CN112608500A - Method for preparing high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing - Google Patents
Method for preparing high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing Download PDFInfo
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- CN112608500A CN112608500A CN202011417994.9A CN202011417994A CN112608500A CN 112608500 A CN112608500 A CN 112608500A CN 202011417994 A CN202011417994 A CN 202011417994A CN 112608500 A CN112608500 A CN 112608500A
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- polyvinyl alcohol
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- thermoplastic processing
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 94
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000012545 processing Methods 0.000 title claims abstract description 22
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 22
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 22
- 229920000858 Cyclodextrin Polymers 0.000 claims description 24
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- 238000000071 blow moulding Methods 0.000 claims description 19
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001116 FEMA 4028 Substances 0.000 claims description 11
- 229960004853 betadex Drugs 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 11
- 239000012744 reinforcing agent Substances 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 10
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 8
- 125000002252 acyl group Chemical group 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- CUJVBAPGYBSBHJ-YWBSARSQSA-N 2-[[(1R,3R,5R,6S,8R,10R,11S,13R,15R,16S,18R,20R,21R,23R,25R,26R,28R,30R,31R,33R,35R,36R,37R,38R,39R,40R,41R,42R,43R,44R,45R,46R,47R,48R,49R)-36,38,40,42-tetrakis(carboxymethoxy)-10,15-bis(carboxymethoxymethyl)-37,39,41,43,44,45,46,47,48,49-decahydroxy-20,25,30,35-tetrakis(hydroxymethyl)-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontan-5-yl]methoxy]acetic acid Chemical compound OC[C@H]1O[C@@H]2O[C@H]3[C@H](O)[C@@H](O)[C@H](O[C@@H]3COCC(O)=O)O[C@H]3[C@H](O)[C@@H](O)[C@H](O[C@@H]3COCC(O)=O)O[C@H]3[C@H](O)[C@@H](O)[C@H](O[C@@H]3COCC(O)=O)O[C@@H]3[C@@H](CO)O[C@H](O[C@@H]4[C@@H](CO)O[C@H](O[C@@H]5[C@@H](CO)O[C@H](O[C@H]1[C@H](OCC(O)=O)[C@H]2O)[C@H](O)[C@H]5OCC(O)=O)[C@H](O)[C@H]4OCC(O)=O)[C@H](O)[C@H]3OCC(O)=O CUJVBAPGYBSBHJ-YWBSARSQSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 230000008961 swelling Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical group CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000007385 chemical modification Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- -1 allyloxy trisilane Chemical compound 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- FQNOJZPNRQOYQR-UHFFFAOYSA-N trimethyl prop-2-enyl silicate Chemical compound CO[Si](OC)(OC)OCC=C FQNOJZPNRQOYQR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 3
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MNMVKGDEKPPREK-UHFFFAOYSA-N trimethyl(prop-2-enoxy)silane Chemical compound C[Si](C)(C)OCC=C MNMVKGDEKPPREK-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
-
- 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
- C08J2351/00—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
-
- 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
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
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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 Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a method for preparing a high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing, which relates to the technical field of film materials, wherein the melting point of polyvinyl alcohol is effectively reduced by carrying out chemical modification treatment on the polyvinyl alcohol, so that the melting point of the polyvinyl alcohol is far lower than the decomposition temperature of the polyvinyl alcohol, a polyvinyl alcohol blown film is prepared by a thermoplastic processing mode, and the defect that the traditional polyvinyl alcohol film can only adopt a solution method to prepare a cast film is overcome; and the modification treatment can also keep the hydrophilicity of the polyvinyl alcohol, ensure the biodegradability of the polyvinyl alcohol and improve the comprehensive performance of the polyvinyl alcohol film, thereby widening the application range of the polyvinyl alcohol film.
Description
The technical field is as follows:
the invention relates to the technical field of film materials, in particular to a method for preparing a high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing.
Background art:
polyvinyl alcohol (PVA) is a water-soluble polymer, and features high crystallinity, strong adhesion, no poison and harm, high flexibility, high oil and solvent resistance, and high resistance to wear and gas permeation. In addition, PVA is a vinyl polymer which can be used as a carbon source and an energy source by bacteria, is degraded under the action of the bacteria and enzymes, and belongs to a biodegradable high polymer material.
The application of PVA is based on a solution method, a film material is prepared by tape casting, but solution processing and forming need to go through the dissolving and drying processes, the defects of complex process, high cost, low yield and the like exist, products with complex wall thickness and shape are difficult to prepare, and meanwhile, the PVA can not be co-extruded and blown with other materials to prepare a multilayer composite film. PVA films are typically solution processed because PVA has a melting point of about 226 ℃ and a decomposition temperature of about 200 ℃ to 250 ℃ and cannot be processed by thermoplastic processing.
The blown film is one of the plastic film forming processes, which is to melt, plasticize and extrude resin into thin-wall pipe with extruder, blow the thin-wall pipe with compressed air into required thickness under the action of drawing unit and the polymer is in good flowing state, and cool and set to form the film. Compared with other plastic film production methods, the extrusion blow molding film has the advantages of simple equipment, less investment, simple operation and low cost. In order to prepare the blow-molded PVA film, the inventor researches a preparation method of a high-performance environment-friendly PVA film through a plurality of tests, realizes thermoplastic processing of the PVA film and optimizes the comprehensive application performance of the film.
The invention content is as follows:
the invention aims to solve the technical problem of providing a method for preparing a high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing, which reduces the melting point of polyvinyl alcohol by preparing modified polyvinyl alcohol, increases the thermal stability of polyvinyl alcohol, realizes the thermoplastic processing of polyvinyl alcohol and prepares the high-performance environment-friendly polyvinyl alcohol film.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing comprises the following preparation steps:
(1) under the anhydrous condition, adding carboxymethyl-beta-cyclodextrin into tetrahydrofuran, then dropwise adding thionyl chloride, reacting at normal temperature, vacuumizing after the reaction is finished, and removing redundant thionyl chloride and tetrahydrofuran to obtain acyl chloride-beta-cyclodextrin;
(2) adding polyvinyl alcohol into the prepared acyl chloride-beta-cyclodextrin, heating for swelling, performing dehydration reaction, washing with water, performing suction filtration, and drying to obtain cyclodextrin grafted polyvinyl alcohol;
(3) adding a plasticizer and a reinforcing agent into the prepared cyclodextrin grafted polyvinyl alcohol, and uniformly mixing to obtain a premix;
(4) adding the prepared premix into a double-screw extruder, and extruding and granulating to obtain master batches;
(5) and (3) carrying out blow molding on the prepared master batch by using a blow molding machine to form a film, thus obtaining the film.
The mass ratio of the polyvinyl alcohol to the carboxymethyl-beta-cyclodextrin to the thionyl chloride is 100:30-80: 20-50.
The temperature for heating and swelling is 60-80 ℃.
The temperature of the dehydration reaction is 110-130 ℃.
The mass ratio of the cyclodextrin grafted polyvinyl alcohol to the plasticizer to the reinforcing agent is 100:10-30: 5-20.
The plasticizer is dioctyl terephthalate or dibutyl phthalate.
The reinforcing agent is white carbon black or calcium carbonate.
The temperature of the extrusion granulation is 145-175 ℃.
The temperature of the blow molding film is 140-160 ℃.
According to the invention, carboxymethyl-beta-cyclodextrin is used as a modifier, on one hand, part of hydroxyl groups in a polyvinyl alcohol structure are converted into ester groups and grafted with beta-cyclodextrin molecules, and the remaining hydroxyl groups enable the prepared/cyclodextrin grafted copolymer to still have good hydrophilicity; on the other hand, the beta-cyclodextrin also has biodegradability, so the prepared polyvinyl alcohol/cyclodextrin graft copolymer still has good biodegradability, and the melting point is reduced to about 138 ℃ which is far lower than the decomposition temperature of the polyvinyl alcohol, thereby the thermal stability of the polyvinyl alcohol is obviously improved.
Although the polyvinyl alcohol/cyclodextrin graft copolymer in the above technical scheme has good biodegradability, the plasticity and strength of beta-cyclodextrin are poor, so that the film forming property of polyvinyl alcohol can be directly influenced, and thus, a certain amount of plasticizer and reinforcing agent must be added when the film is thermoplastically processed, otherwise, the comprehensive property of the film can be directly influenced.
Aiming at the problems, the invention also selects allyloxy trimethyl silane as a modifier, and the allyloxy trimethyl silane grafted polyvinyl alcohol is prepared through graft copolymerization, so that the melting point is reduced to about 125 ℃, the plasticity and the strength of the polyvinyl alcohol can be improved, the addition amount of a plasticizer and a reinforcing agent is reduced, and the film with excellent comprehensive performance is prepared through thermoplastic processing.
The technical problem to be solved by the invention can also be realized by adopting the following technical scheme:
the method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing comprises the following preparation steps:
(1) heating and dissolving polyvinyl alcohol in water, adding allyloxy trisilane, dropwise adding alkali liquor to adjust the pH value to 7-8, then adding an initiator, heating for reaction, and performing vacuum dehydration after the reaction is finished to obtain allyloxy trisilane grafted polyvinyl alcohol;
(2) adding a plasticizer and a reinforcing agent into the prepared allyloxy trisilane grafted polyvinyl alcohol, and uniformly mixing to obtain a premix;
(3) adding the prepared premix into a double-screw extruder, and extruding and granulating to obtain master batches;
(4) and (3) carrying out blow molding on the prepared master batch by using a blow molding machine to form a film, thus obtaining the film.
The mass ratio of the polyvinyl alcohol to the allyloxy-trimethoxysilane is 100: 30-80.
The alkali liquor is sodium hydroxide solution.
The reaction temperature is 60-90 ℃.
The initiator is a water-soluble free radical initiator.
The mass ratio of the allyloxy trisilane grafted polyvinyl alcohol to the plasticizer to the reinforcing agent is 100:5-15: 1-10.
The plasticizer is dioctyl terephthalate or dibutyl phthalate.
The reinforcing agent is carbon black or white carbon black.
The temperature of the extrusion granulation was 135-165 ℃.
The temperature of the blow molding film is 130-150 ℃.
The invention has the beneficial effects that: the invention effectively reduces the melting point of the polyvinyl alcohol by carrying out chemical modification treatment on the polyvinyl alcohol, so that the melting point of the polyvinyl alcohol is far lower than the decomposition temperature of the polyvinyl alcohol, the polyvinyl alcohol blown film is prepared in a thermoplastic processing mode, and the defect that the traditional polyvinyl alcohol film can only adopt a solution method to prepare a cast film is overcome; and the modification treatment can also keep the hydrophilicity of the polyvinyl alcohol, ensure the biodegradability of the polyvinyl alcohol and improve the comprehensive performance of the polyvinyl alcohol film, thereby widening the application range of the polyvinyl alcohol film.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
The polyvinyl alcohol in the following embodiment is the cola PVA 224.
Example 1
(1) Under the anhydrous condition, adding 15g of carboxymethyl-beta-cyclodextrin into 500mL of tetrahydrofuran, then dropwise adding 10g of thionyl chloride, reacting at normal temperature for 2 hours, vacuumizing after the reaction is finished, and removing redundant thionyl chloride and tetrahydrofuran to obtain acyl chloride-beta-cyclodextrin.
(2) Adding 25g of polyvinyl alcohol into the prepared acyl chloride-beta-cyclodextrin, heating to 80 ℃, swelling for 30min, continuing to heat to 120 ℃, performing dehydration reaction for 3h, washing with water, performing suction filtration, and drying to obtain cyclodextrin grafted polyvinyl alcohol.
(3) And adding 20g of dibutyl phthalate and 15g of white carbon black into 100g of the prepared cyclodextrin grafted polyvinyl alcohol, and uniformly mixing to obtain the premix.
(4) Adding the prepared premix into a double-screw extruder, wherein the temperature of each section of a charging barrel of the double-screw extruder is 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃ and 165 ℃ in sequence, and extruding and granulating to obtain master batches.
(5) The master batch prepared above was blown into a film by a blow molding machine, and the temperature of each section of the cylinder of the blow molding machine was 145 ℃, 150 ℃, 155 ℃, 160 ℃, 155 ℃ in this order, to obtain a film having a thickness of 30 μm.
Example 2
(1) Under the anhydrous condition, 18g of carboxymethyl-beta-cyclodextrin is added into 500mL of tetrahydrofuran, 10g of thionyl chloride is added dropwise, the reaction is carried out for 2 hours at normal temperature, the reaction is finished, the vacuum is pumped, and the redundant thionyl chloride and tetrahydrofuran are removed to obtain the acyl chloride-beta-cyclodextrin.
(2) Adding 25g of polyvinyl alcohol into the prepared acyl chloride-beta-cyclodextrin, heating to 80 ℃, swelling for 30min, continuing to heat to 120 ℃, performing dehydration reaction for 3h, washing with water, performing suction filtration, and drying to obtain cyclodextrin grafted polyvinyl alcohol.
(3) And adding 20g of dibutyl phthalate and 15g of white carbon black into 100g of the prepared cyclodextrin grafted polyvinyl alcohol, and uniformly mixing to obtain the premix.
(4) Adding the prepared premix into a double-screw extruder, wherein the temperature of each section of a charging barrel of the double-screw extruder is 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃ and 165 ℃ in sequence, and extruding and granulating to obtain master batches.
(5) The master batch prepared above was blown into a film by a blow molding machine, and the temperature of each section of the cylinder of the blow molding machine was 145 ℃, 150 ℃, 155 ℃, 160 ℃, 155 ℃ in this order, to obtain a film having a thickness of 30 μm.
Example 3
(1) Heating and dissolving 25g of polyvinyl alcohol in water, adding 15g of allyloxy-trimethoxysilane, dropwise adding a sodium hydroxide solution with the concentration of 20 wt% to adjust the pH value to 7-8, then adding 0.5g of ammonium persulfate, heating to 85 ℃, reacting for 3 hours, and after the reaction is finished, carrying out vacuum dehydration to obtain the allyloxy-trimethoxysilane grafted polyvinyl alcohol.
(2) And adding 12g of dibutyl phthalate and 10g of white carbon black into 100g of the prepared allyloxy trisilane grafted polyvinyl alcohol, and uniformly mixing to obtain the premix.
(3) Adding the prepared premix into a double-screw extruder, wherein the temperature of each section of a charging barrel of the double-screw extruder is 140 ℃, 145 ℃, 150 ℃, 160 ℃, 155 ℃ and 155 ℃ in sequence, and extruding and granulating to obtain master batches.
(4) The master batch prepared above was blown into a film by a blow molding machine, and the temperature of each section of the cylinder of the blow molding machine was 135 ℃, 140 ℃, 145 ℃ and 140 ℃ in this order, to obtain a film having a thickness of 30 μm.
Example 4
(1) Heating and dissolving 25g of polyvinyl alcohol in water, adding 20g of allyloxy-trimethoxysilane, dropwise adding a sodium hydroxide solution with the concentration of 20 wt% to adjust the pH value to 7-8, then adding 0.5g of ammonium persulfate, heating to 85 ℃, reacting for 3 hours, and after the reaction is finished, carrying out vacuum dehydration to obtain the allyloxy-trimethoxysilane grafted polyvinyl alcohol.
(2) And adding 12g of dibutyl phthalate and 10g of white carbon black into 100g of the prepared allyloxy trisilane grafted polyvinyl alcohol, and uniformly mixing to obtain the premix.
(3) Adding the prepared premix into a double-screw extruder, wherein the temperature of each section of a charging barrel of the double-screw extruder is 140 ℃, 145 ℃, 150 ℃, 160 ℃, 155 ℃ and 155 ℃ in sequence, and extruding and granulating to obtain master batches.
(4) The master batch prepared above was blown into a film by a blow molding machine, and the temperature of each section of the cylinder of the blow molding machine was 135 ℃, 140 ℃, 145 ℃ and 140 ℃ in this order, to obtain a film having a thickness of 30 μm.
Comparative example 1
Comparative example 1 differs from example 4 in that allyloxytrimethylsilane is replaced with acrylic acid.
(1) Heating and dissolving 25g of polyvinyl alcohol in water, adding 20g of acrylic acid, dropwise adding a sodium hydroxide solution with the concentration of 20 wt% to adjust the pH value to 7-8, then adding 0.5g of ammonium persulfate, heating to 85 ℃ to react for 3 hours, and after the reaction is finished, performing vacuum dehydration to obtain the acrylic acid grafted polyvinyl alcohol, wherein the melting point is about 158 ℃.
(2) And adding 12g of dibutyl phthalate and 10g of white carbon black into 100g of the prepared acrylic acid grafted polyvinyl alcohol, and uniformly mixing to obtain the premix.
(3) Adding the prepared premix into a double-screw extruder, wherein the temperature of each section of a charging barrel of the double-screw extruder is 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ and 185 ℃ in sequence, and extruding and granulating to obtain master batches.
(4) The master batch prepared above is blown into a film by a blow molding machine, the temperature of each section of a charging barrel of the blow molding machine is 165 ℃, 170 ℃, 175 ℃ and 170 ℃ in sequence, and a film with the thickness of 30 μm is obtained.
Comparative example 2
Comparative example 2 is different from example 1 in that a polyvinyl alcohol film was prepared by a casting method.
Dissolving 100g of polyvinyl alcohol in hot water, adding 20g of dibutyl phthalate and 15g of white carbon black, uniformly mixing, casting to form a film, and drying at the temperature of below 70 ℃ to obtain the film with the thickness of 30 microns.
The tensile strength of the film was tested according to the national Standard GB/T13022-1991 method for testing the tensile Properties of Plastic films.
The gas permeability of the film was tested according to the pressure differential method of GB/T1038-2000 "test methods for gas permeability of Plastic films and sheets".
The light transmittance of the film is tested according to the national standard GB/T2410-.
The test results are shown in Table 1.
TABLE 1 film Performance test results
As can be seen from table 1, the examples can effectively improve the mechanical strength, gas barrier property and transmittance of the film by chemical modification treatment of polyvinyl alcohol.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing is characterized by comprising the following steps of: the preparation method comprises the following preparation steps:
(1) under the anhydrous condition, adding carboxymethyl-beta-cyclodextrin into tetrahydrofuran, then dropwise adding thionyl chloride, reacting at normal temperature, vacuumizing after the reaction is finished, and removing redundant thionyl chloride and tetrahydrofuran to obtain acyl chloride-beta-cyclodextrin;
(2) adding polyvinyl alcohol into the prepared acyl chloride-beta-cyclodextrin, heating for swelling, performing dehydration reaction, washing with water, performing suction filtration, and drying to obtain cyclodextrin grafted polyvinyl alcohol;
(3) adding a plasticizer and a reinforcing agent into the prepared cyclodextrin grafted polyvinyl alcohol, and uniformly mixing to obtain a premix;
(4) adding the prepared premix into a double-screw extruder, and extruding and granulating to obtain master batches;
(5) and (3) carrying out blow molding on the prepared master batch by using a blow molding machine to form a film, thus obtaining the film.
2. The method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing according to claim 1, characterized in that: the mass ratio of the polyvinyl alcohol to the carboxymethyl-beta-cyclodextrin to the thionyl chloride is 100:30-80: 20-50.
3. The method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing according to claim 1, characterized in that: the temperature for heating and swelling is 60-80 ℃.
4. The method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing according to claim 1, characterized in that: the temperature of the dehydration reaction is 110-130 ℃.
5. The method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing according to claim 1, characterized in that: the mass ratio of the cyclodextrin grafted polyvinyl alcohol to the plasticizer to the reinforcing agent is 100:10-30: 5-20.
6. The method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing according to claim 1, characterized in that: the plasticizer is dioctyl terephthalate or dibutyl phthalate.
7. The method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing according to claim 1, characterized in that: the reinforcing agent is white carbon black or calcium carbonate.
8. The method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing according to claim 1, characterized in that: the temperature of the extrusion granulation is 145-175 ℃.
9. The method for preparing the high-performance environment-friendly polyvinyl alcohol film by thermoplastic processing according to claim 1, characterized in that: the temperature of the blow molding film is 140-160 ℃.
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