CN112194811A - Preparation method of PE film - Google Patents
Preparation method of PE film Download PDFInfo
- Publication number
- CN112194811A CN112194811A CN202011069796.8A CN202011069796A CN112194811A CN 112194811 A CN112194811 A CN 112194811A CN 202011069796 A CN202011069796 A CN 202011069796A CN 112194811 A CN112194811 A CN 112194811A
- Authority
- CN
- China
- Prior art keywords
- prepare
- mixture
- controlling
- polyethylene
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
-
- 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
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a preparation method of a PE film, which comprises the following raw materials in parts by weight: 50-70 parts of composite polyethylene, 15-25 parts of calcium carbonate, 10-20 parts of carbon black and 2-5 parts of plasticizer; sequentially adding composite polyethylene, calcium carbonate, carbon black and a plasticizer into a stirrer, uniformly mixing, controlling the rotation speed of the stirrer to be 450-480r/min, the temperature to be 75-85 ℃ and the stirring time to be 15min to prepare a mixture B, then transferring the mixture B into a plasticizing machine for plasticizing and mixing, performing blow molding extrusion to prepare a composite film, and then coating a waterproof coating with the thickness of 3 mu m on the surface of one side of the composite film to prepare a PE film; the maleic anhydride grafted polyethylene is prepared by mixing maleic anhydride and low density polyethylene, and then the first mixed material and the second mixed material are uniformly mixed in step S4 to prepare the composite polyethylene, and the excellent heat resistance is endowed by the mixed materials.
Description
Technical Field
The invention belongs to the technical field of PE film preparation, and particularly relates to a preparation method of a PE film.
Background
PE film, polyethylene film, refers to a film produced with PE film. The PE film has the advantages of moisture resistance and small moisture permeability, and is further widely applied to protecting products from being polluted, corroded and scratched in the production, processing, transportation, storage and use processes and protecting the original bright and clean surface, but the PE film prepared by the traditional process has poor oxidation resistance, is easy to age, has poor heat resistance and is easy to turn yellow.
The Chinese invention patent CN108276640A discloses a bidirectional easy-tearing casting PE film and a preparation method thereof, the PE film has a three-layer structure of an inner layer, a middle layer and an outer layer, and the preparation raw materials of the PE film comprise: calcium carbonate, titanium dioxide, alumina, silicon dioxide, an antioxidant, a light stabilizer, a dispersing agent, a lubricant, a tackifier, a slipping agent, a coupling agent, acetate fibers, PP, COC, m-LLDPE, nano-magnesia and HDPE; the PE film is prepared by selecting different raw materials to prepare an inner layer film forming material, a middle layer film forming material and an outer layer film forming material and then adding the film forming materials into a three-layer co-extrusion casting stretcher.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a preparation method of a PE film.
The added methyl methacrylate and the free radical on the polyethylene are subjected to free radical polymerization, and then the two processes of chlorination and grafting can be combined in the reaction process, and the added methyl methacrylate can be used as a monomer to be grafted on a polyethylene side chain to prepare an intermediate A; in the step S2, deionized water is firstly used for extraction for three times, hydrogen chloride formed by combining chlorine free radicals with hydrogen atoms on polyethylene is removed, and finally a first mixture is prepared; in the step S3, maleic anhydride and low-density polyethylene are mixed to prepare a second mixed material, the second mixed material is polyethylene grafted by maleic anhydride, then in the step S4, the first mixed material and the second mixed material are uniformly mixed to prepare composite polyethylene, and the excellent heat resistance is endowed to the composite polyethylene through the mixed material.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a PE film comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 50-70 parts of composite polyethylene, 15-25 parts of calcium carbonate, 10-20 parts of carbon black and 2-5 parts of plasticizer;
and secondly, sequentially adding the composite polyethylene, the calcium carbonate, the carbon black and the plasticizer into a stirrer to be uniformly mixed, controlling the rotating speed of the stirrer to be 450-480r/min, the temperature to be 75-85 ℃ and the stirring time to be 15min to prepare a mixture B, then transferring the mixture B into a plasticizing machine to be plasticized and mixed, performing blow molding extrusion to prepare a composite film, and then coating waterproof paint with the thickness of 3 mu m on one side surface of the composite film to prepare the PE film.
Further, the plasticizer is any one of dimethyl phthalate and diethyl phthalate.
Further, the composite polyethylene is prepared by the following method:
step S1, grinding and crushing high-density polyethylene, adding methyl methacrylate and the high-density polyethylene into a reaction kettle, uniformly mixing, introducing nitrogen to discharge oxygen, adding a separant, continuously stirring for 15min, heating to 75 ℃, heating for 10min, introducing chlorine, controlling the flow of the chlorine to be 0.5mL/S, heating to 100 ℃, exchanging air and pumping chlorine for 1h after the reaction is finished to prepare an intermediate A, and controlling the weight ratio of the high-density polyethylene to the methyl methacrylate to the separant to be 5: 2-3: 1;
step S2, adding the intermediate A prepared in the step S1 into a beaker filled with dimethylbenzene, heating in a water bath at 45 ℃ and magnetically stirring until the mixture is completely dissolved, then extracting for three times by using deionized water, precipitating and filtering the upper solution in methanol to prepare a filtrate, then drying the precipitate at 80 ℃, crushing and drying at 110 ℃ to constant weight at 100 ℃ to prepare a first mixture, wherein the weight ratio of the intermediate A to the dimethylbenzene is controlled to be 1: 2;
step S3, adding xylene and deionized water into a three-neck flask according to the weight ratio of 1: 10, then sequentially adding low-density polyethylene, maleic anhydride and benzoyl peroxide, ultrasonically swelling for 2 hours, controlling the ultrasonic power to be 50-60W, then transferring into an oil bath pan at 85-90 ℃ for magnetic stirring and reacting for 5 hours to prepare a second mixture, extracting the second mixture for 24 hours through acetone, and then drying for 4 hours at 50-60 ℃ to prepare a purified second mixture;
and S4, uniformly mixing the first mixture prepared in the step S1 and the second mixture prepared in the step S2 according to the weight ratio of 1-3: 1 to prepare the composite polyethylene.
In the step S1, methyl methacrylate and high-density polyethylene are mixed, then a separant is added to prevent the crushed high-density polyethylene from aggregating and agglomerating, then chlorine gas is introduced, the chlorine gas is decomposed into chlorine free radicals under the heating condition, the chlorine free radicals can be combined with hydrogen atoms on the polyethylene to form new free radicals on the polyethylene, the added methyl methacrylate and the free radicals on the polyethylene are subjected to free radical polymerization, and the two processes of chlorination and grafting can be combined in the reaction process, and the added methyl methacrylate can be grafted on a polyethylene side chain as a monomer to prepare an intermediate A; in the step S2, deionized water is firstly used for extraction for three times, hydrogen chloride formed by combining chlorine free radicals with hydrogen atoms on polyethylene is removed, and finally a first mixture is prepared; in the step S3, maleic anhydride and low-density polyethylene are mixed to prepare a second mixed material, the second mixed material is polyethylene grafted by maleic anhydride, then in the step S4, the first mixed material and the second mixed material are uniformly mixed to prepare composite polyethylene, and the excellent heat resistance is endowed to the composite polyethylene through the mixed material.
Further, in step S1, the isolation agent is one or two of stearic acid soap and talc powder, and is mixed according to any proportion.
Further, in step S3, the dosage ratio of the low-density polyethylene, the maleic anhydride, the benzoyl peroxide and the xylene is controlled to be 150-180 g: 30-50 g: 1-2 g: 30-50 mL.
Further, the waterproof coating is prepared by the following method:
s11, adding polyether glycol into a three-neck flask, reducing the pressure to-0.09 MPa, heating to 110-120 ℃ and vacuumizing and dehydrating for 3h at the temperature, then cooling to 30-35 ℃, dropping toluene diisocyanate, controlling the dropping time to be 30min, controlling the dropping temperature to be 35-40 ℃, heating the oil bath to 70-75 ℃ after dropping is finished, stirring at the temperature at the rotation speed of 100-120r/min and reacting for 3h, cooling and discharging after the reaction is finished, and obtaining a prepolymer C;
and step S12, adding the prepared prepolymer C into a three-neck flask, adding acetone, controlling the amount of the acetone to be one half of the mass of the prepolymer C, uniformly stirring for 30min, then adding 1, 4-butanediol while stirring, uniformly stirring for 10min, then adding stannous octoate, continuously stirring for 10min, heating to 60-65 ℃, reacting for 5h at the temperature, cooling to 30-35 ℃ after the reaction is finished, adding triethylamine, and dispersing at the rotating speed of 380 plus 400r/min for 3min to obtain the waterproof coating.
In the step S11, polyether diol and toluene diisocyanate are mixed, and by controlling the reaction conditions, the polyether diol and toluene diisocyanate react to generate an adduct with isocyanate groups at both ends, that is, the prepolymer C prepared in the step S11; in the step S12, the prepolymer C is dispersed in acetone, 1, 4-butanediol is added as a chain extender, and then a waterproof coating is prepared under the catalytic action of added stannous octoate, wherein the waterproof coating is coated on the surface of a composite film, so that on one hand, a complete coating can be formed to prevent water permeation or water molecule permeation, on the other hand, the water molecules and the coating are incompatible, the permeation of the water molecules is prevented, and the prepared PE film has excellent waterproof performance.
Further, in step S11, the weight ratio of polyether diol to toluene diisocyanate is controlled to be 2.5-2.8: 1-1.2, and in step S12, the weight ratio of prepolymer C, 1, 4-butanediol, stannous octoate and triethylamine is controlled to be 10-15: 1-1.2: 0.5-0.8: 1-2.
The invention has the beneficial effects that:
(1) the invention relates to a PE film comprising composite polyethylene and waterproof paint coated on the surface of the film, wherein in the preparation process of the composite polyethylene, in step S1, methyl methacrylate and high-density polyethylene are mixed firstly, then a separant is added to prevent the crushed high-density polyethylene from aggregating and agglomerating, then chlorine is introduced, the chlorine is decomposed into chlorine free radicals under the heating condition, the chlorine free radicals can be combined with hydrogen atoms on the polyethylene to form new free radicals on the polyethylene, the added methyl methacrylate and the free radicals on the polyethylene are subjected to free radical polymerization, and the chlorination process and the grafting process can be combined in the reaction process, and the added methyl methacrylate can be used as a monomer to be grafted on a polyethylene side chain to prepare an intermediate A; in the step S2, deionized water is firstly used for extraction for three times, hydrogen chloride formed by combining chlorine free radicals with hydrogen atoms on polyethylene is removed, and finally a first mixture is prepared; in the step S3, maleic anhydride and low-density polyethylene are mixed to prepare a second mixed material, the second mixed material is polyethylene grafted by maleic anhydride, then in the step S4, the first mixed material and the second mixed material are uniformly mixed to prepare composite polyethylene, and the excellent heat resistance is endowed to the composite polyethylene through the mixed material.
(2) The invention prepares a waterproof coating, in the preparation process, polyether diol and toluene diisocyanate are mixed in step S11, and the polyether diol and the toluene diisocyanate react to generate an addition compound with two ends containing isocyanate groups by controlling the reaction conditions, namely a prepolymer C prepared in step S11; in the step S12, the prepolymer C is dispersed in acetone, 1, 4-butanediol is added as a chain extender, and then a waterproof coating is prepared under the catalytic action of added stannous octoate, wherein the waterproof coating is coated on the surface of a composite film, so that on one hand, a complete coating can be formed to prevent water permeation or water molecule permeation, on the other hand, the water molecules and the coating are incompatible, the permeation of the water molecules is prevented, and the prepared PE film has excellent waterproof performance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a PE film comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 50 parts of composite polyethylene, 15 parts of calcium carbonate, 10 parts of carbon black and 2 parts of dimethyl phthalate;
and secondly, sequentially adding the composite polyethylene, the calcium carbonate, the carbon black and the dimethyl phthalate into a stirrer to be uniformly mixed, controlling the rotating speed of the stirrer to be 450r/min, the temperature to be 75 ℃ and the stirring time to be 15min to prepare a mixture B, then transferring the mixture B into a plasticizing machine to be plasticized and mixed, performing blow molding extrusion to prepare a composite film, and then coating waterproof paint with the thickness of 3 mu m on the surface of one side of the composite film to prepare the PE film.
The composite polyethylene is prepared by the following method:
step S1, grinding and crushing high-density polyethylene, adding methyl methacrylate and the high-density polyethylene into a reaction kettle, uniformly mixing, introducing nitrogen to discharge oxygen, adding stearic acid soap, continuously stirring for 15min, heating to 75 ℃, heating for 10min, passing chlorine, controlling the flow of the chlorine to be 0.5mL/S, heating to 100 ℃, ventilating and pumping chlorine for 1h after the reaction is finished to prepare an intermediate A, and controlling the weight ratio of the high-density polyethylene to the methyl methacrylate to the stearic acid soap to be 5: 2: 1;
step S2, adding the intermediate A prepared in the step S1 into a beaker filled with dimethylbenzene, heating in a water bath at 45 ℃ and magnetically stirring until the mixture is completely dissolved, extracting for three times by using deionized water, precipitating and filtering an upper layer solution in methanol to prepare a filtrate, drying the precipitate at 80 ℃, crushing and drying at 100 ℃ to constant weight to prepare a first mixture, wherein the weight ratio of the intermediate A to the dimethylbenzene is controlled to be 1: 2;
step S3, adding xylene and deionized water into a three-neck flask according to the weight ratio of 1: 10, then sequentially adding low-density polyethylene, maleic anhydride and benzoyl peroxide, ultrasonically swelling for 2 hours, controlling the ultrasonic power to be 50W, then transferring the mixture into an oil bath kettle at 85 ℃, magnetically stirring and reacting for 5 hours to prepare a second mixture, extracting the second mixture for 24 hours through acetone, then drying for 4 hours at 50 ℃ to prepare a purified second mixture, and controlling the dosage ratio of the low-density polyethylene, the maleic anhydride, the benzoyl peroxide and the xylene to be 150 g: 30 g: 1 g: 30 mL;
and S4, uniformly mixing the first mixture prepared in the step S1 and the second mixture prepared in the step S2 according to the weight ratio of 1: 1 to prepare the composite polyethylene.
The waterproof coating is prepared by the following method:
step S11, adding polyether glycol into a three-neck flask, reducing the pressure to-0.09 MPa, heating to 110 ℃, vacuumizing and dehydrating for 3h at the temperature, then cooling to 30 ℃, dropping toluene diisocyanate, controlling the dropping time to be 30min, controlling the temperature during dropping to be 35 ℃, heating to 70 ℃ in an oil bath after dropping, stirring at the speed of 100r/min at the temperature, reacting for 3h, cooling and discharging after the reaction is finished to obtain a prepolymer C, and controlling the weight ratio of the polyether glycol to the toluene diisocyanate to be 2.5: 1;
step S12, adding the prepared prepolymer C into a three-neck flask, adding acetone, controlling the amount of acetone to be one half of the mass of the prepolymer C, stirring at a constant speed for 30min, then adding 1, 4-butanediol while stirring, stirring at a constant speed for 10min, then adding stannous octoate, continuing stirring for 10min, heating to 60 ℃, reacting for 5h at the temperature, cooling to 30 ℃ after the reaction is finished, adding triethylamine, dispersing for 3min at a rotating speed of 380r/min to prepare the waterproof coating, and controlling the weight ratio of the prepolymer C, the 1, 4-butanediol, the stannous octoate and the triethylamine to be 10: 1: 0.5: 1.
Example 2
A preparation method of a PE film comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 55 parts of composite polyethylene, 18 parts of calcium carbonate, 12 parts of carbon black and 3 parts of dimethyl phthalate;
and secondly, sequentially adding the composite polyethylene, the calcium carbonate, the carbon black and the dimethyl phthalate into a stirrer to be uniformly mixed, controlling the rotating speed of the stirrer to be 450r/min, the temperature to be 75 ℃ and the stirring time to be 15min to prepare a mixture B, then transferring the mixture B into a plasticizing machine to be plasticized and mixed, performing blow molding extrusion to prepare a composite film, and then coating waterproof paint with the thickness of 3 mu m on the surface of one side of the composite film to prepare the PE film.
The composite polyethylene is prepared by the following method:
step S1, grinding and crushing high-density polyethylene, adding methyl methacrylate and the high-density polyethylene into a reaction kettle, uniformly mixing, introducing nitrogen to discharge oxygen, adding stearic acid soap, continuously stirring for 15min, heating to 75 ℃, heating for 10min, passing chlorine, controlling the flow of the chlorine to be 0.5mL/S, heating to 100 ℃, ventilating and pumping chlorine for 1h after the reaction is finished to prepare an intermediate A, and controlling the weight ratio of the high-density polyethylene to the methyl methacrylate to the stearic acid soap to be 5: 2: 1;
step S2, adding the intermediate A prepared in the step S1 into a beaker filled with dimethylbenzene, heating in a water bath at 45 ℃ and magnetically stirring until the mixture is completely dissolved, extracting for three times by using deionized water, precipitating and filtering an upper layer solution in methanol to prepare a filtrate, drying the precipitate at 80 ℃, crushing and drying at 100 ℃ to constant weight to prepare a first mixture, wherein the weight ratio of the intermediate A to the dimethylbenzene is controlled to be 1: 2;
step S3, adding xylene and deionized water into a three-neck flask according to the weight ratio of 1: 10, then sequentially adding low-density polyethylene, maleic anhydride and benzoyl peroxide, ultrasonically swelling for 2 hours, controlling the ultrasonic power to be 50W, then transferring the mixture into an oil bath kettle at 85 ℃, magnetically stirring and reacting for 5 hours to prepare a second mixture, extracting the second mixture for 24 hours through acetone, then drying for 4 hours at 50 ℃ to prepare a purified second mixture, and controlling the dosage ratio of the low-density polyethylene, the maleic anhydride, the benzoyl peroxide and the xylene to be 150 g: 30 g: 1 g: 30 mL;
and S4, uniformly mixing the first mixture prepared in the step S1 and the second mixture prepared in the step S2 according to the weight ratio of 1: 1 to prepare the composite polyethylene.
The waterproof coating is prepared by the following method:
step S11, adding polyether glycol into a three-neck flask, reducing the pressure to-0.09 MPa, heating to 110 ℃, vacuumizing and dehydrating for 3h at the temperature, then cooling to 30 ℃, dropping toluene diisocyanate, controlling the dropping time to be 30min, controlling the temperature during dropping to be 35 ℃, heating to 70 ℃ in an oil bath after dropping, stirring at the speed of 100r/min at the temperature, reacting for 3h, cooling and discharging after the reaction is finished to obtain a prepolymer C, and controlling the weight ratio of the polyether glycol to the toluene diisocyanate to be 2.5: 1;
step S12, adding the prepared prepolymer C into a three-neck flask, adding acetone, controlling the amount of acetone to be one half of the mass of the prepolymer C, stirring at a constant speed for 30min, then adding 1, 4-butanediol while stirring, stirring at a constant speed for 10min, then adding stannous octoate, continuing stirring for 10min, heating to 60 ℃, reacting for 5h at the temperature, cooling to 30 ℃ after the reaction is finished, adding triethylamine, dispersing for 3min at a rotating speed of 380r/min to prepare the waterproof coating, and controlling the weight ratio of the prepolymer C, the 1, 4-butanediol, the stannous octoate and the triethylamine to be 10: 1: 0.5: 1.
Example 3
A preparation method of a PE film comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 65 parts of composite polyethylene, 22 parts of calcium carbonate, 15 parts of carbon black and 4 parts of dimethyl phthalate;
and secondly, sequentially adding the composite polyethylene, the calcium carbonate, the carbon black and the dimethyl phthalate into a stirrer to be uniformly mixed, controlling the rotating speed of the stirrer to be 450r/min, the temperature to be 75 ℃ and the stirring time to be 15min to prepare a mixture B, then transferring the mixture B into a plasticizing machine to be plasticized and mixed, performing blow molding extrusion to prepare a composite film, and then coating waterproof paint with the thickness of 3 mu m on the surface of one side of the composite film to prepare the PE film.
The composite polyethylene is prepared by the following method:
step S1, grinding and crushing high-density polyethylene, adding methyl methacrylate and the high-density polyethylene into a reaction kettle, uniformly mixing, introducing nitrogen to discharge oxygen, adding stearic acid soap, continuously stirring for 15min, heating to 75 ℃, heating for 10min, passing chlorine, controlling the flow of the chlorine to be 0.5mL/S, heating to 100 ℃, ventilating and pumping chlorine for 1h after the reaction is finished to prepare an intermediate A, and controlling the weight ratio of the high-density polyethylene to the methyl methacrylate to the stearic acid soap to be 5: 2: 1;
step S2, adding the intermediate A prepared in the step S1 into a beaker filled with dimethylbenzene, heating in a water bath at 45 ℃ and magnetically stirring until the mixture is completely dissolved, extracting for three times by using deionized water, precipitating and filtering an upper layer solution in methanol to prepare a filtrate, drying the precipitate at 80 ℃, crushing and drying at 100 ℃ to constant weight to prepare a first mixture, wherein the weight ratio of the intermediate A to the dimethylbenzene is controlled to be 1: 2;
step S3, adding xylene and deionized water into a three-neck flask according to the weight ratio of 1: 10, then sequentially adding low-density polyethylene, maleic anhydride and benzoyl peroxide, ultrasonically swelling for 2 hours, controlling the ultrasonic power to be 50W, then transferring the mixture into an oil bath kettle at 85 ℃, magnetically stirring and reacting for 5 hours to prepare a second mixture, extracting the second mixture for 24 hours through acetone, then drying for 4 hours at 50 ℃ to prepare a purified second mixture, and controlling the dosage ratio of the low-density polyethylene, the maleic anhydride, the benzoyl peroxide and the xylene to be 150 g: 30 g: 1 g: 30 mL;
and S4, uniformly mixing the first mixture prepared in the step S1 and the second mixture prepared in the step S2 according to the weight ratio of 1: 1 to prepare the composite polyethylene.
The waterproof coating is prepared by the following method:
step S11, adding polyether glycol into a three-neck flask, reducing the pressure to-0.09 MPa, heating to 110 ℃, vacuumizing and dehydrating for 3h at the temperature, then cooling to 30 ℃, dropping toluene diisocyanate, controlling the dropping time to be 30min, controlling the temperature during dropping to be 35 ℃, heating to 70 ℃ in an oil bath after dropping, stirring at the speed of 100r/min at the temperature, reacting for 3h, cooling and discharging after the reaction is finished to obtain a prepolymer C, and controlling the weight ratio of the polyether glycol to the toluene diisocyanate to be 2.5: 1;
step S12, adding the prepared prepolymer C into a three-neck flask, adding acetone, controlling the amount of acetone to be one half of the mass of the prepolymer C, stirring at a constant speed for 30min, then adding 1, 4-butanediol while stirring, stirring at a constant speed for 10min, then adding stannous octoate, continuing stirring for 10min, heating to 60 ℃, reacting for 5h at the temperature, cooling to 30 ℃ after the reaction is finished, adding triethylamine, dispersing for 3min at a rotating speed of 380r/min to prepare the waterproof coating, and controlling the weight ratio of the prepolymer C, the 1, 4-butanediol, the stannous octoate and the triethylamine to be 10: 1: 0.5: 1.
Example 4
A preparation method of a PE film comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 70 parts of composite polyethylene, 25 parts of calcium carbonate, 20 parts of carbon black and 5 parts of dimethyl phthalate;
and secondly, sequentially adding the composite polyethylene, the calcium carbonate, the carbon black and the dimethyl phthalate into a stirrer to be uniformly mixed, controlling the rotating speed of the stirrer to be 450r/min, the temperature to be 75 ℃ and the stirring time to be 15min to prepare a mixture B, then transferring the mixture B into a plasticizing machine to be plasticized and mixed, performing blow molding extrusion to prepare a composite film, and then coating waterproof paint with the thickness of 3 mu m on the surface of one side of the composite film to prepare the PE film.
The composite polyethylene is prepared by the following method:
step S1, grinding and crushing high-density polyethylene, adding methyl methacrylate and the high-density polyethylene into a reaction kettle, uniformly mixing, introducing nitrogen to discharge oxygen, adding stearic acid soap, continuously stirring for 15min, heating to 75 ℃, heating for 10min, passing chlorine, controlling the flow of the chlorine to be 0.5mL/S, heating to 100 ℃, ventilating and pumping chlorine for 1h after the reaction is finished to prepare an intermediate A, and controlling the weight ratio of the high-density polyethylene to the methyl methacrylate to the stearic acid soap to be 5: 2: 1;
step S2, adding the intermediate A prepared in the step S1 into a beaker filled with dimethylbenzene, heating in a water bath at 45 ℃ and magnetically stirring until the mixture is completely dissolved, extracting for three times by using deionized water, precipitating and filtering an upper layer solution in methanol to prepare a filtrate, drying the precipitate at 80 ℃, crushing and drying at 100 ℃ to constant weight to prepare a first mixture, wherein the weight ratio of the intermediate A to the dimethylbenzene is controlled to be 1: 2;
step S3, adding xylene and deionized water into a three-neck flask according to the weight ratio of 1: 10, then sequentially adding low-density polyethylene, maleic anhydride and benzoyl peroxide, ultrasonically swelling for 2 hours, controlling the ultrasonic power to be 50W, then transferring the mixture into an oil bath kettle at 85 ℃, magnetically stirring and reacting for 5 hours to prepare a second mixture, extracting the second mixture for 24 hours through acetone, then drying for 4 hours at 50 ℃ to prepare a purified second mixture, and controlling the dosage ratio of the low-density polyethylene, the maleic anhydride, the benzoyl peroxide and the xylene to be 150 g: 30 g: 1 g: 30 mL;
and S4, uniformly mixing the first mixture prepared in the step S1 and the second mixture prepared in the step S2 according to the weight ratio of 1: 1 to prepare the composite polyethylene.
The waterproof coating is prepared by the following method:
step S11, adding polyether glycol into a three-neck flask, reducing the pressure to-0.09 MPa, heating to 110 ℃, vacuumizing and dehydrating for 3h at the temperature, then cooling to 30 ℃, dropping toluene diisocyanate, controlling the dropping time to be 30min, controlling the temperature during dropping to be 35 ℃, heating to 70 ℃ in an oil bath after dropping, stirring at the speed of 100r/min at the temperature, reacting for 3h, cooling and discharging after the reaction is finished to obtain a prepolymer C, and controlling the weight ratio of the polyether glycol to the toluene diisocyanate to be 2.5: 1;
step S12, adding the prepared prepolymer C into a three-neck flask, adding acetone, controlling the amount of acetone to be one half of the mass of the prepolymer C, stirring at a constant speed for 30min, then adding 1, 4-butanediol while stirring, stirring at a constant speed for 10min, then adding stannous octoate, continuing stirring for 10min, heating to 60 ℃, reacting for 5h at the temperature, cooling to 30 ℃ after the reaction is finished, adding triethylamine, dispersing for 3min at a rotating speed of 380r/min to prepare the waterproof coating, and controlling the weight ratio of the prepolymer C, the 1, 4-butanediol, the stannous octoate and the triethylamine to be 10: 1: 0.5: 1.
Comparative example 1
This comparative example compares to example 1 with polyethylene instead of polyethylene composite.
Comparative example 2
This comparative example was not coated with a water repellent coating, as compared with example 1.
Comparative example 3
This comparative example is a PE film in the market.
Tensile strength, elongation at break and water impermeability of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in the following table;
as can be seen from the above table, the tensile strength of examples 1-4 is 65-68MPa, the elongation at break is 283-; therefore, in step S3, a second blend is prepared by mixing maleic anhydride and low density polyethylene, and the second blend is polyethylene grafted with maleic anhydride, and then in step S4, the first blend and the second blend are mixed uniformly to prepare composite polyethylene, which is endowed with excellent heat resistance by the blend.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. The preparation method of the PE film is characterized by comprising the following steps:
firstly, weighing the following raw materials in parts by weight: 50-70 parts of composite polyethylene, 15-25 parts of calcium carbonate, 10-20 parts of carbon black and 2-5 parts of plasticizer;
and secondly, sequentially adding the composite polyethylene, the calcium carbonate, the carbon black and the plasticizer into a stirrer to be uniformly mixed, controlling the rotating speed of the stirrer to be 450-480r/min, the temperature to be 75-85 ℃ and the stirring time to be 15min to prepare a mixture B, then transferring the mixture B into a plasticizing machine to be plasticized and mixed, performing blow molding extrusion to prepare a composite film, and then coating waterproof paint with the thickness of 3 mu m on one side surface of the composite film to prepare the PE film.
2. The method of claim 1, wherein the plasticizer is any one of dimethyl phthalate and diethyl phthalate.
3. The method for preparing a PE film according to claim 1, wherein the composite polyethylene is prepared by the following steps:
step S1, grinding and crushing high-density polyethylene, adding methyl methacrylate and the high-density polyethylene into a reaction kettle, uniformly mixing, introducing nitrogen to discharge oxygen, adding a separant, continuously stirring for 15min, heating to 75 ℃, heating for 10min, introducing chlorine, controlling the flow of the chlorine to be 0.5mL/S, heating to 100 ℃, exchanging air and pumping chlorine for 1h after the reaction is finished to prepare an intermediate A, and controlling the weight ratio of the high-density polyethylene to the methyl methacrylate to the separant to be 5: 2-3: 1;
step S2, adding the intermediate A prepared in the step S1 into a beaker filled with dimethylbenzene, heating in a water bath at 45 ℃ and magnetically stirring until the mixture is completely dissolved, then extracting for three times by using deionized water, precipitating and filtering the upper solution in methanol to prepare a filtrate, then drying the precipitate at 80 ℃, crushing and drying at 110 ℃ to constant weight at 100 ℃ to prepare a first mixture, wherein the weight ratio of the intermediate A to the dimethylbenzene is controlled to be 1: 2;
step S3, adding xylene and deionized water into a three-neck flask according to the weight ratio of 1: 10, then sequentially adding low-density polyethylene, maleic anhydride and benzoyl peroxide, ultrasonically swelling for 2 hours, controlling the ultrasonic power to be 50-60W, then transferring into an oil bath pan at 85-90 ℃ for magnetic stirring and reacting for 5 hours to prepare a second mixture, extracting the second mixture for 24 hours through acetone, and then drying for 4 hours at 50-60 ℃ to prepare a purified second mixture;
and S4, uniformly mixing the first mixture prepared in the step S1 and the second mixture prepared in the step S2 according to the weight ratio of 1-3: 1 to prepare the composite polyethylene.
4. The method of claim 3, wherein the separator is one or two of stearic acid soap and talc mixed at any ratio in step S1.
5. The method as claimed in claim 3, wherein the amount ratio of the low density polyethylene, the maleic anhydride, the benzoyl peroxide and the xylene is controlled to be 150-180 g: 30-50 g: 1-2 g: 30-50mL in step S3.
6. The method for preparing a PE film according to claim 1, wherein the waterproof coating is prepared by the following steps:
s11, adding polyether glycol into a three-neck flask, reducing the pressure to-0.09 MPa, heating to 110-120 ℃ and vacuumizing and dehydrating for 3h at the temperature, then cooling to 30-35 ℃, dropping toluene diisocyanate, controlling the dropping time to be 30min, controlling the dropping temperature to be 35-40 ℃, heating the oil bath to 70-75 ℃ after dropping is finished, stirring at the temperature at the rotation speed of 100-120r/min and reacting for 3h, cooling and discharging after the reaction is finished, and obtaining a prepolymer C;
and step S12, adding the prepared prepolymer C into a three-neck flask, adding acetone, controlling the amount of the acetone to be one half of the mass of the prepolymer C, uniformly stirring for 30min, then adding 1, 4-butanediol while stirring, uniformly stirring for 10min, then adding stannous octoate, continuously stirring for 10min, heating to 60-65 ℃, reacting for 5h at the temperature, cooling to 30-35 ℃ after the reaction is finished, adding triethylamine, and dispersing at the rotating speed of 380 plus 400r/min for 3min to obtain the waterproof coating.
7. The method of claim 1, wherein the weight ratio of polyether diol to toluene diisocyanate in step S11 is controlled to 2.5-2.8: 1-1.2, and the weight ratio of prepolymer C, 1, 4-butanediol, stannous octoate and triethylamine in step S12 is controlled to 10-15: 1-1.2: 0.5-0.8: 1-2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011069796.8A CN112194811A (en) | 2020-09-30 | 2020-09-30 | Preparation method of PE film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011069796.8A CN112194811A (en) | 2020-09-30 | 2020-09-30 | Preparation method of PE film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112194811A true CN112194811A (en) | 2021-01-08 |
Family
ID=74013614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011069796.8A Pending CN112194811A (en) | 2020-09-30 | 2020-09-30 | Preparation method of PE film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112194811A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116813965A (en) * | 2023-07-17 | 2023-09-29 | 江苏黎彬新材料科技有限公司 | High-toughness tensile polyolefin film and preparation process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456984A (en) * | 2009-01-05 | 2009-06-17 | 四川大学 | Method for preparing polyethylene blown film filled with coal slack powder |
| CN111350006A (en) * | 2020-03-10 | 2020-06-30 | 王巧云 | Modified polyethylene-based composite fabric and preparation method thereof |
-
2020
- 2020-09-30 CN CN202011069796.8A patent/CN112194811A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456984A (en) * | 2009-01-05 | 2009-06-17 | 四川大学 | Method for preparing polyethylene blown film filled with coal slack powder |
| CN111350006A (en) * | 2020-03-10 | 2020-06-30 | 王巧云 | Modified polyethylene-based composite fabric and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 惠彦涛: "《建筑施工技术》", 28 February 2019, 上海交通大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116813965A (en) * | 2023-07-17 | 2023-09-29 | 江苏黎彬新材料科技有限公司 | High-toughness tensile polyolefin film and preparation process thereof |
| CN116813965B (en) * | 2023-07-17 | 2024-03-19 | 江苏黎彬新材料科技有限公司 | High-toughness tensile polyolefin film and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106957514B (en) | PBAT base biodegradation composite material with high water vapor barrier property | |
| CN110982402A (en) | Pipeline heavy-duty anti-corrosion polyurea protective material and preparation method thereof | |
| CN111286168A (en) | Biodegradable polyester/cellulose composite blown film material and preparation method thereof | |
| CN112029173B (en) | Polyethylene breathable film and preparation method thereof | |
| WO1996019521A1 (en) | Aliphatic polyester resin and process for producing the same | |
| CN109608843B (en) | Reinforced and toughened polylactic acid modified material and preparation method thereof | |
| CN109575311A (en) | A kind of preparation method of vinyl copolymer emulsion | |
| CN112194811A (en) | Preparation method of PE film | |
| CN112250924A (en) | Formula and production process of environment-friendly recycled high-wear-resistance rubber and plastic material | |
| CN114193890A (en) | Degradable low-water-vapor-permeability heat-sealable two-way stretching polylactic acid cigarette film and preparation method thereof | |
| TWI377229B (en) | Polymeric films | |
| CN111533980A (en) | Preparation method of stretch-resistant polyethylene film | |
| CN114316272B (en) | Preparation process of structure control agent | |
| CN116476496A (en) | High-barrier crease-resistant PP (Polypropylene) isolating film | |
| CN111286293B (en) | PP plastic shell adhesive for storage battery and preparation method of PP plastic shell adhesive | |
| CN113121932B (en) | PVC-U drainage pipe fitting and preparation method and application thereof | |
| CN113637313A (en) | Anti-aging PC film label material and preparation method thereof | |
| JPS60255107A (en) | Porous permeable polyethylene film | |
| CN114350125A (en) | Hydrophobic environment-friendly degradable composite packaging film | |
| CN109575545B (en) | Fiber/polyurethane/polylactic acid blend and preparation method thereof | |
| CN113603908A (en) | Degradable environment-friendly plastic master batch and preparation method thereof | |
| CN110922746A (en) | TPU plastic particle processing technology for improving peeling and watermark phenomena | |
| CN113817401B (en) | Single-component polyurethane waterproof coating and preparation method thereof | |
| CN115286904B (en) | Biodegradable breathable material, biodegradable breathable master batch, biodegradable breathable film and application thereof | |
| CN114316105B (en) | Method for removing coating film in PVC (polyvinyl chloride) by suspension method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210108 |
|
| RJ01 | Rejection of invention patent application after publication |