CN114854180B - Thermoplastic cellulose/PBAT composite film and preparation method thereof - Google Patents
Thermoplastic cellulose/PBAT composite film and preparation method thereof Download PDFInfo
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- CN114854180B CN114854180B CN202210312883.4A CN202210312883A CN114854180B CN 114854180 B CN114854180 B CN 114854180B CN 202210312883 A CN202210312883 A CN 202210312883A CN 114854180 B CN114854180 B CN 114854180B
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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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- 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
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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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
- C08J2401/04—Oxycellulose; Hydrocellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention provides a thermoplastic cellulose/PBAT composite film and a preparation method thereof. The material is prepared from the following raw materials in percentage by weight: PBAT resin: 78-90%, thermoplastic cellulose: 8-18%, lubricant: 0.5-2.0%, antioxidant: 0.3-0.5% of chain extender: 0.1-1.0%, and an anti-hydrolysis agent: 0.1-0.5%, and an opening agent: 1-3.0%. The thermoplastic cellulose can be melt blended with a matrix material to realize thermoplastic processing, so that the interfacial compatibility is effectively improved, the interfacial binding force is enhanced, the good dispersion of the cellulose in a PBAT matrix is promoted, and the thermoplastic cellulose reacts with hydrophilic polar functional groups carboxyl and hydroxyl on a PBAT molecular chain to weaken the hydrophilicity, so that the problems that the ultraviolet shielding performance, the water vapor blocking performance and the mechanical performance of the PBAT composite film are difficult to balance are solved, and the comprehensive performance of the composite film is effectively optimized.
Description
Technical Field
The invention belongs to the technical field of full-biodegradation polymer materials, and particularly relates to a thermoplastic cellulose/PBAT composite film and a preparation method thereof.
Background
The full biodegradable materials have gained great attention due to the increasing shortage of petroleum resources and the huge white pollution problems brought by traditional petroleum-based plastics. The PBAT is a copolymer of Butanediol Adipate (BA) and Butanediol Terephthalate (BT), has the excellent characteristics of the polybutylene adipate (BA) and the polybutylene terephthalate (BT), has the mechanical strength equivalent to PE, has higher elongation at break and good flexibility, and has bright prospect in the fields of agriculture, food packaging, biological medicine and the like at present. However, despite the numerous potential application directions, the disadvantages of high cost, poor gas barrier, poor ultraviolet radiation resistance, poor water resistance, etc. severely limit the wide range of applications.
In recent years, in order to solve the serious pollution of the traditional plastics to the environment, and meanwhile, due to the concern of increasingly exhausting petrochemical resources and the importance of biomass resource utilization, the use of biomass modified degradable plastics becomes a current research hot spot. Cellulose is a natural organic macromolecule existing in mature cell walls of higher plants, has quite abundant sources and has the characteristics of high efficiency, ultraviolet aging resistance and high barrier. Therefore, the thermoplastic cellulose is utilized to modify the PBAT, so that the PBAT is endowed with excellent ultraviolet shielding performance and water vapor blocking performance, meanwhile, the production and manufacturing cost of the PBAT related products is effectively reduced, the high-value utilization of cellulose is realized, and the thermoplastic cellulose has important epoch-making significance for promoting the effective utilization of biomass resources and the green development of high polymer materials.
The cellulose contains a large amount of hydrogen bonds and crystal networks, so that the structure is highly compact, the chemical reactivity of the cellulose is greatly influenced, and the traditional thermoplastic processing such as extrusion, injection molding and the like is difficult to realize. Meanwhile, the cellulose is poor in compatibility with a matrix and difficult to uniformly disperse, and the cellulose is directly introduced into the PBAT matrix, so that serious phase separation is necessarily caused, and the comprehensive performance of the material is seriously damaged.
CN113248798A directly blends cellulose with PBAT and a processing aid, the problem of compatibility between cellulose and PBAT interface is not solved, and the obtained composite material has reduced elongation at break and poor toughness. The ultraviolet resistance of the composite material obtained by the CN113337013A is improved to some extent, but the whole process is complicated, the cellulose loading amount is low, and the production and manufacturing cost of the product cannot be effectively reduced. CN112552655A improves the interfacial compatibility between PBAT/PLA and industrial cellulose by adopting various strategies such as blending modified cellulose and PBAT/PLA and adding maleic anhydride grafted PBAT as a compatibilizer, and the like, and the cellulose content in the composite material prepared by the method reaches 40-60 percent, but the mechanical strength is poor, so that the composite material is difficult to be practically applied.
Disclosure of Invention
The invention aims to solve the thermoplastic processing problem of cellulose in a PBAT composite film in the prior art and overcome the problems of dispersibility, compatibility and the like of the cellulose in a PBAT matrix, and provides a thermoplastic cellulose/PBAT composite film and a preparation method thereof. The PBAT composite film has the characteristics of good ultraviolet resistance, excellent barrier, high strength and low cost.
In order to achieve the aim of the invention, the invention is realized by the following technical scheme:
the thermoplastic cellulose/PBAT composite film is prepared from the following raw materials in percentage by weight:
PBAT resin: 78-90%
Thermoplastic cellulose: 8 to 18 percent
And (3) a lubricant: 0.5 to 2.0 percent
An antioxidant: 0.3 to 0.5 percent
Chain extender: 0.1 to 1.0 percent
Hydrolysis inhibitor: 0.1 to 0.5 percent
And (3) an opening agent: 1 to 3 percent.
In the present invention, the thermoplastic cellulose is produced in supercritical carbon dioxide (ScCO) 2 ) Thermoplastic cellulose with permanently isolated hydrogen bond network structure constructed under the condition;
the preparation method of the thermoplastic cellulose comprises the following steps:
(1) Cellulose was dissolved in NaOH solution at room temperature, and the resulting milky suspension was frozen to a solid, and then thawed at room temperature, and distilled water was added while stirring to prepare a cellulose solution. Adding the cellulose solution into a coagulating bath, filtering, washing until the system is neutral, and obtaining Regenerated Cellulose (RC) through dissolution and regeneration;
wherein, the mass ratio of cellulose, naOH solution and distilled water is 1:3-10:3-10,
the mass ratio of the cellulose solution to the coagulating bath is 1:3-10;
(2) RC, plasticizer and catalyst were added to the autoclave. Before starting the reaction, CO was introduced into the reactor 2 And is released circularly to remove air therein, after which the CO is again removed 2 Pumped into a reactor, and converted into ScCO of 1-15 MPa by heating 2 Stirring is started, and the temperature of the reactor is raised to 80-140 ℃ and kept for 3-12 h. After the reaction is completed, the mechanical stirring is turned off, and the ScCO is released 2 Terminating the polymerization when the pressure in the system reaches normal pressure;
wherein, the mass ratio of RC, plasticizer and catalyst is 1:5-10:0.0004 to 0.006;
(3) Adding the product into an organic solvent, stirring for 1-3 hours, carrying out suction filtration on the obtained turbid liquid, and then washing the product to be neutral by using distilled water to obtain a primary product; and then the primary product is dried and then extracted by an organic solvent for 24-48 hours to remove a small amount of byproducts, and the purified product is dried to obtain the thermoplastic cellulose.
In the preparation method of the thermoplastic cellulose, in the step (1), the cellulose is microcrystalline cellulose, and the average particle size is 20-80 mu m;
the concentration range of the NaOH solution is preferably 9-16 wt%;
the coagulating bath is one or more of distilled water, L-lactic acid, ethanol, glycerol and dimethyl sulfoxide;
in the step (2), the plasticizer is one or more of L-lactic acid, epsilon-caprolactone, lauric acid and lactide, preferably L-lactic acid;
the catalyst is stannous octoate and/or stannous chloride;
in the step (3), the organic solvent is one or more of dichloromethane, chloroform, tetrahydrofuran and acetone.
According to the preparation method, a hydrogen bond network and a crystal structure of cellulose are temporarily split through a dissolution regeneration pretreatment method, RC with improved accessibility is used as a precursor, a flexible long chain with high reactivity is introduced to break and split a dense structure of the cellulose under the condition of supercritical carbon dioxide, and a structure for permanently isolating the hydrogen bond network is constructed, so that the molecular chain distance of the cellulose is increased, and the flow capacity of molecular chains is improved, so that the thermoplastic cellulose is prepared. On one hand, the cellulose prepared by the method can be processed with the matrix material by melt blending, so that the interface compatibility is effectively improved, the interface binding force is enhanced, and the defect of poor dispersibility of the cellulose in a PBAT matrix in a similar method is overcome; on the other hand, the thermoplastic cellulose reacts with hydrophilic polar functional groups carboxyl and hydroxyl on the PBAT molecular chain to weaken the hydrophilicity, so that the problems that the ultraviolet shielding performance, the water vapor barrier performance and the mechanical performance of the PBAT composite film are difficult to balance are solved, and the comprehensive performance of the composite film is effectively optimized.
In the invention, the molecular weight of the PBAT resin is 5-20 ten thousand, and the melt index is 2-10 g/10min (190 ℃,2.16 kg).
In the invention, the lubricant is one or more of stearic acid amine lubricant, white mineral oil and silicone oil;
the antioxidant is one or more of 1076, 1010, 618, DLTP and DSTP.
In the invention, the chain extender is one or more of epoxy chain extender, hexamethylene diisocyanate and ethylene-methyl acrylate-glycidyl methacrylate terpolymer;
the anti-hydrolysis agent is one or more of carbodiimide monomer, N' -bis (2, 6-diisopropylphenyl) carbodiimide, toluene-2, 4-diisocyanate and diphenylmethane diisocyanate;
the opening agent is one or more of erucamide, oleamide, talcum powder, diatomite and ethylene bis-stearamide.
The invention also provides a preparation method of the thermoplastic cellulose/PBAT composite film, which comprises the following steps:
(1) Optionally, drying the PBAT resin and the thermoplastic cellulose at 60-90 ℃ for 2-6 hours before use;
(2) Adding the dried PBAT resin, thermoplastic cellulose, a lubricant, an antioxidant, a chain extender, an anti-hydrolysis agent and an opening agent into a high-speed mixer according to a certain proportion, fully mixing for 5-20 min, adding the uniformly mixed materials into a double-screw extruder with the length-diameter ratio of more than or equal to 35 through a feeder, extruding and granulating in the range of 60-180 ℃, and drying the prepared granules for 1-3 hours at the temperature of 60-100 ℃;
(3) Adding the dried granules into a film extrusion blow molding machine with the length-diameter ratio of more than or equal to 25, and controlling the blowing ratio to be 1-3 within the range of 150-190 ℃:1, preparing a thermoplastic cellulose/PBAT composite film through an extrusion blow molding process; preferably, the film has a thickness of 0.006 to 0.015mm.
The invention has the beneficial effects that:
according to the invention, a certain amount of thermoplastic cellulose is added, so that the interfacial compatibility of the thermoplastic cellulose and the matrix PBAT resin is improved when the thermoplastic cellulose and the matrix PBAT resin are melt-blended, and the thermoplastic cellulose is well dispersed in the matrix, so that the effect can be better exerted; simultaneously, the stress transmission of cellulose in the polymer is promoted, the simultaneous reinforcement and toughening of the composite film are realized, and the obtained thermoplastic cellulose/PBAT composite film balances the ultraviolet shielding performance, the water vapor blocking performance and the mechanical performance and has more excellent comprehensive performance.
The invention utilizes the ultraviolet shielding and water vapor blocking effects of cellulose to adjust the degradation period of the PBAT composite film, delay the aging process, improve the weather resistance of outdoor products, and has simple preparation method and process, low cost and stable processing process, thus being very suitable for industrial production.
Detailed Description
The raw material information used in the following examples and comparative examples is:
PABT is 801T, purchased from Xinjiang blue mountain Tunche; the lubricant is amine stearate EBS, purchased from Japan flower king; antioxidants 618 and 1076, purchased from angelicas An Long; the chain extender is an epoxy ADR 4468, available from BASF, germany; the hydrolysis resistance agent is N, N' -bis (2, 6-diisopropylphenyl) carbodiimide, available from Nicotine New chemical; the opener is erucamide, available from Shanghai He Dagae chemical.
The invention will be further elucidated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the description of the invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The parts described in the examples are all parts by mass.
Example 1
Preparation of thermoplastic cellulose: 10 parts of cellulose are dissolved in 30 parts of 16% NaOH solution at room temperature, the milky suspension obtained is frozen to a solid in a refrigerator, and then taken out and placed at room temperatureThawing was performed under stirring, and 40 parts of distilled water was added to obtain a colorless transparent cellulose solution. Adding 5 parts of cellulose solution into 20 parts of ethanol, filtering, washing until the system is neutral, and obtaining RC through dissolution and regeneration; then, 0.3 part of RC, 1.5 parts of plasticizer L-lactic acid and 0.001 part of catalyst stannous octoate were added to a 100ml high-pressure stainless steel reactor, and the mixture was placed in a high-pressure reaction vessel. Before starting the reaction, CO was introduced into the reactor 2 And is released circularly to remove air therein, after which the CO is again removed 2 Pumped into a reactor, and converted into 5MPa of ScCO by heating 2 Stirring was started and the reactor was warmed to 85 ℃ and incubated for 10h. After the reaction is completed, the mechanical stirring is turned off, and the ScCO is released 2 The polymerization was terminated until the pressure in the system reached normal pressure. And then adding the product into dichloromethane, stirring for 1h, pouring the obtained turbid liquid into a glass sand funnel for suction filtration, and then washing the product to be neutral by using distilled water to obtain a primary product. And then the primary product is dried and placed in a Soxhlet extractor, dichloromethane is used as a solvent for extraction for 24 hours to remove a small amount of byproducts, and the purified product is dried to obtain the thermoplastic cellulose.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT resin: 90 percent of
Thermoplastic cellulose: 8%
EBS：0.5％
1076 and 618:0.3%
ADR 4468：0.1％
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.1%
Erucamide: 1%.
Adding the dried PBAT resin, thermoplastic cellulose, a lubricant, an antioxidant, a chain extender, an anti-hydrolysis agent and an opening agent into a high-speed mixer, fully mixing for 10min, adding the uniformly mixed materials into a double-screw extruder with the length-diameter ratio of=35 through a feeder, extruding and granulating at the temperature of 60-180 ℃, and drying the prepared granules for 3 hours at the temperature of 80 ℃;
adding the dried granules into a film extrusion blow molding machine with the length-diameter ratio of=25, and controlling the blowing ratio to be 3 within the range of 150-190 ℃:1, preparing the thermoplastic cellulose/PBAT composite film through an extrusion blow molding process, wherein the thickness of the film is 0.01mm.
Example 2
Preparation of thermoplastic cellulose: 15 parts of cellulose was dissolved in 75 parts of a 12% NaOH solution at room temperature, the resulting milky suspension was frozen in a refrigerator to a solid, and then taken out and left at room temperature for thawing, and 75 parts of distilled water was added while stirring, to prepare a colorless transparent cellulose solution. Adding 10 parts of cellulose solution into 40 parts of L-lactic acid, filtering, washing until the system is neutral, and obtaining RC through dissolution and regeneration; then, 1.5 parts of RC, 10 parts of plasticizer epsilon-caprolactone and 0.008 parts of catalyst stannous octoate were charged into a 150ml high-pressure stainless steel reactor, and then placed in a high-pressure reaction kettle. Before starting the reaction, CO was introduced into the reactor 2 And is released circularly to remove air therein, after which the CO is again removed 2 Pumped into a reactor, and converted into 5MPa of ScCO by heating 2 Stirring was started and the reactor was warmed to 100 ℃ and incubated for 6h. After the reaction is completed, the mechanical stirring is turned off, and the ScCO is released 2 The polymerization was terminated until the pressure in the system reached normal pressure. And then adding the product into dichloromethane, stirring for 2 hours, pouring the obtained turbid liquid into a glass sand funnel for suction filtration, and then washing the product to be neutral by using distilled water to obtain a primary product. And then the primary product is dried and placed in a Soxhlet extractor, dichloromethane is used as a solvent for extraction for 36 hours to remove a small amount of byproducts, and the purified product is dried to obtain the thermoplastic cellulose.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT resin: 85%
Thermoplastic cellulose: 12%
EBS：1％
1076 and 618:0.5%
ADR 4468：0.2％
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.3%
Erucamide: 1%
The preparation method is the same as in example 1.
Example 3
Thermoplastic cellulose: 20 parts of cellulose was dissolved in 90 parts of 9% NaOH solution at room temperature, the resulting milky suspension was frozen to a solid in a refrigerator, and then taken out and left at room temperature for thawing, and 120 parts of distilled water was added while stirring, to prepare a colorless transparent cellulose solution. Adding 15 parts of cellulose solution into 90 parts of L-lactic acid, filtering, washing until the system is neutral, and obtaining RC through dissolution and regeneration; then 3 parts of RC, 20 parts of plasticizer L-lactic acid and 0.004 parts of catalyst stannous octoate were added to a 200ml high pressure stainless steel reactor and placed in a high pressure reaction kettle. Before starting the reaction, CO was introduced into the reactor 2 And is released circularly to remove air therein, after which the CO is again removed 2 Pumped into a reactor, and converted into ScCO of 10MPa by heating 2 Stirring was started and the reactor was warmed to 120℃and incubated for 9h. After the reaction is completed, the mechanical stirring is turned off, and the ScCO is released 2 The polymerization was terminated until the pressure in the system reached normal pressure. And then adding the product into dichloromethane, stirring for 3 hours, pouring the obtained turbid liquid into a glass sand funnel for suction filtration, and then washing the product to be neutral by using distilled water to obtain a primary product. And then the primary product is dried and placed in a Soxhlet extractor, dichloromethane is used as a solvent for extraction for 48 hours to remove a small amount of byproducts, and the purified product is dried to obtain the thermoplastic cellulose.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT resin: 80 percent of
Thermoplastic cellulose: 15%
EBS：1.5％
1076 and 618:0.5%
ADR 4468：0.3％
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.2%
Erucamide: 2.5%.
The preparation method is the same as in example 1.
Example 4
Thermoplastic cellulose: 20 parts of cellulose was dissolved in 160 parts of a 9% NaOH solution at room temperature, the resulting milky suspension was frozen to a solid in a refrigerator, and then taken out and left at room temperature for thawing, and 180 parts of distilled water was added with stirring to prepare a colorless transparent cellulose solution. Then adding 20 parts of cellulose solution into 180 parts of L-lactic acid, filtering, washing until the system is neutral, and obtaining RC through dissolution and regeneration; then, 4.5 parts of RC, 45 parts of plasticizer L-lactic acid and 0.003 part of catalyst stannous octoate were charged into a 300ml high-pressure stainless steel reactor, and placed in a high-pressure reaction vessel. Before starting the reaction, CO was introduced into the reactor 2 And is released circularly to remove air therein, after which the CO is again removed 2 Pumped into a reactor, and converted into ScCO of 15MPa by heating 2 Stirring was started and the reactor was warmed to 140 ℃ and incubated for 5h. After the reaction is completed, the mechanical stirring is turned off, and the ScCO is released 2 The polymerization was terminated until the pressure in the system reached normal pressure. And then adding the product into dichloromethane, stirring for 3 hours, pouring the obtained turbid liquid into a glass sand funnel for suction filtration, and then washing the product to be neutral by using distilled water to obtain a primary product. And then the primary product is dried and placed in a Soxhlet extractor, dichloromethane is used as a solvent for extraction for 30 hours to remove a small amount of byproducts, and the purified product is dried to obtain the thermoplastic cellulose.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT resin: 78%
Thermoplastic cellulose: 18%
EBS：1％
1076 and 618:0.3%
ADR 4468：0.5％
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.2%
Erucamide: 2%.
The preparation method is the same as in example 1.
Comparative example 1
Thermoplastic cellulose: at room temperature, 6 parts of cellulose was dissolved in 30 parts of NaOH/urea/water=7/12/81 system, and the resulting milky suspension was frozen to a solid in a refrigerator, and after thawing, rapidly stirred to obtain a homogeneous and transparent aqueous cellulose/NaOH/urea solution. Subsequently 15 parts of cellulose/NaOH/urea aqueous solution were gelled for 3h at 60℃and the gel was repeatedly soaked with 60 parts of distilled water to neutrality. Finally, soaking the gel in liquid nitrogen, and rapidly placing the gel into a vacuum freeze dryer for drying to prepare cellulose aerogel (RCA); then 3 parts of RCA, 20 parts of plasticizer L-lactic acid and 0.004 parts of catalyst stannous octoate were added to a 200ml high pressure stainless steel reactor and placed in a high pressure reactor. Before starting the reaction, CO was introduced into the reactor 2 And is released circularly to remove air therein, after which the CO is again removed 2 Pumped into a reactor, and converted into ScCO of 10MPa by heating 2 Stirring was started and the reactor was warmed to 120℃and incubated for 9h. After the reaction is completed, the mechanical stirring is turned off, and the ScCO is released 2 The polymerization was terminated until the pressure in the system reached normal pressure. And then adding the product into dichloromethane, stirring for 3 hours, pouring the obtained turbid liquid into a glass sand funnel for suction filtration, and then washing the product to be neutral by using distilled water to obtain a primary product. And then the primary product is dried and placed in a Soxhlet extractor, dichloromethane is used as a solvent for extraction for 48 hours to remove a small amount of byproducts, and the purified product is dried to obtain the thermoplastic cellulose.
The PBAT resin and various components are prepared into special raw materials according to the following proportion (weight percentage) and the preparation method:
PBAT resin: 80 percent of
Thermoplastic cellulose: 15%
EBS：1.5％
1076 and 618:0.5%
ADR 4468：0.3％
N, N' -bis (2, 6-diisopropylphenyl) carbodiimide: 0.2%
Erucamide: 2.5%.
The preparation method is the same as in example 1.
The conventional ultraviolet shielding performance, the barrier performance and the mechanical performance of the composite mulch film are tested according to the following standards, and the results are shown in Table 1.
Artificial weathering performance: according to GB/T16422.2-2014, the irradiation mode adopts method A, and irradiance is 0.51W/(m) of narrow band (340 nm) 2 Nm), temperature control using a black mark thermometer, exposure cycle using cycle number 1, test duration 100h;
water Vapor Transmission (WVT): the test conditions were as defined in GB/T1037: the temperature is 38+/-0.6 ℃ and the relative humidity is 90+/-2%;
tensile strength: the film and sheet were tested for tensile properties according to GB/T1040.3-2006 plastics at a tensile rate of 200mm/min.
TABLE 1
From the test results of examples 1 to 4 and comparative example 1 in Table 1, it can be seen that the thermoplastic cellulose/PBAT composite film prepared by selecting the thermoplastic cellulose prepared by the invention solves the problems of thermoplastic processing of cellulose and poor dispersibility and compatibility in PBAT matrix, can reduce the water vapor transmission amount, delay the ageing degradation period of the film, improve the barrier property and ultraviolet shielding property, and effectively optimize the comprehensive performance of the composite film while improving the mechanical strength of the film.
It should be understood that the above examples of the present invention are provided for clarity of illustration only and are not intended to limit the embodiments of the present invention. Various other changes and modifications may be made by one skilled in the art in light of the above teachings, and it is not necessary or desirable to exemplify all embodiments herein. Any modification, equivalent replacement or variation which comes within the spirit and principle of the present invention shall fall within the protection scope of the claims of the present invention.
Claims (10)
1. A thermoplastic cellulose/PBAT composite film, characterized by: the material is prepared from the following raw materials in percentage by weight:
PBAT resin: 78-90%
Thermoplastic cellulose: 8-18%
And (3) a lubricant: 0.5 to 2.0%
An antioxidant: 0.3 to 0.5%
Chain extender: 0.1 to 1.0%
Hydrolysis inhibitor: 0.1 to 0.5%
And (3) an opening agent: 1-3%;
the preparation method of the thermoplastic cellulose comprises the following steps:
(1) Dissolving cellulose in NaOH solution, freezing the obtained suspension to solid, thawing, and adding water to obtain cellulose solution; the cellulose is microcrystalline cellulose, and the average particle size is 20-80 mu m;
adding the cellulose solution into a coagulating bath, filtering, and washing to be neutral to obtain regenerated cellulose RC;
(2) Adding RC, plasticizer and catalyst into high-pressure reactor, pumping CO 2 Converting into supercritical carbon dioxide with the pressure of 1-15 MPa, starting stirring, heating and preserving heat of a reactor, and then drying a product to obtain thermoplastic cellulose; the plasticizer is one or more of L-lactic acid, epsilon-caprolactone and lactide.
2. The composite film according to claim 1, wherein: in the step (1), the mass ratio of cellulose, naOH solution and water is 1:3-10:3-10.
3. The composite film according to claim 1 or 2, wherein: in the step (1), the coagulating bath is one or more of distilled water, L-lactic acid, ethanol, glycerol and dimethyl sulfoxide;
the mass ratio of the cellulose solution to the coagulating bath is 1:3-10.
4. The composite film according to claim 1, wherein: in the step (2), the catalyst is stannous octoate and/or stannous chloride;
the mass ratio of RC, plasticizer and catalyst is 1:5-10:0.0004-0.006.
5. The composite film according to claim 1, wherein: the molecular weight of the PBAT resin is 5-20 ten thousand, and the melt index is 2-10 g/10min under the conditions of 190 ℃ and 2.16 kg;
the lubricant is one or more of stearic acid amine lubricant, white mineral oil and silicone oil;
the antioxidant is one or more of 1076, 1010, 618, DLTP and DSTP.
6. The composite film according to claim 1, wherein: the chain extender is one or more of epoxy chain extender, hexamethylene diisocyanate and ethylene-methyl acrylate-glycidyl methacrylate terpolymer;
the anti-hydrolysis agent is one or more of carbodiimide monomer, N' -bis (2, 6-diisopropylphenyl) carbodiimide, toluene-2, 4-diisocyanate and diphenylmethane diisocyanate;
the opening agent is one or more of erucamide, oleamide, talcum powder, diatomite and ethylene bis-stearamide.
7. The method for producing a composite film according to any one of claims 1 to 6, comprising:
fully mixing PBAT resin, thermoplastic cellulose, a lubricant, an antioxidant, a chain extender, an anti-hydrolysis agent and an opening agent, extruding and granulating the uniformly mixed materials, and drying the prepared granules;
and extruding and blow molding the dried granules to obtain the thermoplastic cellulose/PBAT composite film.
8. The method of manufacturing according to claim 7, wherein: the thickness of the film is 0.006-0.015 mm.
9. The method of manufacturing according to claim 7, wherein: drying the PBAT resin and the thermoplastic cellulose for 2-6 hours at the temperature of 60-90 ℃ before using; the temperature of extrusion granulation is 60-180 ℃.
10. The preparation method according to any one of claims 7 to 9, characterized in that: extrusion blow molding is carried out in a film extrusion blow molding machine with the length-diameter ratio of more than or equal to 25, the temperature is 150-190 ℃, and the blow ratio is 1-3: 1.
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| US20120231165A1 (en) * | 2011-03-11 | 2012-09-13 | Nadya Belcheva | Application of Supercritical Fluid Technology for Manufacturing Soft Tissue Repair Medical Articles |
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| CN104195835A (en) * | 2014-09-18 | 2014-12-10 | 哈尔滨工业大学 | Method for grafting polymer on surface of carbon fiber under supercritical condition |
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