CN110577658B - Low-shrinkage degradable plastic film and preparation method thereof - Google Patents
Low-shrinkage degradable plastic film and preparation method thereof Download PDFInfo
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- CN110577658B CN110577658B CN201910819152.7A CN201910819152A CN110577658B CN 110577658 B CN110577658 B CN 110577658B CN 201910819152 A CN201910819152 A CN 201910819152A CN 110577658 B CN110577658 B CN 110577658B
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- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 39
- 239000002985 plastic film Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 130
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 130
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000000378 calcium silicate Substances 0.000 claims abstract description 17
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 17
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000004115 Sodium Silicate Substances 0.000 claims description 19
- 159000000007 calcium salts Chemical class 0.000 claims description 19
- 239000012266 salt solution Substances 0.000 claims description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 19
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229920002678 cellulose Polymers 0.000 claims description 13
- 239000001913 cellulose Substances 0.000 claims description 13
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- 238000003490 calendering Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 241000589220 Acetobacter Species 0.000 claims description 3
- 241000589158 Agrobacterium Species 0.000 claims description 3
- 241000589180 Rhizobium Species 0.000 claims description 3
- 241000192023 Sarcina Species 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- BQRPSOKLSZSNAR-UHFFFAOYSA-N ethenyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C=C BQRPSOKLSZSNAR-UHFFFAOYSA-N 0.000 claims description 3
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 3
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 12
- 239000004033 plastic Substances 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 10
- 238000000465 moulding Methods 0.000 abstract description 5
- 229920006255 plastic film Polymers 0.000 abstract description 5
- 235000012438 extruded product Nutrition 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000835 fiber Substances 0.000 description 7
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- -1 polypropylene Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000008104 plant cellulose Substances 0.000 description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
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- 210000004911 serous fluid Anatomy 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 241001474374 Blennius Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- 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
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to the field of plastic films, and discloses a low-shrinkage degradable plastic film and a preparation method thereof. The preparation method comprises the following preparation processes: (1) preparing broken filamentous bacterial cellulose; (2) uniformly precipitating calcium silicate containing pore-forming agent on the surface of the broken filamentous bacterial cellulose to obtain modified bacterial cellulose; (3) heating the modified bacterial cellulose to prepare modified bacterial cellulose with porous surface; (4) preparing modified bacterial cellulose treated by a silane coupling agent; (5) mixing with compatilizer and matrix resin, melting, extruding, rolling and stretching to obtain the low-shrinkage degradable plastic film. In the degradable plastic film prepared by the invention, the modified filamentous bacterial cellulose is coated by the porous calcium silicate, so that the self-performance of the bacterial cellulose is effectively ensured, the dispersibility in a plastic matrix is improved, the molding shrinkage rate of an extruded product is reduced, the mechanical property of the composite film is improved, and the degradable plastic film has good biodegradability.
Description
Technical Field
The invention relates to the field of plastic films, and discloses a low-shrinkage degradable plastic film and a preparation method thereof.
Background
The plastic products generally have the defect of difficult decomposition, and particularly, the disposable plastic products are discarded at will, thus having great harm to the environment. Therefore, degradable plastic products, including degradable films, have the functions and characteristics of traditional plastics, and can be split and degraded in natural environment through the action of microorganisms in soil and water or the action of ultraviolet rays in sunlight after the service life is reached, and finally enter ecological environment again in a reduction form to return to nature, so that people pay attention to the degradable plastic products.
At present, degradable films have covered photodegradation, photobiodegradation, photooxidative biodegradation, high starch content type biodegradation, high calcium carbonate filled type photooxidative degradation, full biodegradation, and the like. Among them, a degradable film by adding a biodegradable filler is widely spotlighted for use. In recent years, the molecular structure of bacterial cellulose is similar to that of plant cellulose, has unique properties superior to those of plant cellulose, such as high tensile strength, high porosity, nanofiber-like structure and the like, and is increasingly applied as a degradable plastic filler.
The novel green environment-friendly composite material is formed by compounding the regenerated plant fiber of the bacterial cellulose and the high polymer resin through a special process, has similar performance to that of common thermoplastic plastics, is suitable for processing various plastics, and has the advantages of being green, environment-friendly, excellent in performance, safe, non-toxic and the like. Such as polypropylene, but the molding shrinkage of polypropylene articles is large; in the research of the preparation technology of degradable plastics, aiming at the condition that bacterial cellulose and plastics are incompatible materials, some technical measures have been developed at present to change the compatibility of the bacterial cellulose and the plastics, such as alkali liquor leaching, coupling, grafting modification, steam explosion and the like, and certain effect has been achieved.
The Chinese patent application No. 201510646381.5 discloses a polypropylene/bacterial cellulose composite material and a preparation method thereof, wherein the polypropylene/bacterial cellulose composite material comprises the following components in percentage by weight: 97-99.5 wt% of polypropylene homopolymer and 0.5-3 wt% of esterified modified bacterial cellulose powder. The invention also provides a preparation method of the composite material, which comprises the steps of mixing the polypropylene homopolymer and the esterified modified bacterial cellulose powder, and carrying out melt blending extrusion, belt casting, granulation and injection molding on the mixture at the temperature of 170-200 ℃ by using a double-screw extruder to obtain the composite material. According to the invention, the polypropylene homopolymer and the esterification modified bacterial cellulose powder are blended through the double-screw extruder, so that the bacterial cellulose powder can be uniformly dispersed in the polypropylene homopolymer matrix, and the mechanical property of the obtained composite material is improved.
The Chinese invention patent application No. 201710789965.7 discloses a preparation method of a bacterial cellulose/PVA biodegradable composite plastic film, which comprises the steps of fully crushing bacterial cellulose, adding a small amount of distilled water for dilution and stirring to obtain BC serous fluid, and blending the BC serous fluid with a prepared PVA aqueous solution for a period of time in a water bath at 90 ℃; and (2) putting a certain amount of starch and a small amount of distilled water into a three-neck flask, gelatinizing under the same condition, blending with the PVA system for 30min, adding a certain amount of plasticizer, continuously reacting for 45-60 min, carrying out vacuum defoaming, and carrying out tape casting on a flat plate to form a film. The bacterial cellulose/PVA composite plastic film prepared by the method has excellent mechanical properties.
According to the above, in the existing scheme, the added bacterial cellulose is used as a modification method for preparing the degradable plastic, so that inherent properties of the plastic are easily damaged, heat resistance is deteriorated, and a plastic product is easily shrunk, thereby affecting the application range of the plastic.
Disclosure of Invention
In the existing widely-applied degradable plastics, the added biomass material bacterial cellulose has the defects of poor compatibility with a resin matrix and poor heat resistance and is easy to shrink, and the conventional modification process is easy to destroy the performance of the biomass material, so that the application of the bacterial cellulose in the degradable plastics is restricted. Therefore, the invention provides a low-shrinkage degradable plastic film and a preparation method thereof, which can effectively solve the technical problems.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of a low-shrinkage degradable plastic film comprises the following specific steps:
(1) firstly, mechanically crushing bacterial cellulose into filaments, and then removing impurities to obtain crushed filamentous bacterial cellulose which is sieved by a 100-mesh sieve;
(2) firstly, spraying a sodium silicate solution and a calcium salt solution on the surface of the broken filamentous bacterial cellulose prepared in the step (1) for reaction, then spraying an aqueous dispersion of a refined naphthalene pore-forming agent in the reaction process, continuing the reaction to uniformly precipitate a layer of calcium silicate containing the pore-forming agent on the surface of the bacterial cellulose, and then performing sedimentation separation and filtration to obtain modified bacterial cellulose;
(3) heating and drying the modified bacterial cellulose prepared in the step (2), and further heating to 145-150 ℃ to sublimate the pore-forming agent to prepare modified bacterial cellulose with porous surface;
(4) fully mixing and stirring modified bacterial cellulose and a vinyl silane coupling agent to obtain modified bacterial cellulose treated by the silane coupling agent;
(5) and (3) taking maleic anhydride grafted polyethylene as a compatilizer, mixing the modified bacterial cellulose treated by the silane coupling agent obtained in the step (4) with matrix resin, then performing melt extrusion at the temperature of 160-180 ℃ through a double-screw extruder, and performing calendering and stretching through a calender to obtain the low-shrinkage degradable plastic film.
Bacterial cellulose and natural cellulose produced by plants or seaweeds have the same molecular building blocks, but bacterial cellulose fibers have many unique properties. Compared with plant cellulose, the bacterial cellulose has no associated products such as lignin, pectin, hemicellulose and the like, and has high crystallinity (up to 95 percent and 65 percent of plant cellulose) and high degree of polymerization (DP value is 2000-8000); a hyperfine network structure: the bacterial cellulose fiber is a fiber bundle with the thickness of 40-60 nanometers and is formed by combining microfibers with the diameter of 3-4 nanometers, and the fibers are mutually interwoven to form a developed hyperfine network structure; the elastic modulus of the bacterial cellulose is several times to more than ten times of that of common plant fiber, and the tensile strength is high; the bacterial cellulose has high biocompatibility, adaptability and biodegradability.
Preferably, the bacterial cellulose in the step (1) is a porous reticular nano-scale biopolymer synthesized by fermenting bacterial microorganisms, and at least one of cellulose of acetobacter, cellulose of agrobacterium, cellulose of rhizobium and cellulose of sarcina is selected.
Preferably, the mass concentration of the sodium silicate solution in the step (2) is 20-30%.
Preferably, the calcium salt solution in the step (2) is at least one of a calcium chloride solution and a calcium nitrate solution with a mass concentration of 5-10%.
Preferably, the mass concentration of the aqueous dispersion of the refined naphthalene pore-forming agent in the step (2) is 10-20%. The fine naphthalene is fine water insoluble crystal grains, is dispersed in water for convenient spraying, and is dispersed in a calcium silicate precipitation layer difficultly after final filtration so as to promote the calcium silicate to form micropores at subsequent high temperature.
Preferably, in step (2): 16-20 parts of sodium silicate solution, 22-25 parts of calcium salt solution, 38-48 parts of broken filamentous bacterial cellulose and 3-5 parts of water dispersion of refined naphthalene pore-forming agent.
Preferably, the vinyl silane coupling agent in the step (4) is at least one of vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri-tert-butoxy silane and vinyl triacetoxy silane.
Preferably, in step (4): 35-45 parts of modified bacterial cellulose and 4-6 parts of vinyl silane coupling agent.
Preferably, in step (5): 8-14 parts of maleic anhydride grafted polyethylene, 10-20 parts of modified bacterial cellulose treated by a silane coupling agent, and 66-82 parts of matrix resin. Wherein the matrix resin is selected from one of polyethylene and polypropylene.
The invention further provides a low-shrinkage degradable plastic film prepared by the method, the bacterial cellulose is crushed into threads, impurities are removed for standby, a sodium silicate solution and a calcium salt solution are sprayed and deposited on the surface of the crushed thread-shaped bacterial cellulose, an aqueous dispersion of a refined naphthalene pore-forming agent is sprayed in the reaction process, after the reaction is finished, a layer of calcium silicate containing the pore-forming agent is uniformly deposited on the surface of the bacterial cellulose, and the modified bacterial cellulose is filtered through sedimentation separation; heating and drying, and further subliming the pore-forming agent to obtain modified bacterial cellulose with porous surface; then, treating the modified bacterial cellulose by adopting a vinyl silane coupling agent; and then, mixing maleic anhydride grafted polyethylene serving as a compatilizer with matrix resin, performing melt extrusion through a double-screw extruder, and performing calendering and stretching to form a film through a calender.
The invention provides a low-shrinkage degradable plastic film and a preparation method thereof, and compared with the prior art, the low-shrinkage degradable plastic film has the outstanding characteristics and excellent effects that:
1. provides a method for preparing a low-shrinkage degradable plastic film by using porous calcium silicate coated filamentous bacterial cellulose as a raw material.
2. By adding pore-forming agent and carrying out precipitation reaction, a porous calcium silicate coating layer is formed on the surface of filamentous bacterial cellulose, the inorganic coating layer can effectively protect the bacterial cellulose, the degradation during hot processing is avoided, the performance of the bacterial cellulose is retained to the maximum extent, and meanwhile, the thermal shrinkage of the bacterial cellulose in plastic is reduced due to the protection of silicic acid fiber.
3. The filamentous bacterial cellulose coated with the porous calcium silicate is prepared, and the surface is in the calcium silicate shape, and the pores are formed on the surface, so that the bonding strength with a resin matrix can be effectively improved, and the molding shrinkage rate of an extruded product is reduced.
4. The preparation process is simple, the compatibility of the bacterial cellulose is easily modified, and the dispersibility of the bacterial cellulose in a plastic matrix is favorably improved, so that the mechanical property of the composite film is effectively improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Firstly, mechanically crushing bacterial cellulose into filaments, and then removing impurities to obtain the crushed filamentous bacterial cellulose which is sieved by a 00-mesh sieve; the bacterial cellulose is cellulose of Acetobacter;
(2) firstly, spraying a sodium silicate solution and a calcium salt solution on the surface of the broken filamentous bacterial cellulose prepared in the step (1) for reaction, then spraying an aqueous dispersion of a refined naphthalene pore-forming agent in the reaction process, continuing the reaction to uniformly precipitate a layer of calcium silicate containing the pore-forming agent on the surface of the bacterial cellulose, and then performing sedimentation separation and filtration to obtain modified bacterial cellulose; the mass concentration of the sodium silicate solution is 26 percent; the calcium salt solution is a calcium chloride solution with the mass concentration of 7 percent; the mass concentration of the water dispersion of the refined naphthalene pore-forming agent is 14 percent;
wherein: 17 parts of sodium silicate solution, 24 parts of calcium salt solution, 44 parts of broken thread-shaped bacterial cellulose and 5 parts of water dispersion of refined naphthalene pore-forming agent;
(3) heating and drying the modified bacterial cellulose prepared in the step (2), and further heating to 147 ℃ to sublimate the pore-forming agent to prepare modified bacterial cellulose with porous surface;
(4) fully mixing and stirring modified bacterial cellulose and a vinyl silane coupling agent to obtain modified bacterial cellulose treated by the silane coupling agent; the vinyl silane coupling agent is vinyl trichlorosilane;
wherein: 39 parts of modified bacterial cellulose and 5 parts of vinyl silane coupling agent;
(5) taking maleic anhydride grafted polyethylene 900E as a compatilizer, mixing the modified bacterial cellulose treated by the silane coupling agent obtained in the step (4) with LLDPE7042 matrix resin, then performing melt extrusion at 165 ℃ through a double-screw extruder, and performing calendering and stretching film forming through a four-roll calender to obtain a low-shrinkage degradable plastic film with the thickness of 0.1 mm;
wherein: 10 parts of maleic anhydride grafted polyethylene, 15 parts of modified bacterial cellulose treated by a silane coupling agent and 75 parts of LLDPE7042 matrix resin.
Example 2
(1) Firstly, mechanically crushing bacterial cellulose into filaments, and then removing impurities to obtain crushed filamentous bacterial cellulose which is sieved by a 100-mesh sieve; the bacterial cellulose is Agrobacterium cellulose;
(2) firstly, spraying a sodium silicate solution and a calcium salt solution on the surface of the broken filamentous bacterial cellulose prepared in the step (1) for reaction, then spraying an aqueous dispersion of a refined naphthalene pore-forming agent in the reaction process, continuing the reaction to uniformly precipitate a layer of calcium silicate containing the pore-forming agent on the surface of the bacterial cellulose, and then performing sedimentation separation and filtration to obtain modified bacterial cellulose; the mass concentration of the sodium silicate solution is 22 percent; the calcium salt solution is a calcium nitrate solution with the mass concentration of 6 percent; the mass concentration of the water dispersion of the refined naphthalene pore-forming agent is 12 percent;
wherein: 17 parts of sodium silicate solution, 23 parts of calcium salt solution, 45 parts of broken thread-shaped bacterial cellulose and 4 parts of water dispersion of refined naphthalene pore-forming agent;
(3) heating and drying the modified bacterial cellulose prepared in the step (2), and further heating to 146 ℃ to sublimate the pore-forming agent to prepare modified bacterial cellulose with porous surface;
(4) fully mixing and stirring modified bacterial cellulose and a vinyl silane coupling agent to obtain modified bacterial cellulose treated by the silane coupling agent; the vinyl silane coupling agent is vinyl trimethoxy silane;
wherein: 37 parts of modified bacterial cellulose and 5 parts of vinyl silane coupling agent;
(5) taking maleic anhydride grafted polyethylene as a compatilizer, mixing the modified bacterial cellulose treated by the silane coupling agent obtained in the step (4) with LLDPE7042 matrix resin, then performing melt extrusion at the temperature of 170 ℃ through a double-screw extruder, and performing calendering and stretching film forming through a four-roll calender to obtain a low-shrinkage degradable plastic film with the thickness of 0.1 mm;
wherein: 9 parts of maleic anhydride grafted polyethylene, 12 parts of modified bacterial cellulose treated by a silane coupling agent and 79 parts of LLDPE7042 matrix resin.
Example 3
(1) Firstly, mechanically crushing bacterial cellulose into filaments, and then removing impurities to obtain crushed filamentous bacterial cellulose which is sieved by a 100-mesh sieve; the bacterial cellulose is Rhizobium cellulose;
(2) firstly, spraying a sodium silicate solution and a calcium salt solution on the surface of the broken filamentous bacterial cellulose prepared in the step (1) for reaction, then spraying an aqueous dispersion of a refined naphthalene pore-forming agent in the reaction process, continuing the reaction to uniformly precipitate a layer of calcium silicate containing the pore-forming agent on the surface of the bacterial cellulose, and then performing sedimentation separation and filtration to obtain modified bacterial cellulose; the mass concentration of the sodium silicate solution is 28 percent; the calcium salt solution is a calcium chloride solution with the mass concentration of 9%; the mass concentration of the water dispersion of the refined naphthalene pore-forming agent is 18 percent;
wherein: 19 parts of sodium silicate solution, 24 parts of calcium salt solution, 41 parts of broken thread-shaped bacterial cellulose and 5 parts of water dispersion of refined naphthalene pore-forming agent;
(3) heating and drying the modified bacterial cellulose prepared in the step (2), further heating to 149 ℃, and subliming a pore-forming agent to prepare modified bacterial cellulose with porous surface;
(4) fully mixing and stirring modified bacterial cellulose and a vinyl silane coupling agent to obtain modified bacterial cellulose treated by the silane coupling agent; the vinyl silane coupling agent is vinyl triethoxysilane;
wherein: 42 parts of modified bacterial cellulose and 6 parts of vinyl silane coupling agent;
(5) taking maleic anhydride grafted polyethylene as a compatilizer, mixing the modified bacterial cellulose treated by the silane coupling agent obtained in the step (4) with LLDPE7042 matrix resin, then performing melt extrusion at 160 ℃ through a double-screw extruder, and performing calendering and stretching film forming through a four-roll calender to obtain a low-shrinkage degradable plastic film with the thickness of 0.1 mmd;
wherein: 12 parts of maleic anhydride grafted polyethylene, 17 parts of modified bacterial cellulose treated by a silane coupling agent and 71 parts of LLDPE7042 matrix resin.
Example 4
(1) Firstly, mechanically crushing bacterial cellulose into filaments, and then removing impurities to obtain crushed filamentous bacterial cellulose which is sieved by a 100-mesh sieve; the bacterial cellulose is sarcina cellulose;
(2) firstly, spraying a sodium silicate solution and a calcium salt solution on the surface of the broken filamentous bacterial cellulose prepared in the step (1) for reaction, then spraying an aqueous dispersion of a refined naphthalene pore-forming agent in the reaction process, continuing the reaction to uniformly precipitate a layer of calcium silicate containing the pore-forming agent on the surface of the bacterial cellulose, and then performing sedimentation separation and filtration to obtain modified bacterial cellulose; the mass concentration of the sodium silicate solution is 30 percent; the calcium salt solution is a calcium chloride solution with the mass concentration of 10 percent; the mass concentration of the water dispersion of the refined naphthalene pore-forming agent is 20 percent;
wherein: 20 parts of sodium silicate solution, 25 parts of calcium salt solution, 38 parts of broken thread-shaped bacterial cellulose and 3 parts of water dispersion of refined naphthalene pore-forming agent;
(3) heating and drying the modified bacterial cellulose prepared in the step (2), and further heating to 150 ℃ to sublimate the pore-forming agent to prepare modified bacterial cellulose with porous surface;
(4) fully mixing and stirring modified bacterial cellulose and a vinyl silane coupling agent to obtain modified bacterial cellulose treated by the silane coupling agent; the vinyl silane coupling agent is vinyl tri-tert-butoxy silane;
wherein: 45 parts of modified bacterial cellulose and 6 parts of vinyl silane coupling agent;
(5) taking maleic anhydride grafted polyethylene as a compatilizer, mixing the modified bacterial cellulose treated by the silane coupling agent obtained in the step (4) with LLDPE7042 matrix resin, then performing melt extrusion at 160 ℃ through a double-screw extruder, and performing calendering and stretching film forming through a calender to obtain a low-shrinkage degradable plastic film with the thickness of 0.1 mm;
wherein: 14 parts of maleic anhydride grafted polyethylene, 20 parts of modified bacterial cellulose treated by a silane coupling agent and 66 parts of LLDPE7042 matrix resin.
Comparative example 1
Comparative example 1 in which no pore-forming agent was added and no calcium silicate was coated, the same conditions as in example 4 were applied to obtain a degradable plastic film having heat resistance and heat shrinkability as shown in Table 1.
Comparative example 2
Comparative example 2 in which no pore-forming agent was added, the degradable plastic film obtained under the same conditions as in example 4 was shown in Table 1 in the heat resistance and heat shrinkability of the film.
Comparative example 3
Comparative example 3 is a plastic film with a thickness of 0.1mm, which is prepared by melt-extruding LLDPE7042 through a twin-screw extruder at a temperature of 160 ℃, calendering by a calender and stretching into a film, and is used as a blank comparative sample.
The performance index testing method comprises the following steps:
(1) heat resistance: in order to facilitate qualitative analysis test, the matrix resins of examples 1-4 and comparative examples 1-3 are all conventional film-grade resin LLDPE7042, samples of the examples and comparative examples are respectively cut by 15cm multiplied by 15cm and are tightly attached to the surface of a stainless steel plate with the thickness of 1mm, the other surface of the stainless steel is baked by an alcohol lamp until the film is wound, and the temperature of the stainless steel surface is tested to measure the heat resistance of the film.
(2) Molding shrinkage rate: the films of examples 1 to 4 and comparative examples 1 to 3 were cut into 15cm × 15cm, then stacked in groups of 10 sheets, hot-press-compounded in a 120 ℃ flat plate machine, 1 hour after the mold release, the side length of the test specimen was L1, the cavity length was L0, and the molding shrinkage was calculated according to the formula: s ═ L0-L1)/L0 × 100%.
(3) Tensile break strength is tested with reference to QB/T1040.
Table 1:
through qualitative comparison test of the film, after the bacterial cellulose is treated, the mechanical strength of the degradable plastic film prepared by the invention is close to that of a blank 7042 film, and the formed shrinkage aluminum is obviously reduced. Comparative example 1 no pore-forming agent and coated calcium silicate were added, which affected the dispersion and compatibility of the bacterial cellulose, reduced strength, poor heat resistance, and greater heat shrinkage.
Claims (10)
1. A preparation method of a low-shrinkage degradable plastic film is characterized by comprising the following specific steps:
(1) firstly, mechanically crushing bacterial cellulose into filaments, and then removing impurities to obtain crushed filamentous bacterial cellulose which is sieved by a 100-mesh sieve;
(2) firstly, spraying a sodium silicate solution and a calcium salt solution on the surface of the broken filamentous bacterial cellulose prepared in the step (1) for reaction, then spraying an aqueous dispersion of a refined naphthalene pore-forming agent in the reaction process, continuing the reaction to uniformly precipitate a layer of calcium silicate containing the pore-forming agent on the surface of the bacterial cellulose, and then performing sedimentation separation and filtration to obtain modified bacterial cellulose;
(3) heating and drying the modified bacterial cellulose prepared in the step (2), and further heating to 145-150 ℃ to sublimate the pore-forming agent to prepare modified bacterial cellulose with porous surface;
(4) fully mixing and stirring modified bacterial cellulose and a vinyl silane coupling agent to obtain modified bacterial cellulose treated by the silane coupling agent;
(5) and (3) mixing the compatilizer maleic anhydride grafted polyethylene, the modified bacterial cellulose treated by the silane coupling agent obtained in the step (4) and matrix resin, then performing melt extrusion at the temperature of 160-180 ℃ through a double-screw extruder, and performing calendering and stretching through a calender to obtain the low-shrinkage degradable plastic film.
2. The method for preparing a low-shrinkage degradable plastic film according to claim 1, wherein the method comprises the following steps: the bacterial cellulose in the step (1) is at least one of cellulose of acetobacter, cellulose of agrobacterium, cellulose of rhizobium and cellulose of sarcina.
3. The method for preparing a low-shrinkage degradable plastic film according to claim 1, wherein the method comprises the following steps: and (3) the mass concentration of the sodium silicate solution in the step (2) is 20-30%.
4. The method for preparing a low-shrinkage degradable plastic film according to claim 1, wherein the method comprises the following steps: and (3) the calcium salt solution in the step (2) is at least one of a calcium chloride solution and a calcium nitrate solution with the mass concentration of 5-10%.
5. The method for preparing a low-shrinkage degradable plastic film according to claim 1, wherein the method comprises the following steps: and (3) the mass concentration of the water dispersion of the refined naphthalene pore-forming agent in the step (2) is 10-20%.
6. The method for preparing a low-shrinkage degradable plastic film according to claim 1, wherein the method comprises the following steps: in the step (2): 16-20 parts of sodium silicate solution, 22-25 parts of calcium salt solution, 38-48 parts of broken filamentous bacterial cellulose and 3-5 parts of water dispersion of refined naphthalene pore-forming agent.
7. The method for preparing a low-shrinkage degradable plastic film according to claim 1, wherein the method comprises the following steps: the vinyl silane coupling agent in the step (4) is at least one of vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri-tert-butoxy silane and vinyl triacetoxy silane.
8. The method for preparing a low-shrinkage degradable plastic film according to claim 1, wherein the method comprises the following steps: in the step (4): 35-45 parts of modified bacterial cellulose and 4-6 parts of vinyl silane coupling agent.
9. The method for preparing a low-shrinkage degradable plastic film according to claim 1, wherein the method comprises the following steps: in the step (5): 8-14 parts of maleic anhydride grafted polyethylene, 10-20 parts of modified bacterial cellulose treated by a silane coupling agent, and 66-82 parts of matrix resin.
10. A low shrinkage degradable plastic film prepared by the method of any one of claims 1 to 9.
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