CN113150625B - PVOH emulsion for PE coating film and preparation method thereof - Google Patents
PVOH emulsion for PE coating film and preparation method thereof Download PDFInfo
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 73
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 73
- 235000019422 polyvinyl alcohol Nutrition 0.000 title claims abstract description 73
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- 239000000839 emulsion Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 239000000080 wetting agent Substances 0.000 claims abstract description 17
- 239000008234 soft water Substances 0.000 claims abstract description 14
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- -1 dimethyl imidate Chemical compound 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000004698 Polyethylene Substances 0.000 description 36
- 238000001035 drying Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000013530 defoamer Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C08J2323/06—Polyethene
-
- 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
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a PVOH emulsion for PE coating film and a preparation method thereof, wherein the PVOH emulsion comprises the following raw materials: 70 to 80 percent of soft water, 16 to 20 percent of PVOH master batch, 2 to 8 percent of cross-linking agent, 1 to 5 percent of dispersing agent, 0.4 to 0.8 percent of wetting agent and 0.3 to 0.5 percent of defoaming agent; the polymerization degree of the PVOH master batch is 500-1000, and the alcoholysis degree is 90-99%; the cross-linking agent is dimethyl imidate and/or dimethyl diimidate. The invention adopts the compound containing the imine ester group as the cross-linking agent, and the imine ester group is cross-linked with the hydroxyl in the PVOH molecules, so that branched macromolecules of the PVOH are converted into a three-dimensional network structure, and the adhesive force of the coating to a PE film is improved. The oxygen transmission rate of the PVOH emulsion is 0.5-1.0 cc/m 2 Day, water vapor transmission rate 0.5-1.0 g/m 2 ·day。
Description
Technical Field
The invention belongs to the technical field of polyvinyl alcohol (PVOH) emulsion, and particularly relates to PVOH emulsion for a PE (polyethylene) coating film and a preparation method thereof.
Background
The PE film is a colorless and tasteless packaging material, and is widely used as an inner layer of a packaging bag for a material of a frozen packaging product due to the characteristics of excellent water vapor blocking performance, good heat sealing strength, good freezing resistance and the like. However, the PE film has poor oxygen barrier performance, and if the PE film is used in a single layer, oxygen can permeate through the PE packaging bag and enter food, so that favorable conditions are provided for the propagation and growth of bacteria, and the food is rotten and deteriorated. Therefore, in the market, high-barrier KOP or KPET is mainly used as the outer layer to be compounded with PE for use. However, in the structure, because the outer layer is made of a high-barrier material, the organic solvent contained in the composite glue of the middle layer cannot diffuse to the outer layer and can only permeate into the PE inner bag layer with poor barrier property, the quality and quality of the packing material are affected to a certain extent, and if a barrier material coated on the PE film can be developed, the application field of the PE film can be further widened.
PVOH is a polyhydroxy polymer with good water solubility and film forming properties at moderate alcoholysis levels. The oxygen barrier property of the composite material is superior to that of EVOH (ethylene-vinyl alcohol copolymer) and PVDC (polyvinylidene chloride) in a dry environment due to the action of intermolecular hydrogen bonds. However, because hydrophilic hydroxyl groups exist in the PVOH molecules, pure PVOH films easily absorb water under high humidity (relative humidity of 60% to 90%), and the barrier property to oxygen is greatly reduced or even eliminated. Therefore, in the current practical application, PVOH is generally modified to prepare water-based emulsion, and patent CN102304314A relates to a water-resistant barrier polyvinyl alcohol coating for coating and a preparation method thereof, but the solid content of the coating prepared by the method can only reach 5% -7%, in the practical application, in order to volatilize 93-95% of water, higher drying humidity is needed, the melting point of a PE film is 85-105 ℃, and the PE film can not be used due to thermal deformation before the water is completely dried.
Disclosure of Invention
In view of the above, the present invention aims to provide a PVOH emulsion for PE coating film having high adhesion to PE film and a method for preparing the same.
The invention provides a PVOH emulsion for a PE coating film, which comprises the following raw materials in percentage by mass:
70 to 80 percent of soft water, 16 to 20 percent of PVOH master batch, 2 to 8 percent of cross-linking agent, 1 to 5 percent of dispersing agent, 0.4 to 0.8 percent of wetting agent and 0.3 to 0.5 percent of defoaming agent;
the polymerization degree of the PVOH master batch is 500-1000, and the alcoholysis degree is 90-99%;
the cross-linking agent is dimethyl imino ester and/or dimethyl diimine ester.
The polymerization degree of the raw material PVOH master batch adopted in the PVOH emulsion for preparing the PE coating film is 500-1000, the alcoholysis degree is 90-99%, the solid content of the emulsion is improved to 16-20% under the action of the dispersing agent, the heat required by coating and drying the PVOH emulsion is reduced, and the problem that the PE film is deformed due to coating and drying of the common low-solid PVOH emulsion is solved.
In the present invention, the dispersant is selected from sodium polyacrylate and/or sodium hexametaphosphate.
In the present invention, the wetting agent is selected from ethanol and/or ethylene glycol. According to the invention, the wetting agent of the above kind is selected to effectively reduce the surface tension of the emulsion, improve the leveling effect of the emulsion on the PE film, form a uniform and compact coating after drying, and improve the oxygen and water vapor barrier property of the PE coating film.
In the present invention, the defoamer is selected from silicone defoamers.
In the present invention, the PVOH emulsion comprises soft water 70%, PVOH masterbatch 20%, crosslinker 6%, dispersant 3%, wetting agent 0.7% and defoamer 0.3%;
or the PVOH emulsion comprises 73% of soft water, 17% of PVOH master batch, 4% of cross-linking agent, 5% of dispersing agent, 0.5% of wetting agent and 0.5% of defoaming agent;
or the PVOH emulsion comprises 80% of soft water, 16% of PVOH masterbatch, 2% of cross linker, 1% of dispersant, 0.6% of wetting agent and 0.4% of defoamer.
In the present invention, the PVOH emulsion has an oxygen transmission rate of 0.5 to 1.0cc/m 2 Day, water vapor transmission rate of 0.5 to 1.0g/m 2 ·day；
The shrinkage rate of the film dried by the coating prepared by the PVOH emulsion is 0.2-0.5%.
The invention provides a preparation method of PVOH emulsion for PE coating film, which comprises the following steps:
mixing soft water, PVOH master batch and a dispersing agent, heating to 92-95 ℃, keeping for 3-4 h, then cooling to 65-70 ℃, and adding a cross-linking agent to carry out cross-linking reaction;
and after the crosslinking reaction is finished, adding a wetting agent and a defoaming agent, fully stirring, standing and cooling to obtain the PVOH emulsion for the PE coating film.
The PVOH emulsion is coated on a PE (polyethylene) substrate film with the thickness of 45-60 mu m, and the coating weight of the coating is 0.5-1.0 g/m 2 。
The invention provides a PVOH emulsion for a PE coating film, which comprises the following raw materials in percentage by mass: 70-80% of soft water, 16-20% of PVOH master batch, 2-8% of cross-linking agent, 1-5% of dispersing agent, 0.4-0.8% of wetting agent and 0.3-0.5% of defoaming agent; the polymerization degree of the PVOH master batch is 500-1000, and the alcoholysis degree is 90-99%; the cross-linking agent is dimethyl imino esterAnd/or dimethyl diimidate. According to the invention, a compound containing an imino ester group is used as a cross-linking agent, and the imino ester group is cross-linked with hydroxyl in PVOH molecules, so that branched macromolecules of PVOH are converted into a three-dimensional network structure, and the adhesion of a coating to a PE film is improved. The experimental results show that: the oxygen transmission rate of the PVOH emulsion is 0.5-1.0 cc/m 2 Day, water vapor transmission rate of 0.5 to 1.0g/m 2 Day; the shrinkage rate of the film dried by the coating prepared by the PVOH emulsion is 0.2-0.5%.
Detailed Description
To further illustrate the present invention, the PVOH emulsion for PE coating film and the preparation method thereof provided by the present invention are described in detail below with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
Soft water (70 wt%), PVOH masterbatch (degree of polymerization 500, degree of alcoholysis 99%) and sodium polyacrylate (3 wt%) were charged into the reactor. Starting stirring, setting the speed at 200 r/min, heating to 92 ℃ and keeping for 4 hours to completely dissolve the materials; then cooling to 65 ℃, adding 6wt% of dimethyl diimidate, preserving heat for 1 hour, after the crosslinking reaction is completed, adding 0.7wt% of wetting agent and 0.3wt% of organic silicon defoaming agent, fully stirring for 1 hour, standing, cooling to room temperature, and discharging to obtain PVOH emulsion;
coating the PVOH emulsion on a PE (polyethylene) substrate film with the thickness of 60 mu m, wherein the coating weight is 0.5g/m 2 After coating and drying, the film samples are detected for oxygen transmission rate, water vapor transmission rate, shrinkage condition and the like, and the results are shown in table 1:
TABLE 1 Performance test results for PVOH emulsions prepared in examples 1-3 and comparative examples
Example 2
73wt% of soft water, 17wt% of PVOH masterbatch (degree of polymerization 800, degree of alcoholysis 95%), 5wt% of sodium hexametaphosphate were added to the reaction vessel. Starting stirring, setting the speed at 230 r/min, heating to 93 ℃ and keeping for 3.5 hours to completely dissolve; then cooling to 67 ℃, adding 4wt% of dimethyl imino ester, preserving the heat for 1 hour, after the crosslinking reaction is completed, adding 0.5wt% of wetting agent and 0.5wt% of organic silicon defoaming agent, fully stirring for 1.5 hours, standing, cooling to room temperature, and discharging to obtain PVOH emulsion;
coating the PVOH emulsion on a PE substrate film with the thickness of 45 mu m, wherein the coating weight is 0.7g/m 2 After coating and drying, the film samples were tested for oxygen transmission rate, water vapor transmission rate, shrinkage, etc., and the results are shown in table 1.
Example 3
80wt% of soft water, 169wt% of PVOH masterbatch (degree of polymerization 1000, degree of alcoholysis 90%), 1wt% from sodium polyacrylate, was added to the reaction kettle. Starting stirring, setting the speed at 250 rpm, heating to 95 ℃ and keeping for 3 hours to completely dissolve the materials; then cooling to 70 ℃, adding 2wt% of aziridine cross-linking agent, preserving heat for 1 hour, adding 0.6wt% of wetting agent and 0.4wt% of organic silicon defoaming agent after the cross-linking reaction is completed, fully stirring for 2 hours, standing, cooling to room temperature, and discharging to obtain PVOH emulsion;
coating the PVOH emulsion on a PE substrate film with the thickness of 50 mu m, wherein the coating weight is 1.0g/m 2 After coating and drying, the film samples were tested for oxygen transmission rate, water vapor transmission rate, shrinkage, etc., and the results are shown in table 1.
Comparative example 1
Weighing 6kg of polyvinyl alcohol and 92kg of deionized water, mixing and stirring at a stirring speed of 60 revolutions per minute, heating to 98 ℃, keeping the temperature constant for 1 hour, adding 65g of organic silicon defoamer, cooling to 50 ℃, adding 10g of sodium dodecyl sulfate, then slowly dropwise adding 120g of toluene diisocyanate, heating to 60 ℃, keeping the temperature constant for 1 hour after the dropwise adding is finished, adding 30g of citric acid and 500g of methylated melamine resin again, keeping the temperature constant for 2.5 hours, fully stirring at a stirring speed of 150 revolutions per minute, cooling to room temperature, filtering and discharging.
Coating the PVOH emulsion on a PE (polyethylene) base material film with the thickness of 60 mu m, wherein the coating weight is 0.5g/m 2 After coating and drying, the film samples were tested for oxygen transmission rate, water vapor transmission rate, shrinkage, etc., and the results are shown in table 1.
Comparative example 2
73wt% of soft water, 17wt% of PVOH masterbatch (degree of polymerization 800, degree of alcoholysis 95%), 5wt% of sodium hexametaphosphate were added to the reaction vessel. Starting stirring, setting the speed at 230 r/min, heating to 93 ℃ and keeping for 3.5 hours to completely dissolve the materials; then cooling to 67 ℃, adding 4wt% aziridine, preserving the heat for 1 hour, adding 0.5wt% wetting agent and 0.5wt% organic silicon defoamer after the crosslinking reaction is completed, fully stirring for 1.5 hours, standing, cooling to room temperature, and discharging to obtain PVOH emulsion;
coating the PVOH emulsion on a PE substrate film with the thickness of 45 mu m, wherein the coating weight is 0.7g/m 2 After coating and drying, the film samples were tested for oxygen transmission rate, water vapor transmission rate, shrinkage, etc., and the results are shown in table 1.
As can be seen from the above examples, the present invention provides a PVOH emulsion for PE coating film, which comprises the following raw materials in mass fraction: 65 to 85 percent of soft water, 16 to 20 percent of PVOH master batch, 2 to 8 percent of cross-linking agent, 1 to 5 percent of dispersing agent, 0.4 to 0.8 percent of wetting agent and 0.3 to 0.5 percent of defoaming agent; the polymerization degree of the PVOH master batch is 500-1000, and the alcoholysis degree is 90-99%; the cross-linking agent is dimethyl imidate and/or dimethyl diimidate. According to the invention, a compound containing an imino ester group is used as a cross-linking agent, and the imino ester group is cross-linked with hydroxyl in PVOH molecules, so that branched macromolecules of PVOH are converted into a three-dimensional network structure, and the adhesion of a coating to a PE film is improved. The experimental results show that: the oxygen transmission rate of the PVOH emulsion is 0.5-1.0 cc/m 2 Day, water vapor transmission rate of 0.5 to 1.0g/m 2 Day; the shrinkage rate of the film dried by the coating prepared by the PVOH emulsion is 0.2-0.5%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A PVOH emulsion for PE coating film comprises the following raw materials in mass fraction:
70% of soft water, 20% of PVOH master batch, 6% of cross-linking agent, 3% of dispersing agent, 0.7% of wetting agent and 0.3% of defoaming agent;
the polymerization degree of the PVOH master batch is 500, and the alcoholysis degree is 99%;
the cross-linking agent is dimethyl diimidate;
the dispersant is selected from sodium polyacrylate;
the wetting agent is selected from ethanol and/or glycol;
the defoaming agent is selected from organic silicon defoaming agents;
the preparation method of the PVOH emulsion for the PE coating film comprises the following steps:
mixing soft water, PVOH master batch and a dispersing agent, heating to 92-95 ℃, keeping for 3-4 h, then cooling to 65-70 ℃, and adding a crosslinking agent for crosslinking reaction;
and after the crosslinking reaction is finished, adding a wetting agent and a defoaming agent, fully stirring, standing and cooling to obtain the PVOH emulsion for the PE coating film.
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| CN113717588A (en) * | 2021-09-02 | 2021-11-30 | 海南必凯水性新材料有限公司 | PVA emulsion for stone paper, preparation method and application thereof |
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| US6364987B1 (en) * | 1999-03-10 | 2002-04-02 | Kuraray Co., Ltd. | Method for producing gas barrier film |
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