Die: 155 °C

The single screw extrusion blown film temperature range is:

One zone: 180 °C

Zone 2: 180 °C

Three zones: 190 °C

Processing parameters are as follows - blow ratio: 1 : 3

Bowing I speed - 4 m/miri.

Main engine speed: 80 rpm.

The mechanical properties of the obtained film materials are as follows: longitudinal tensile strength 38 MPa, transverse tensile strength 30 MPa, longitudinal elongation at break 190%, transverse elongation at break 150%, right angle tear strength 130 MPa _o Example 5

Weigh the components in the following parts by mass: PLA 100 parts (number average molecular weight 80,000), P3, 4HB 30 parts (4HB content 25 mol%), acetyl citrate tris(2-ethylhexyl ester) 10 parts , 0.5 parts of magnesium oxide, 1 part of ethyl pitylate, 0.2 parts of ethylene bisstearamide, 1 part of talc, 0.3 parts of glycerol dilaurate, and the above components are stirred in a high-speed mixer for 5 minutes. Thereafter, after twin-screw granulation, the film was blown by single-screw extrusion, and a film of 40 μm was obtained.

The extrusion blown film system temperature setting and processing parameters were the same as in Example 4.

The mechanical properties of the obtained film material are as follows: longitudinal tensile strength 32 MPa, transverse tensile strength 28 MPa, longitudinal elongation at break 250%, transverse elongation at break 200%, right angle tear strength 120 MPa _o Example 6

Weigh the components in the following parts by mass: PLA 100 parts (number average molecular weight 80,000), P3, 4HB 15 parts (4HB content 7 mol%), di(2-ethylhexyl) adipate 10 parts 0.5 parts of maleic acid tin, 1 part of ethyl phosphite, 0.2 parts of ethylene bisstearamide, 1 part of talc, 0.3 parts of glycerol dilaurate, and the above components are stirred in a high-speed mixer After 5 minutes, after twin-screw granulation, the film was blown by single-screw extrusion, and a film product of 40 μm was obtained.

The mechanical properties of the obtained film material were as follows: longitudinal tensile strength 35 MPa, transverse tensile strength 30 MPa, longitudinal elongation at break 130%, transverse elongation at break 100%, right angle tear strength HOMPao Example 7

Weigh the components in the following parts by mass: PLA 100 parts (number average molecular weight 80,000), P3, 4HB 25 parts (4HB content 15 mol%), polyethylene glycol 5 parts, polypropylene glycol oxalate 5 Butene 0.5 parts of dibutyltin, 1 part of ethyl phosphite, 0.2 part of ethylene bisstearamide, 1 part of talc, 0.3 parts of glycerol dilaurate, and the above components were stirred in a high-speed mixer for 5 minutes. After twin-screw granulation, a single-screw extrusion blown film can obtain a film product of 50 μm.

The mechanical properties of the obtained film material were as follows: longitudinal tensile strength 38 MPa, transverse tensile strength 30 MPa, longitudinal elongation at break 240%, transverse elongation at break 160%, and right angle tear strength 128 MPa. Example 8

Weigh the components in the following parts by mass: PLA 100 parts (number average molecular weight 80,000), P3, 4HB 25 parts (4HB content 15 mol%), polypropylene glycol oxalate 10 parts, epoxy soybean oil 5 Parts, 0.5 parts of butylene oxide, 1 part of bisphenol A phosphite, 0.2 part of ethylene bisstearamide, 1 part of boron nitride, 0.3 parts of dilaurate, 0.3 parts of the above components at high speed After stirring for 5 minutes in a mixer, after twin-screw granulation, the film was blown by single-screw extrusion to obtain a film product of 45 μm.

The mechanical properties of the obtained film materials are as follows: longitudinal tensile strength 36 MPa, transverse tensile strength

28MPa, longitudinal elongation at break 225%, transverse elongation at break 150%, right angle tear strength lllMPao

Example 9

Weigh the components in the following parts by mass: PLA 100 parts (number average molecular weight is 55,000), P3, 4HB 15 parts (4HB content 7 mol%), acetylated tributyl citrate 6 parts, maleic acid 0.5 parts of anhydride, 0.1 part of silica, 0.1 part of stearic acid amide, and the above components were stirred in a high-speed mixer for 3 minutes, and after twin-screw granulation, the film was blown by single-screw extrusion to obtain a film of 40 μm. product.

The twin screw extrusion system temperature is set to: One zone: 70 °C

Zone 2: 120 °C

Three zones: 150 °C

Four zones: 170 °C

Five zones: 190 °C

Six districts: 180 °C

District 7: 170 °C

Die: 150 °C

The single screw extrusion blow filming temperature is set to:

One zone: 140 °C

Zone 2: 150 °C

Three zones: 150 °C

Processing parameters are as follows - blow up ratio: 1 : 2.5

Bowing I speed: 3 m/min.

Main engine speed: 50 rpm.

Mechanical properties of the obtained film material: longitudinal tensile strength 38 MPa, transverse tensile strength 35 MPa, longitudinal elongation at break 150%, transverse elongation at break 120%, and right angle tear strength 80 MPa.

Example 10

Weigh the components in the following parts by mass: PLA 100 parts (number average molecular weight 80,000), P3, 4HB 25 parts (4HB content 12 mol%), epoxidized soybean oil 4 parts, succinic anhydride 0.5, dioxide After 0.3 parts of silicon, the above components were stirred in a high-speed mixer for 3 minutes, and after twin-screw granulation, a single-screw extrusion blown film was used to obtain a film product of 50 μm.

The twin screw extrusion system temperature is set to:

One zone: 70 °C Zone 2: 120 °C

Three zones: 160 °C

Four zones: 180 °C

Five zones: 190 °C

Six districts: 190 °C

District 7: 170 °C

Die: 150 °C

The single screw extrusion blow filming temperature is set to:

One zone: 140 °C

Zone 2: 150 V

Three zones: 150 V

Processing parameters are as follows:

Blowing ratio: 1 : 3.0

Traction speed: 2.8 m/mino

Main engine speed: 50 rpm.

Mechanical properties of the obtained film material: longitudinal tensile strength 35 MPa, transverse tensile strength 38 MPa, longitudinal elongation at break 180%, transverse elongation at break 140%, and right angle tear 105 105 MPa.

Comparative Example 1:

Weigh the components in the following parts by mass: 100 parts of PLA, number average molecular weight of 30,000, 2 parts of diethyl phthalate, 0.1 parts of silica, 0.1 parts of triphenyl phosphite, stearamide 0.1 Parts, 0.1 parts of dibenzylidene sorbitol, 0.1 parts of fatty amine. After the above components were stirred in a high-speed mixer for 3 minutes, after twin-screw granulation, single-screw extrusion blown film, extrusion blown film system temperature setting and processing parameters were the same as in Example 1, and a film of 80 μm was obtained. product. Mechanical properties of the obtained film material - longitudinal tensile strength 45 MPa, transverse tensile strength 40 MPa, longitudinal elongation at break 7%, transverse The elongation at break is 5%, and the right-angle tear strength is 40 MPa. Due to the lack of P3, 4HB in the composition, the resulting film has poor toughness and tear resistance. Further, the resulting film was inferior in flatness.

Comparative Example 2:

The components were weighed according to the following parts: PLA 100 parts, number average molecular weight 80,000, P3, 4HB 15 parts, 4HB content 7 mol%, acetylated tributyl citrate 18 parts, maleic anhydride 0.5 Serving, 0.2 parts of ethyl phosphite, 0.2 parts of sulfhydryl di-fatty acid amide, 1 part of talc, 0.3 parts of glycerol dilaurate, and the above components were stirred in a high-speed mixer for 5 minutes, and then made by twin-screw. Granules, granules appear, single-screw extrusion blown film, film opening properties are reduced, failing to meet quality requirements. Comparative Example 3

Weigh each component according to the following parts: PLA 100 parts, number average molecular weight 80,000, P3, 4HB 15 parts, 4HB content 10 mol%, di(2-ethylhexyl) adipate 10 parts, cis 2.5 parts of dibutyltin butene (exceeding the amount of heat stabilizer of the present invention), 0.2 parts of ethyl phosphite, 0.2 parts of sulfhydryl di-fatty acid amide, 1 part of talc, 0.3 parts of dilauric acid, and the above components After stirring for 5 minutes in a high-speed mixer, the twin-screw granulation, single-screw extrusion blown film, extrusion blown film system temperature setting and processing parameters were the same as in Example 1, and a film of 40 μm was obtained. However, the resulting film exhibited more gel points and did not meet quality requirements. Comparative Example 4

Weigh the components in the following parts by mass: 100 parts of PLA, number average molecular weight of 80,000, Ρ3,4ΗΒ 25 parts, 4ΗΒ content 10 mol%, epoxidized soybean oil 8 parts, maleic anhydride 0.5 parts, sub 0.2 parts of ethyl phosphate, 0.2 parts of sulfhydryl di-fatty acid amide, 5 parts of talc, and 0.3 parts of glycerol dilaurate. After mixing the above components in a high-speed mixer for 5 minutes, after twin-screw granulation, Single-screw extrusion blown film, extrusion blown film system temperature setting and processing parameters were the same as in Example 4, and a film product of 30 μm was obtained. However, the obtained film loses transparency, the performance at the hem is deteriorated, and the quality is not achieved. begging.

Comparative Example 5

Weigh the components according to the following parts: PLA 100 parts, number average molecular weight 80,000, P3, 4HB 15 parts, 4HB content 7 mol%, di(2-ethylhexyl) adipate 10 parts, cis 0.5 parts of dibutyltin butene, 0.2 parts of ethyl phosphite, 0.2 parts of sulfhydryl di-fatty acid amide, 1 part of talc, 0.3 parts of glycerol dilaurate, and the above components were stirred in a high-speed mixer for 5 minutes. After twin-screw granulation, the single-screw extrusion blown film, the single-screw three-zone temperature settings are:

One zone: 180 V

Zone 2: 220 °C

Three zones: 210 °C

It is not possible to form a stable bubble to achieve blow molding.

Claims

Claim

1. A fully biodegradable multi-component film material comprising polylactic acid PLA, 3-hydroxybutyric acid-4-hydroxybutyric acid copolymer P3, 4HB, plasticizer, wherein polylactic acid PLA, 3-hydroxybutyrate The mass ratio of the acid-4-hydroxybutyric acid copolymer P3, 4HB and the plasticizer is 100: 5-40: 2-15, and the number average molecular weight of the polylactic acid PLA is 30,000-200,000, 3-hydroxyl The 4-hydroxybutyric acid 4HB content of the butyric acid 4-hydroxybutyric acid copolymer P3, 4HB is 5-40 mol%.

2. The fully biodegradable multicomponent film material according to claim 1, further comprising a heat resistant stabilizer, and polylactic acid PLA, 3-hydroxybutyric acid-4-hydroxybutyric acid copolymer P3, 4HB, plasticized The mass ratio of the agent and the heat resistant stabilizer is 100: 5-40: 2-15: 0.1-2.

3. The fully biodegradable multi-component film material according to claim 2, further comprising a lubricant, and polylactic acid PLA, 3-hydroxybutyric acid-4-hydroxybutyric acid copolymer P3, 4HB, a plasticizer, The mass fraction ratio of the heat resistant stabilizer to the lubricant is 100: 5-40: 2-15: 0.1-2: 0.1-2.

The fully biodegradable multicomponent film material according to claim 3, further comprising an antioxidant and a nucleating agent, and polylactic acid PLA, 3-hydroxybutyric acid-4-hydroxybutyric acid copolymer P3, 4HB , plasticizer, heat stabilizer, lubricant, antioxidant and nucleating agent mass ratio of 100: 5-40: 2-15: 0.1-2: 0.1-2: 0.1-2: 0.1-2 .

5. The fully biodegradable multi-component film material according to claim 4, further comprising an antistatic agent, and polylactic acid PLA, 3-light-based butyric acid-4-hydroxybutyric acid copolymer P3, 4HB, plasticized The mass ratio of the agent, heat stabilizer, antioxidant, lubricant, nucleating agent and antistatic agent is 100: 5-40: 2-15: 0.1-2: 0.1-2: 0.1-2: 0.1 -2: 0.1-2.

The fully biodegradable multi-component film material according to any one of claims 1 to 5, wherein the plasticizer is dioctyl phthalate, diethyl phthalate, phthalic acid Diisooctyl ester, tributyl citrate, acetyl tris(2-ethylhexyl citrate), butyl hexanoyl citrate, di(2-ethylhexyl) adipate, polyethylene glycol, One or a combination of polypropylene glycol oxalate, epoxidized soybean oil.

The fully biodegradable multi-component film material according to any one of claims 2 to 5, The heat resistant stabilizer is one or more of montmorillonite, silica, kaolin, zinc oxide, magnesium oxide, calcium stearate, succinic anhydride, maleic anhydride, and butylene oxide.

The fully biodegradable multi-component film material according to any one of claims 3 to 5, wherein the lubricant is stearic acid amide, oleic acid amide, erucic acid amide, zinc stearate, ethylene double Stearic acid amide.

The fully biodegradable multi-component film material according to claim 4 or 5, wherein the antioxidant is one of tribimonium phosphite, ethyl benzoate or bisphenol A sub-acid; The nucleating agent is one of dibenzylidene sorbitol, terephthalic acid, aluminum hydroxide, aluminum oxide, talc, and boron nitride.

The fully biodegradable multicomponent film material according to claim 5, wherein the antistatic agent is one of laurylamine, decyl sulfonate, glycerol monolaurate, and glycerol dilaurate.

11. A method of preparing the fully biodegradable multicomponent film material according to any one of claims 1 to 10, which is an extrusion blow molding, that is, the components are stirred in a high speed mixer 3-10 After a minute, it is granulated by twin-screw extrusion, and then blown into a film by a single-screw extrusion blown film unit; wherein: the temperature of the twin-screw extrusion system is set to:

One zone: 70-80 °C

Second District: 120-160. C

Three zones: 120-160 °C

Four zones: 140-180 °C

Five districts: 150-200 "C

Six districts: 150-180 °C

Seven districts: 150-170 °C

Die: 140-160 °C

The single screw extrusion blow filming temperature is set to:

One area: 140-180 °C

Zone 2: 150-200 °C

Three zones: 150-200 °C The processing parameters are as follows: Blowing ratio: 1: 2.5-1: 4 Stroke I speed - 3-6 m/min Main engine speed: 50-110 rpm.