CN116535549A - Nanometer microsphere and modified polyethylene-vinyl alcohol resin and preparation method thereof - Google Patents

Nanometer microsphere and modified polyethylene-vinyl alcohol resin and preparation method thereof Download PDF

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Publication number
CN116535549A
CN116535549A CN202310624070.3A CN202310624070A CN116535549A CN 116535549 A CN116535549 A CN 116535549A CN 202310624070 A CN202310624070 A CN 202310624070A CN 116535549 A CN116535549 A CN 116535549A
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vinyl alcohol
alcohol resin
polyethylene
emulsifier
reaction
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盖婷婷
林兴旺
李羽航
许红丽
赵新新
史庆昊
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Shandong Haike Innovation Research Institute Co Ltd
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Shandong Haike Innovation Research Institute Co Ltd
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    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C08L23/0861—Saponified vinylacetate
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Abstract

The invention provides a nano microsphere, a modified polyethylene-vinyl alcohol resin and a preparation method thereof, belonging to the technical field of resin modification. The nanometer microsphere for modifying the polyethylene-vinyl alcohol resin is prepared by the following steps: 1) Mixing and heating an emulsifier and water to obtain an emulsifier aqueous solution; 2) Mixing the reaction monomer, the active hybrid and the emulsifier aqueous solution for reaction, purifying and drying after the reaction is finished to obtain the nano microsphere; the reaction monomer is hydroxyl-containing acrylic acid monomer or hydroxyl-containing acrylic acid resin; the hybrid comprises one or more of silane-containing organic matters, titanium dioxide, boron oxide, phosphorus oxide and boric acid compounds. The nano microsphere provided by the invention is directly mixed with polyethylene-vinyl alcohol for melt extrusion, the original preparation method of EVOH is not changed, and the forming processability and heat resistance can be effectively improved.

Description

Nanometer microsphere and modified polyethylene-vinyl alcohol resin and preparation method thereof
Technical Field
The invention belongs to the technical field of resin modification, and particularly relates to a nano microsphere, a modified polyethylene-vinyl alcohol resin and a preparation method thereof.
Background
Polyethylene-vinyl alcohol polymer (EVOH resin) is the resin material with the best barrier property in the current synthetic resin, and is widely applied to packaging materials and the like, and EVOH is a green environment-friendly material, does not contain nitrogen and dioxin, and has the components of carbon, oxygen and hydrogen only, and no toxic and harmful gas is generated after combustion. The worldwide demand for EVOH is still rapidly increasing, and the application range is also expanding. Generally, EVOH resins are first melt-molded into films, sheets, bottles, cups, and tubes, and then the resulting molded articles are processed for practical use. And a long time of high temperature (generally, the processing temperature is 200 ℃ to 240 ℃) must be passed during the melt forming and processing. Therefore, the moldability and heat resistance of EVOH resins are very important properties.
In the conventional technology, the coordination structure of the boric acid compound is generally changed to improve the molding processability of the EVOH resin, but the excessive addition amount of the boric acid compound or the localization of the boric acid compound can cause tiny fish eyes of the EVOH and lower the quality of molded products.
In CN1271095C, the heat resistance is improved by acid treatment of the prepared EVOH resin. However, the method has limited improvement degree, can only improve heat resistance, and has no improvement effect on forming processability.
Disclosure of Invention
The invention provides a nanometer microsphere, a modified polyethylene-vinyl alcohol resin and a preparation method, wherein the nanometer microsphere is directly mixed with polyethylene-vinyl alcohol, the original preparation method of EVOH is not changed, and the forming processability and heat resistance can be effectively improved.
In order to achieve the above purpose, the invention provides a nanoparticle for modifying polyethylene-vinyl alcohol resin, which is prepared by the following steps:
1) Mixing and heating an emulsifier and water to obtain an emulsifier aqueous solution;
2) Mixing the reaction monomer, the active hybrid and the emulsifier aqueous solution for reaction, purifying and drying after the reaction is finished to obtain the nano microsphere;
the reaction monomer is hydroxyl-containing acrylic acid monomer or hydroxyl-containing acrylic acid resin;
the active hybrid comprises one or more of silane-containing organic matters, titanium dioxide, boron oxide, phosphorus oxide and boric acid compounds.
Preferably, in step 2), the silane-containing organic matter comprises (3-mercaptopropyl trimethoxysilane, vinyl trimethoxysilane, triethoxyvinyl silane, vinyl triisopropoxysilane, methyl bis (dimethylvinylsiloxy) silane, triethoxyvinyl silane, tetramethyl dioxysilane, tetraethyl dioxysilane and tetraphenyl dioxysilane.
Preferably, in the step 1), the emulsifier comprises one or more of sodium maleic anhydride mono-hexadecyl carboxylate, sodium dodecyl sulfate, octyl phenyl polyoxyethylene ether, alkylphenol polyoxyethylene, benzoin dimethyl ether, sorbitan fatty acid ester, sorbitan monooleate polyoxyethylene, 2-acrylamide-2-tetradecyl ethyl sulfonic acid, methyl methacrylate, sodium disuccinate and peregal O-25.
Preferably, the addition amount of the active hybrid in the step 2) is 1 to 10wt% of the emulsifier aqueous solution.
Preferably, the addition amount of the reaction monomer in the step 2) is 10 to 20wt% of the aqueous solution of the emulsifier.
Preferably, in the step 2), the reaction temperature is 20-100 ℃ and the reaction time is 2-8 h.
The invention provides a modified polyethylene-vinyl alcohol resin, which is modified by adopting any one of the nano microspheres; the mass ratio of the nano microsphere to the polyethylene-vinyl alcohol resin is (0.001-1): (50-100).
Preferably, the polyethylene-vinyl alcohol resin has a molar content of ethylene units of 20% to 50%.
The invention also provides a preparation method of the modified polyethylene-vinyl alcohol resin, which comprises the following steps:
mixing the nano microspheres with polyethylene-vinyl alcohol resin, and performing extrusion molding on the obtained mixture to obtain modified polyethylene-vinyl alcohol resin;
the extrusion molding adopts three temperature areas which are sequentially arranged, and the temperature areas are respectively 70-100 ℃, 180-200 ℃ and 190-220 ℃.
Compared with the prior art, the invention has the advantages and positive effects that:
the nano microsphere provided by the invention is directly mixed with polyethylene-vinyl alcohol, the original preparation method of EVOH is not changed, and the process is simple; meanwhile, the nano microsphere provided by the invention is used for modifying EVOH, so that the consumption of boron compounds can be reduced, the generation of fish eyes can be inhibited, and the forming processability and heat resistance can be effectively improved.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a nanometer microsphere for modified polyethylene-vinyl alcohol resin, which is prepared by the following steps:
1) Mixing and heating an emulsifier and water to obtain an emulsifier aqueous solution;
2) Mixing the reaction monomer, the active hybrid and the emulsifier aqueous solution for reaction, purifying and drying after the reaction is finished to obtain the nano microsphere;
the reaction monomer is hydroxyl-containing acrylic acid monomer or hydroxyl-containing acrylic acid resin;
the active hybrid comprises one or more of silane-containing organic matters, titanium dioxide, boron oxide, phosphorus oxide and boric acid compounds.
The invention mixes and heats the emulsifier and water to obtain the emulsifier water solution. In the present invention, the emulsifier is preferably one or more of sodium maleic anhydride mono-hexadecyl carboxylate, sodium dodecyl sulfate, octyl phenyl polyoxyethylene ether, alkylphenol polyoxyethylene ether, benzoin dimethyl ether, sorbitan fatty acid ester, sorbitan monooleate polyoxyethylene ether, 2-acrylamide-2-tetradecylethyl sulfonic acid, methyl methacrylate, sodium disuccinate sulfonate and peregal O-25, more preferably sodium dodecyl sulfate, alkylphenol polyoxyethylene ether and peregal O-25. In the present invention, the emulsifier is preferably 0.05% to 0.1% by mass of water. The heating temperature is not particularly limited in the present invention, and the emulsifier may be completely dissolved.
After the aqueous solution of the emulsifier is obtained, the reaction monomer, the active hybrid and the aqueous solution of the emulsifier are mixed for reaction, and after the reaction is finished, the mixture is purified and dried to obtain the nano microsphere. In the present invention, the reaction monomer is a hydroxyl group-containing acrylic monomer or a hydroxyl group-containing acrylic resin, preferably hydroxyethyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate or n-butyl methacrylate. In the present invention, the amount of the reactive monomer added is preferably 10 to 20wt% of the aqueous emulsifier solution.
In the invention, the active hybrid comprises one or more of silane-containing organic matters, titanium dioxide, boron oxide, phosphorus oxide and boric acid compounds. The silane-containing organic preferably includes (3-mercaptopropyl trimethoxysilane, vinyl trimethoxysilane, triethoxysilane, vinyl triisopropoxysilane, methyl bis (dimethylvinylsiloxy) silane, triethoxysilane, tetramethyldioxysilane, tetraethyldioxysilane and tetraphenyldioxysilane. In the present invention, the amount of the active hybrid added is preferably 1 to 10wt% of the aqueous emulsifier solution. In the invention, the reaction temperature is 20-100 ℃ and the reaction time is 2-8 h. In the present invention, the purification method is preferably to sequentially subject the reaction solution to centrifugation, water washing and alcohol washing. In the present invention, the drying temperature is preferably 20 to 70℃and the time is preferably 3 to 8 hours.
The main chain structure of the nano microsphere prepared by the invention contains Si-O bonds, B-O bonds and the like with high bond energy, and has large molecular volume and low cohesive energy density, and the acrylic acid can increase the radiation crosslinking frequency, so that the nano microsphere has good high and low temperature resistance, weather resistance, low surface tension and the like. The advantages of the organic silicon, the borane and the acrylic resin can be effectively combined, and the resin processability and the heat resistance are better improved.
The invention provides a modified polyethylene-vinyl alcohol resin, which is modified by adopting any one of the nano microspheres; the mass ratio of the nano microsphere to the polyethylene-vinyl alcohol resin is (0.001-1): (50-100).
In the present invention, the polyethylene-vinyl alcohol resin preferably has a molar content of ethylene units of 20% to 50%. The preparation method of the polyethylene-vinyl alcohol is not particularly limited, and the polyethylene-vinyl alcohol can be prepared by adopting a conventional preparation method in the field.
The invention also provides a preparation method of the modified polyethylene-vinyl alcohol resin, which comprises the following steps:
mixing the nano microspheres with polyethylene-vinyl alcohol resin, and performing extrusion molding on the obtained mixture to obtain modified polyethylene-vinyl alcohol resin;
three temperature areas which are sequentially arranged are adopted in the extrusion molding, and the temperature areas are sequentially 70-100 ℃ and 180-200 ℃ respectively; 190-220 ℃.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
100 parts of water and 0.05 part of octyl phenyl polyoxyethylene ether are added into a four-neck flask with stirring equipment according to parts by mass, heating is carried out to 40 ℃, stirring is started, the stirring speed is set at 200rpm until the emulsifier is completely dissolved, 8 parts of vinyl trimethoxysilane and 16 parts of hydroxyethyl acrylate are dropwise added into the four-neck flask, the reaction is carried out for 2.5 hours, after standing for half an hour, centrifugation (200 rmp), water washing and ethanol washing are sequentially carried out, and drying (vacuum degree 0.1Mpa, temperature 70 ℃) is carried out in a vacuum drying oven, thus obtaining the vinyl silicone resin nano microsphere.
Putting 0.005 part of nano-microspheres and 100 parts of EVOH resin (the molar content of ethylene is 38 percent, and the mass of boron-containing compound is 100ppm based on the EVOH resin) into a stirrer, uniformly mixing, adding into a double-screw extruder, setting the temperature of three areas to be 100 ℃,190 ℃ and 210 ℃, mixing, melting for 10 minutes, extruding, shaping, and granulating in a granulator to obtain the EVOH resin modified by the nano-microspheres.
Example 2
According to the mass parts, 90 parts of water and 0.06 part of octyl phenyl polyoxyethylene ether are added into a four-neck flask provided with stirring equipment, the temperature is raised to 50 ℃, stirring is started, the stirring speed is set at 200rpm until the emulsifier is completely dissolved, 8 parts of vinyl trimethylsilane and 16 parts of hydroxyethyl acrylate are dropwise added into the four-neck flask, the mixture is reacted for 3 hours, after standing for half an hour, centrifugation (200 rmp), water washing and ethanol washing are sequentially carried out, and the mixture is dried in a vacuum drying oven (the vacuum degree is 0.1Mpa and the temperature is 70 ℃), so that the vinyl silicone resin nano microsphere is obtained.
And (3) putting 0.01 part of vinyl silicone resin nano microspheres and 100 parts of EVOH resin (the molar content of ethylene is 38 percent, and the mass of boron-containing compound is 100ppm based on the EVOH resin) into a stirrer, uniformly mixing, adding into a double-screw extruder, setting the temperature of three areas to be 100 ℃,190 ℃ and 210 ℃, mixing, melting for 10 minutes, extruding, shaping, and granulating in a granulator to obtain the EVOH resin modified by the nano microspheres.
Example 3
100 parts of water and 0.05 part of sodium dodecyl sulfate are added into a four-neck flask with stirring equipment according to parts by mass, heating is carried out to 30 ℃, stirring is started, the stirring speed is set at 500rpm until the emulsifier is completely dissolved, 20 parts of methyl methacrylate and 9 parts of (3-oleophobic) propyl trimethoxysilane are dropwise added into the four-neck flask, reaction is carried out for 4 hours, after standing for 2 hours, centrifugation (200 mp), water washing and ethanol washing are sequentially carried out, and drying (vacuum degree 0.1Mpa, temperature 70 ℃) is carried out in a vacuum drying oven, thus obtaining the methoxy silicone resin nano microsphere 1.
Mixing 0.05 part of methoxy silicone resin nanometer microsphere 1 and 100 parts of EVOH resin (the mol content of ethylene is 38 percent, and the mass of boron-containing compound is 50ppm based on EVOH resin) together in a stirrer, adding the mixture into a double-screw extruder, setting the temperature of three areas to be 100 ℃,190 ℃ and 210 ℃ respectively, mixing, melting for 10 minutes, extruding and molding, and granulating in a granulator to obtain the EVOH resin modified by the nanometer microsphere.
Example 4
90 parts of water and 0.05 part of sodium dodecyl sulfate are added into a four-neck flask provided with stirring equipment according to parts by mass, the temperature is raised to 50 ℃, stirring is started, the stirring speed is set at 200rpm until the emulsifier is completely dissolved, 6 parts of tetramethyldioxysilane and 15 parts of n-butyl acrylate are dropwise added into the four-neck flask, the mixture is reacted for 3 hours, and after standing for half an hour, centrifugation (200 rmp), water washing and ethanol washing are sequentially carried out, and drying (the vacuum degree is 0.1Mpa and the temperature is 70 ℃) in a vacuum drying oven, so that the methoxy silicone resin nanometer microsphere 2 is obtained.
Putting 0.05 part of methoxy silicone resin nano microsphere 2 and 100 parts of EVOH resin (the molar content of ethylene is 38 percent, and the mass of boron-containing compound is 100ppm based on the EVOH resin) into a stirrer, uniformly mixing, adding into a double-screw extruder, setting the temperature of three areas to be 100 ℃,190 ℃ and 210 ℃ respectively, mixing, melting for 10 minutes, extruding, shaping, and granulating in a granulator to obtain the EVOH resin modified by the nano microsphere.
Example 5
Adding 90 parts of water and 0.06 part of sodium bis (succinate) sulfonate into a four-neck flask with stirring equipment according to parts by mass, heating to 50 ℃, starting stirring, setting the stirring speed at 200rpm until the emulsifier is completely dissolved, dropwise adding 9 parts of boric acid and 15 parts of methyl methacrylate into the four-neck flask, reacting for 3 hours, standing for half an hour, sequentially centrifuging (200 mmp), washing with water and ethanol, drying in a vacuum drying oven (the vacuum degree is 0.1Mpa and the temperature is 70 ℃), and obtaining the boron oxide resin nano-microspheres.
Putting 0.05 part of boron oxide resin nano-microspheres and 100 parts of EVOH resin (the molar content of ethylene is 38 percent, and the mass of boron-containing compound is 100ppm based on the EVOH resin) into a stirrer, uniformly mixing, adding into a double-screw extruder, setting the temperature of three areas to be 100 ℃,190 ℃ and 210 ℃ respectively, mixing, melting for 10 minutes, extruding and molding, and granulating in a granulator to obtain the EVOH resin modified by the nano-microspheres.
Comparative example 1
The difference from example 1 was that the procedure was exactly the same as in example 1, except that the vinyl silicone resin nanobeads were added while the amount of the boron-containing compound of EVOH was adjusted to 300ppm at the time of preparing the EVOH resin.
Comparative example 2
The difference from example 1 was that the procedure was exactly the same as in example 1, except that the vinyl silicone resin nanobeads were added while the amount of the boron-containing compound of EVOH was adjusted to 500ppm at the time of preparing the EVOH resin.
Comparative example 3
The difference from example 1 is that no vinyltrimethylsilane was added in the preparation of the microspheres, and the specific procedure is as follows:
100 parts of water and 0.05 part of octyl phenyl polyoxyethylene ether are added into a four-neck flask with stirring equipment according to parts by mass, the temperature is raised to 40 ℃, stirring is started, the stirring speed is set at 200rpm until the emulsifier is completely dissolved, 16 parts of hydroxyethyl acrylate is dropwise added into the four-neck flask, the reaction is carried out for 2.5 hours, after standing for half an hour, centrifugation (200 rmp), water washing and ethanol washing are sequentially carried out, and the acrylic resin nano-microsphere is obtained after drying in a vacuum drying oven (the vacuum degree is 0.1Mpa and the temperature is 70 ℃).
Putting 0.005 part of nano-microspheres and 100 parts of EVOH resin (the molar content of ethylene is 38 percent, and the mass of boron-containing compound is 100ppm based on the EVOH resin) into a stirrer, uniformly mixing, adding into a double-screw extruder, setting the temperature of three areas to be 100 ℃,190 ℃ and 210 ℃, mixing, melting for 10 minutes, extruding, shaping, and granulating in a granulator to obtain the EVOH resin modified by the nano-microspheres.
Performance testing
The modified EVOH resins prepared in the above examples and comparative examples were dried in an oven for 1h, and after removal, the melt index of the materials was tested for comparison, wherein the melt index of the materials was tested according to ISO 1133 (190 ℃/2.16 g), the heat resistance of the materials was tested, 10g EVOH resins were placed on a 10 x 5 polytetrafluoroethylene petri dish, and after drying in an oven at 203 ℃ for 30 minutes, were taken out for cooling, and the yellowing index of the EVOH resins was measured for comparison, wherein the yellowing index of the materials after the heat resistance test was tested according to GB/T39822-2021. The single-layer film with the thickness of 0.03mm is prepared by film blowing, the number of crystal points in unit area is measured, when the number of crystal points is more than or equal to 30, the number of crystal points is more, when the number of crystal points is 10-30, the number of crystal points is less, when the number of crystal points is less than 10, the number of crystal points is less, and the specific test results are shown in table 1.
TABLE 1 Performance index data
It can be seen from table 1 that the nano-microspheres prepared by the present experiment improve the heat resistance of the polyethylene-vinyl alcohol resin and inhibit the generation of crystal spots (fish eyes) while reducing the amount of the boron compound.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. The nanometer microsphere for modifying the polyethylene-vinyl alcohol resin is characterized by being prepared by the following steps:
1) Mixing and heating an emulsifier and water to obtain an emulsifier aqueous solution;
2) Mixing the reaction monomer, the active hybrid and the emulsifier aqueous solution for reaction, purifying and drying after the reaction is finished to obtain the nano microsphere;
the reaction monomer is hydroxyl-containing acrylic acid monomer or hydroxyl-containing acrylic acid resin;
the active hybrid comprises one or more of silane-containing organic matters, titanium dioxide, boron oxide, phosphorus oxide and boric acid compounds.
2. The nanoparticle of claim 1, wherein in step 2) the silane-containing organic material comprises (3-mercaptopropyl trimethoxysilane, vinyl trimethoxysilane, triethoxyvinyl silane, vinyl triisopropoxysilane, methyl bis (dimethylvinylsiloxy) silane, triethoxyvinyl silane, tetramethyl dioxysilane, tetraethyl dioxysilane, and tetraphenyl dioxysilane.
3. The nanoparticle according to claim 1, wherein in step 1), the emulsifier comprises one or more of sodium maleic anhydride mono-hexadecyl carboxylate, sodium dodecyl sulfate, octyl phenyl polyoxyethylene ether, alkylphenol polyoxyethylene ether, benzoin dimethyl ether, sorbitan fatty acid ester, sorbitan monooleate polyoxyethylene ether, 2-acrylamide-2-tetradecylethyl sulfonic acid, methyl methacrylate, sodium disuccinate and peregal O-25.
4. The nanoparticle according to claim 1, wherein the amount of active hybrid added in step 2) is 1 to 10wt% of the aqueous emulsifier solution.
5. The nanoparticle according to claim 1, wherein the reactive monomer is added in step 2) in an amount of 10 to 20wt% of the aqueous emulsifier solution.
6. The nanoparticle according to claim 1, wherein in step 2), the reaction temperature is 20 to 100 ℃ for 2 to 8 hours.
7. A modified polyethylene-vinyl alcohol resin, characterized in that it is modified by the nanoparticle according to any one of claims 1 to 6; the mass ratio of the nano microsphere to the polyethylene-vinyl alcohol resin is (0.001-1): (50-100).
8. The modified polyethylene-vinyl alcohol resin of claim 7, wherein the polyethylene-vinyl alcohol resin has a molar content of ethylene units of 20% to 50%.
9. The method for producing a modified polyethylene-vinyl alcohol resin according to any one of claims 7 to 8, comprising the steps of:
mixing the nano microspheres with polyethylene-vinyl alcohol resin, and performing extrusion molding on the obtained mixture to obtain modified polyethylene-vinyl alcohol resin;
the extrusion molding adopts three temperature areas which are sequentially arranged, and the temperature areas are respectively 70-100 ℃, 180-200 ℃ and 190-220 ℃.
CN202310624070.3A 2023-05-30 2023-05-30 Nanometer microsphere and modified polyethylene-vinyl alcohol resin and preparation method thereof Pending CN116535549A (en)

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