CN116903980A - High-wear-resistance film material based on glass fiber and preparation process thereof - Google Patents

High-wear-resistance film material based on glass fiber and preparation process thereof Download PDF

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CN116903980A
CN116903980A CN202311173951.4A CN202311173951A CN116903980A CN 116903980 A CN116903980 A CN 116903980A CN 202311173951 A CN202311173951 A CN 202311173951A CN 116903980 A CN116903980 A CN 116903980A
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glass fiber
temperature
modified
neck flask
film material
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王芳
王映皓
王小龙
王敏
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Shanghai Jingtan Chemical Co ltd
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Shanghai Jingtan Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/14—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers 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
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients

Abstract

The invention discloses a high wear-resistant film material based on glass fiber and a preparation process thereof, which belong to the technical field of film processing, and the high wear-resistant film material comprises composite glass fiber, modified calcium carbonate, modified resin, an additive and terephthalyl diisocyanate which are uniformly mixed, and are subjected to melt extrusion by a double-screw extruder, and then transferred to a blow molding machine for blow molding, wherein the glass fiber is modified, so that the mechanical property of the composite film material is effectively improved, the ageing resistance and the wear resistance of the composite film material are also improved, and the polarity of hydrocarbon is small, the acting force among molecules is minimum, so that the flexibility of the composite glass fiber is better, the flexibility of the composite glass fiber is further improved, the compatibility between the glass fiber and the modified resin is improved by coating a layer of polyolefin coating on the surface of the glass fiber, the weak interface between the glass fiber and the modified resin is eliminated, the thermal conductivity and the wear resistance of the film are improved, and the composite film is processed more easily.

Description

High-wear-resistance film material based on glass fiber and preparation process thereof
Technical Field
The invention relates to the technical field of film processing, in particular to a high-wear-resistance film material based on glass fibers and a preparation process thereof.
Background
By thin film material is meant a material whose thickness in one dimension is relatively thin, typically in the range of nanometers to micrometers. Film materials have a higher surface area to volume ratio than conventional bulk materials and thus exhibit unique physical, chemical and mechanical properties under certain specific conditions. The fiber is a material with a higher length and a smaller cross section, and the fiber material with high performance comprises carbon fiber, glass fiber, aramid fiber and the like.
The glass fiber in the prior art has larger brittleness and poor flexibility, acid and alkali can corrode the surface of the glass fiber when the glass fiber is in strong acid or alkali environments, the surface structure of the glass fiber is damaged, the tensile property and the wear resistance of the glass fiber are reduced, the glass fiber is an inorganic material, the main component of the glass fiber is silicate, the surface energy of the glass fiber is higher, the better wettability is shown, the surface energy of organic materials such as polyolefin and the like is lower, the surface of the glass fiber is exposed in the air, the surface of the glass fiber is in a certain oxidation state and has higher own hardness, so that the surface tension of the polyolefin and the glass fiber has a certain difference, a weak interface is generated, the overall performance of the film is reduced, the heat conductivity coefficient of the glass fiber is lower, the glass fiber composite film material is caused, the heat conductivity and the heat dissipation performance of the glass fiber are poor, the film is greatly influenced by heat aging, and the ageing resistance of the film is required to be further improved, wherein the glass fiber is simply called as the glass fiber.
In view of the technical drawbacks of this aspect, a solution is now proposed.
Disclosure of Invention
The invention aims to provide a high wear-resistant film material based on glass fibers and a preparation process thereof, which are used for solving the technical problems that in the prior art, the film material prepared by combining glass fibers and polypropylene has certain difference in surface tension between polyolefin and glass fibers, a weak interface is generated, the overall performance of the film is reduced, the glass fibers are low in heat conductivity, the heat conductivity and heat dissipation performance of the film material compounded by the glass fibers are poor, and the film is greatly influenced by heat aging, so that the ageing resistance of the film is required to be further improved.
The aim of the invention can be achieved by the following technical scheme:
the high wear-resistant film material is prepared by uniformly mixing composite glass fiber, modified calcium carbonate, modified resin, an additive and terephthalyl diisocyanate, performing melt extrusion by a double-screw extruder, and transferring into a blow molding machine for blow molding;
the composite glass fiber is prepared by washing glass fiber, immersing and modifying the glass fiber by an activating solution, performing ultrasonic dispersion on the glass fiber, nano boron nitride and nano aluminum oxide to prepare modified glass fiber, and coating a polyolefin layer outside the modified glass fiber, wherein the activating solution consists of 68wt% sulfuric acid, hexadecyl trimethyl ammonium sulfate and 15wt% hydrogen peroxide according to the dosage ratio of 10ml to 2g to 5 ml;
the modified calcium carbonate is obtained by using Z-dihydro-5-methyl-5- (3-hexenyl) -2 (3H) -furanone, N-ethyl-N- (2-hydroxyethyl) perfluoro octyl sulfonamide and toluene to generate an intermediate I through esterification reaction under the high temperature effect, and then carrying out free radical polymerization reaction on the intermediate I, crotonamine and allyl alcohol in the catalyst environment to generate polycondensate to cover the outside of nano calcium carbonate;
the modified resin is prepared by reacting carboxyl on 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with isophorone diisocyanate and then reacting with carboxyl on vinyl acetic acid to generate an intermediate I, and carrying out free radical polymerization reaction on the intermediate I, 3-chloropropene and n-decene under the action of an initiator.
Further, the high wear-resistant film material is prepared from composite glass fiber, modified calcium carbonate, modified resin, an additive and terephthalyl diisocyanate according to the dosage ratio of 2g to 1.5g to 12g to 0.6g to 0.2g, wherein the diameter of the glass fiber is 2-3 mu m.
A preparation process of a high wear-resistant film material based on glass fibers comprises the following steps:
step one, adding emulsion, an initiator and ammonium bicarbonate into a three-neck flask, stirring, raising the temperature of the three-neck flask to 75-85 ℃, dropwise adding the first mixed solution into the three-neck flask, carrying out heat preservation reaction for 2-3h after dropwise adding, dropwise adding the second mixed solution into the three-neck flask, carrying out heat preservation reaction for 4-6h after dropwise adding, and reducing the temperature of the three-neck flask to room temperature to obtain an impregnating solution;
the synthesis reaction principle of the impregnating solution is as follows:
step two, completely dipping the modified glass fiber into a beaker filled with dipping liquid, stirring for 30-50min at room temperature, carrying out suction filtration, transferring a filter cake into a drying oven with the temperature of 60-70 ℃ for drying for 30-50min, washing the filter cake with purified water and absolute ethyl alcohol for 3 times in sequence, transferring the filter cake into a drying oven with the temperature of 65-75 ℃ for drying to constant weight, and obtaining the composite glass fiber;
adding 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and toluene into a three-neck flask protected by nitrogen, stirring, dropwise adding 50wt% of isophorone diisocyanate toluene solution into the three-neck flask at room temperature, carrying out heat preservation reaction for 2-3h after the dropwise addition is finished, dropwise adding 50wt% of vinylacetate toluene solution into the three-neck flask after the dropwise addition is finished, carrying out heat preservation reaction for 2-3h, and carrying out aftertreatment to obtain an intermediate I;
the synthesis reaction principle of the intermediate I is as follows:
step four, adding the intermediate I, 3-chloropropene, n-decene and toluene into a polymerization reaction kettle, stirring, increasing the temperature of the polymerization reaction kettle to 50-60 ℃, adding an initiator into the polymerization reaction kettle, carrying out negative pressure reaction for 2-3h, and carrying out post treatment to obtain modified resin;
the synthetic reaction principle of the modified resin is as follows:
and fifthly, adding the composite glass fiber, the modified calcium carbonate, the modified resin, the additive and the terephthalyl diisocyanate into a double-screw extruder, and transferring the mixture into a blow molding machine for blow molding after melt extrusion to obtain a film finished product.
Further, the modified glass fiber is processed by the following steps:
a1, washing glass fiber with clear water, removing surface stains, draining, immersing the glass fiber in a beaker filled with an activating solution, raising the temperature of the flask to 65-75 ℃, performing ultrasonic treatment for 30-50min, and performing post-treatment to obtain pretreated glass fiber;
a2, adding the nano boron nitride, the nano aluminum oxide and the 65vt percent ethanol water solution into a beaker, raising the temperature of the beaker to 50-55 ℃, performing ultrasonic dispersion for 30-50min, adding the pretreated glass fiber into a three-neck flask, performing heat preservation and ultrasonic treatment for 4-6h, and performing post-treatment to obtain the modified glass fiber.
Further, the post-processing operation of step A1 includes: after the reaction is finished, the temperature of the beaker is reduced to room temperature, suction filtration is carried out, a filter cake is washed to be neutral by purified water and then is transferred into a drying oven with the temperature of 65-75 ℃, and the filter cake is dried to constant weight, thus obtaining the pretreated glass fiber; in the step A2, the dosage ratio of the nanometer boron nitride, the nanometer alumina, the 65vt percent ethanol aqueous solution to the pretreated glass fiber is 1g:0.6g:60ml:10g, the post-treatment operation comprising: after the reaction is finished, the temperature of the beaker is reduced to room temperature, suction filtration is carried out, the filter cake is washed three times by purified water and is dried, the filter cake is transferred into a drying oven with the temperature of 55-65 ℃ and is dried to constant weight, and the modified glass fiber is obtained.
Further, the emulsion in the first step is prepared from tween-80, OP-10, hexadecyldimethylamine and purified water according to the dosage ratio of 5g:2g:6g:88ml of the mixture is added into a beaker and stirred uniformly to obtain the product; the first mixed solution is prepared from methyl 2-nonenoate, butyl methacrylate, oleylamine and emulsion according to the dosage ratio of 1g:5g:4.5g:6 ml; the mixed solution II is prepared from methyl acrylate, acrylic acid, styrene, an initiator and an emulsion according to the dosage ratio of 1g:1.6g:3.6g:0.1g:4ml of the emulsion, the initiator, the ammonium bicarbonate, the first mixed solution and the second mixed solution, wherein the dosage ratio of the emulsion to the initiator to the ammonium bicarbonate to the first mixed solution to the second mixed solution is 10ml:0.1g:0.5g:5ml:5ml, wherein the initiator is ammonium persulfate.
Further, the modified calcium carbonate is processed by the following steps:
b1, adding Z-dihydro-5-methyl-5- (3-hexenyl) -2 (3H) -furanone, N-ethyl-N- (2-hydroxyethyl) perfluorooctyl sulfonamide and toluene into a three-mouth beaker, stirring, heating the three-mouth flask to 90-100 ℃, preserving heat, reacting for 4-6H, and post-treating to obtain an intermediate I;
the synthesis reaction principle of the intermediate I is as follows:
and B2, adding nano calcium carbonate and acetone into a three-necked flask, stirring, adding the intermediate I, crotonamine and allyl alcohol into the three-necked flask at room temperature, raising the temperature of the three-necked flask to 50-55 ℃, adding a catalyst into the three-necked flask, carrying out heat preservation reaction for 2-3h, and carrying out post treatment to obtain the modified calcium carbonate.
The synthetic reaction principle of the modified calcium carbonate is as follows:
further, the dosage ratio of Z-dihydro-5-methyl-5- (3-hexenyl) -2 (3H) -furanone, N-ethyl-N- (2-hydroxyethyl) perfluorooctyl sulfonamide in step B1 is 1.1mol:1mol, and the post-treatment operation comprises: after the reaction is completed, the temperature of the three-neck flask is kept at 90-100 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate I; in the step B2, the dosage ratio of nano calcium carbonate, acetone, an intermediate I, crotyl amine, propylene alcohol and a catalyst is 10g:100ml:1g:3g:2g:0.1g, the post-treatment operation comprising: after the reaction is completed, acetone is distilled off under reduced pressure, the temperature of the three-neck flask is reduced to room temperature, the three-neck flask is crushed and passes through a 200-mesh screen to obtain modified calcium carbonate.
Further, in the third step, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, isophorone diisocyanate and vinyl acetic acid were used in an amount ratio of 1mol:1mol:1mol, the toluene amount is 3 times the weight of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, and the post-treatment operation comprises: after the reaction is completed, the temperature of the three-neck flask is increased to 75-85 ℃, and toluene is distilled off under reduced pressure to obtain an intermediate I; in the fourth step, the dosage ratio of the intermediate I, 3-chloropropene, n-decene, toluene and the initiator is 3g to 2g to 3g to 8ml to 0.1g, the initiator is potassium persulfate or sodium persulfate, and the post-treatment operation comprises: after the reaction is finished, adding purified water into the three-neck flask, stirring for 10-15min, standing for liquid separation, transferring the organic phase into a rotary evaporator with the temperature of 70-80 ℃, and evaporating the solvent under reduced pressure to obtain the modified resin.
Further, the additive in the fifth step consists of a plasticizer, a dispersing agent, a lubricant, an anti-aging agent and an antistatic agent according to the dosage ratio of 1g to 2g to 1g, wherein the plasticizer is one or more groups of dioctyl phthalate, dibutyl phthalate, diisodecyl phthalate and tricresyl phosphate, the dispersing agent is one or more groups of calcium stearate, zinc stearate, magnesium stearate and cadmium stearate, the lubricant oleamide and microcrystalline paraffin, the anti-aging agent is one or two of the anti-aging agent DPPD, the anti-aging agent PPD and the anti-aging agent H, the antistatic agent is any one of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and sodium p-nonylphenoxy propyl sulfonate, the temperature of the twin-screw extruder from a feeding end to a discharging end in 6 temperature intervals is 210 ℃, 220 ℃ and 225 ℃, and the spindle rotating speed of the twin-screw extruder is 12r/min.
The invention has the following beneficial effects:
1. in the processing process of the film, the composition ratio of sulfuric acid, cetyltrimethylammonium sulfate and hydrogen peroxide is optimized to synthesize an activating solution, glass fibers are soaked in the activating solution, surface pretreatment is carried out on the glass fibers, inorganic impurities and oxides on the surfaces of the glass fibers are removed, ultrasonic dispersion is carried out on the pretreated glass fibers, nano boron nitride and nano aluminum oxide in an ethanol water environment, active oxygen-containing groups are formed on the surfaces of the pretreated glass fibers, the surface energy and the surface roughness of the glass fibers are increased, physical adsorption or chemical adsorption of nano boron nitride and nano aluminum oxide particles on the surfaces of the glass fibers can be more easily formed, the adsorptivity of the nano particles on the surfaces of the glass fibers is increased, and the thermal conductivity of the surfaces of the glass fibers is improved; under the action of an initiator, methyl 2-nonenoic acid, butyl methacrylate and oleylamine in an emulsifying system generate polycondensate microspheres through free radical polymerization, methyl acrylate, acrylic acid and styrene are added into the reaction system, coating is formed on the surfaces of the polycondensate microspheres, impregnating solution with core-shell coating is prepared, and after the modified glass fiber is impregnated in the impregnating solution, a coating layer is formed on the surfaces of the modified fiber, so that the composite glass fiber is obtained; after modifying the surface of the glass fiber, the active oxygen-containing groups on the surface of the glass fiber can form a more stable coating structure with the coating layer, the coating layer has a long carbon chain structure, and the polarity of hydrocarbon is small, the acting force between molecules is minimum, so that the flexibility is better, the flexibility of the composite glass fiber is further improved, the compatibility between the glass fiber and the modified resin is improved by coating the surface of the glass fiber with a layer of polyolefin coating layer, the weak interface between the glass fiber and the modified resin is eliminated, the thermal conductivity and the wear resistance of the film are improved, and the composite glass fiber is easier to process.
2. In the processing process of the film, Z-dihydro-5-methyl-5- (3-hexenyl) -2 (3H) -furanone, N-ethyl-N- (2-hydroxyethyl) perfluoro octyl sulfonamide and toluene are subjected to esterification reaction under the action of high temperature, furanone ring opening and hydroxyl on N-ethyl-N- (2-hydroxyethyl) perfluoro octyl sulfonamide generate an intermediate I, and then the intermediate I and crotyl amine and allyl alcohol are subjected to free radical polymerization reaction in the presence of a catalyst to generate polycondensate with a network structure to be coated outside nano calcium carbonate, so that the strength, the thermal stability and the chemical corrosion resistance of the calcium carbonate and the compatibility of the calcium carbonate with modified resin are improved, the dispersibility of the calcium carbonate in the modified resin is improved, the modified calcium carbonate and the composite glass fiber are mutually matched, and the mechanical property of the film is improved; the calcium carbonate is not easy to burn, the decomposition temperature is higher at high temperature, and the decomposition products with high heat capacity and release are compounded with the glass fiber, so that a blocking protective layer is formed, the contact of flame and oxygen is isolated, the propagation path of the flame is blocked, the contact between the surface of the material and the flame is slowed down, the flame spreading speed is reduced, and the flame retardant property of the film is improved.
3. In the processing process of the film, after the carboxyl on 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid reacts with the isocyanate group of isophorone diisocyanate, the other isocyanate group on the product reacts with the carboxyl on vinyl acetic acid to generate an intermediate I, and the intermediate I reacts with 3-chloropropene and n-decene under the action of an initiator to obtain modified resin through free radical polymerization; the carboxyl on the fluorocarbon chain is reacted with isocyanate groups to modify the long carbon chain containing olefin at the end of the fluorocarbon chain, so that the compatibility of the fluorocarbon chain with organic solvents and polymers is greatly improved, a fluorocarbon chain segment has excellent hydrophobicity, the fluorocarbon chain segment is introduced into the polymers to improve the surface hydrophobicity of the polymers, so that the water resistance and the moisture resistance of the film are improved, the long branched chain structure on the modified resin increases the volume and the volume staggering of polyolefin molecules, reduces the mutual attraction force between molecules, improves the melt flowability of the polyolefin, reduces the melt index and the density, and the existence of branched chains can increase the activity of molecular chains, prevent the propagation of cracks and improve the toughness and the impact strength of the polyolefin;
4. in the processing process of the film, the plasticizer, the dispersing agent, the lubricant, the anti-aging agent, the antistatic agent and the terephthalyl diisocyanate are added into the composite glass fiber, and when the composite glass fiber is in melt crosslinking, isocyanate groups on the terephthalyl diisocyanate react with active functional groups on the composite glass fiber, the modified calcium carbonate, the modified resin and additive molecules, so that the crosslinking among raw materials of the film is promoted, the mechanical property of the film is further improved, the anti-aging agent is added, the anti-aging property of the film material can be improved, a large amount of heat is generated when the anti-aging agent acts, the high heat conducting property of the composite glass fiber can effectively conduct heat in time, the heat accumulation and the non-dissipation of the film are avoided, and the ageing resistance of the film is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a block diagram of the process flow for synthesizing the high wear resistant film material of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, 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.
Example 1
The preparation process of the high wear-resistant film material based on the glass fiber comprises the following steps:
step one, preparing composite glass fiber
68wt% sulfuric acid, hexadecyl trimethyl ammonium sulfate and 15wt% hydrogen peroxide are added into a flask according to the dosage ratio of 10ml to 2g to 5ml, and the mixture is uniformly mixed to obtain an activated liquid;
washing glass fiber with clear water, removing surface stains, draining, immersing the glass fiber in a beaker filled with an activating solution, raising the temperature of the flask to 65 ℃, carrying out ultrasonic treatment for 30min, reducing the temperature of the beaker to room temperature, carrying out suction filtration, washing a filter cake with purified water to be neutral, transferring to a drying oven with the temperature of 65 ℃, and drying to constant weight to obtain pretreated glass fiber;
weighing: adding 5g of nanometer boron nitride, 3g of nanometer aluminum oxide and 300ml of 65vt percent ethanol water solution into a beaker, raising the temperature of the beaker to 50 ℃, performing ultrasonic dispersion for 30min, adding 50g of pretreated glass fiber into a three-neck flask, performing heat preservation and ultrasonic treatment for 4h, reducing the temperature of the beaker to room temperature, performing suction filtration, washing a filter cake with purified water for three times, performing suction drying, transferring the filter cake into a drying box with the temperature of 55 ℃, and drying to constant weight to obtain modified glass fiber;
tween-80, OP-10, hexadecyldimethylamine and purified water were mixed in an amount of 5g:2g:6g:88ml of the mixture is added into a beaker and stirred uniformly to obtain emulsion;
methyl 2-nonenoate, butyl methacrylate, oleylamine and emulsion are mixed according to the dosage ratio of 1g:5g:4.5g: adding 6ml into a beaker, and uniformly mixing to obtain a first mixed solution;
methyl acrylate, acrylic acid, styrene, ammonium persulfate and emulsion are mixed according to the dosage ratio of 1g:1.6g:3.6g:0.1g: adding 4ml into a beaker, and uniformly mixing to obtain a mixed solution II;
weighing: adding 100ml of emulsion, 1g of ammonium persulfate and 5g of ammonium bicarbonate into a three-neck flask, stirring, raising the temperature of the three-neck flask to 75 ℃, dropwise adding 50ml of mixed solution I into the three-neck flask, carrying out heat preservation reaction for 2 hours after dropwise adding, dropwise adding 50ml of mixed solution II into the three-neck flask, carrying out heat preservation reaction for 4 hours after dropwise adding, and reducing the temperature of the three-neck flask to room temperature to obtain impregnating solution;
and (3) completely immersing the modified glass fiber in a beaker filled with an impregnating solution, stirring at room temperature for 30min, carrying out suction filtration, transferring a filter cake into a drying oven with the temperature of 60 ℃ for drying for 30min, washing the filter cake with purified water and absolute ethyl alcohol for 3 times in sequence, transferring the filter cake into the drying oven with the temperature of 65 ℃, and drying the filter cake to constant weight to obtain the composite glass fiber.
Step two, preparing modified calcium carbonate
Weighing: 20g of Z-dihydro-5-methyl-5- (3-hexenyl) -2 (3H) -furanone and 57.1g of N-ethyl-N- (2-hydroxyethyl) perfluoro octyl sulfonamide and 150ml of toluene are added into a three-neck beaker to be stirred, the temperature of the three-neck flask is increased to 90 ℃, the temperature of the three-neck flask is kept for 4 hours, the temperature of the three-neck flask is kept at 90 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate I;
weighing: adding 50g of nano calcium carbonate and 500ml of acetone into a three-neck flask, stirring, adding 5g of intermediate I, 15g of crotonamine and 10g of allyl alcohol into the three-neck flask at room temperature, increasing the temperature of the three-neck flask to 50 ℃, adding 0.5g of azobisisobutyronitrile into the three-neck flask, carrying out heat preservation reaction for 2 hours, evaporating acetone under reduced pressure, reducing the temperature of the three-neck flask to room temperature, crushing, and sieving with a 200-mesh sieve to obtain the modified calcium carbonate.
Step three, preparing modified resin
Weighing: adding 27.8g of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and 83.4g of toluene into a three-neck flask protected by nitrogen, stirring, dropwise adding 44.4g of 50wt% isophorone diisocyanate toluene solution into the three-neck flask at room temperature, carrying out heat preservation reaction for 2 hours after the dropwise addition, then dropwise adding 17.2g of 50wt% vinylacetate toluene solution into the three-neck flask, carrying out heat preservation reaction for 2 hours after the dropwise addition, and evaporating toluene under reduced pressure until the temperature of the three-neck flask is increased to 75 ℃ to obtain an intermediate I;
weighing: 30g of intermediate I, 20g of 3-chloropropene, 30g of n-decene and 80ml of toluene are added into a polymerization reaction kettle for stirring, the temperature of the polymerization reaction kettle is increased to 50 ℃, then 1g of potassium persulfate is added into the polymerization reaction kettle for negative pressure reaction for 2-3h, 50ml of purified water is added into a three-neck flask for stirring for 10min, standing and separating liquid are carried out, an organic phase is transferred into a rotary evaporator with the temperature of 70 ℃, and the solvent is removed by reduced pressure evaporation, thus obtaining modified resin;
step four, preparing a film
Weighing: 200g of composite glass fiber, 150g of modified calcium carbonate, 1200g of modified resin, 10g of dioctyl phthalate, 20g of calcium stearate, 10g of oleamide, 10g of antioxidant DPPD, 10g of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and 20g of terephthalyl diisocyanate are added into a screw extruder, the temperature of 6 temperature intervals from a feeding end to a discharging end of the twin-screw extruder is set to 210 ℃, 220 ℃ and 225 ℃ in sequence, the main shaft rotating speed of the twin-screw extruder is 12r/min, and after melt extrusion, the mixture is transferred into a blow molding machine for blow molding, so as to obtain a film finished product.
Example 2
The preparation process of the high wear-resistant film material based on the glass fiber comprises the following steps:
step one, preparing composite glass fiber
68wt% sulfuric acid, hexadecyl trimethyl ammonium sulfate and 15wt% hydrogen peroxide are added into a flask according to the dosage ratio of 10ml to 2g to 5ml, and the mixture is uniformly mixed to obtain an activated liquid;
washing glass fiber with clear water, removing surface stains, draining, immersing the glass fiber in a beaker filled with an activating solution, raising the temperature of the flask to 70 ℃, carrying out ultrasonic treatment for 40min, reducing the temperature of the beaker to room temperature, carrying out suction filtration, washing a filter cake with purified water to be neutral, transferring to a drying oven with the temperature of 70 ℃, and drying to constant weight to obtain pretreated glass fiber;
weighing: adding 5g of nanometer boron nitride, 3g of nanometer aluminum oxide and 300ml of 65vt percent ethanol water solution into a beaker, raising the temperature of the beaker to 53 ℃, performing ultrasonic dispersion for 40min, adding 50g of pretreated glass fiber into a three-neck flask, performing heat preservation and ultrasonic treatment for 5h, reducing the temperature of the beaker to room temperature, performing suction filtration, washing a filter cake with purified water for three times, performing suction drying, transferring the filter cake into a drying box with the temperature of 60 ℃, and drying to constant weight to obtain modified glass fiber;
tween-80, OP-10, hexadecyldimethylamine and purified water were mixed in an amount of 5g:2g:6g:88ml of the mixture is added into a beaker and stirred uniformly to obtain emulsion;
methyl 2-nonenoate, butyl methacrylate, oleylamine and emulsion are mixed according to the dosage ratio of 1g:5g:4.5g: adding 6ml into a beaker, and uniformly mixing to obtain a first mixed solution;
methyl acrylate, acrylic acid, styrene, ammonium persulfate and emulsion are mixed according to the dosage ratio of 1g:1.6g:3.6g:0.1g: adding 4ml into a beaker, and uniformly mixing to obtain a mixed solution II;
weighing: adding 100ml of emulsion, 1g of ammonium persulfate and 5g of ammonium bicarbonate into a three-neck flask, stirring, raising the temperature of the three-neck flask to 80 ℃, dropwise adding 50ml of mixed solution I into the three-neck flask, carrying out heat preservation reaction for 2.5h after dropwise adding, dropwise adding 50ml of mixed solution II into the three-neck flask, carrying out heat preservation reaction for 5h after dropwise adding, and reducing the temperature of the three-neck flask to room temperature to obtain an impregnating solution;
and (3) completely immersing the modified glass fiber in a beaker filled with an impregnating solution, stirring at room temperature for 40min, carrying out suction filtration, transferring a filter cake into a drying oven with the temperature of 65 ℃ for drying for 40min, washing the filter cake with purified water and absolute ethyl alcohol for 3 times in sequence, transferring the filter cake into the drying oven with the temperature of 70 ℃, and drying the filter cake to constant weight to obtain the composite glass fiber.
Step two, preparing modified calcium carbonate
Weighing: 20g of Z-dihydro-5-methyl-5- (3-hexenyl) -2 (3H) -furanone and 57.1g of N-ethyl-N- (2-hydroxyethyl) perfluoro octyl sulfonamide and 150ml of toluene are added into a three-neck beaker to be stirred, the temperature of the three-neck flask is increased to 95 ℃, the temperature of the three-neck flask is kept for 5 hours, the temperature of the three-neck flask is kept at 95 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate I;
weighing: 50g of nano calcium carbonate and 500ml of acetone are added into a three-neck flask to be stirred, 5g of intermediate I, 15g of crotonamine and 10g of allyl alcohol are added into the three-neck flask at room temperature, the temperature of the three-neck flask is increased to 53 ℃, 0.5g of azodiisobutyronitrile is added into the three-neck flask to react for 2.5 hours under heat preservation, the acetone is distilled off under reduced pressure, the temperature of the three-neck flask is reduced to room temperature, the three-neck flask is crushed and passes through a 200-mesh screen to obtain the modified calcium carbonate.
Step three, preparing modified resin
Weighing: 27.8g of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and 83.4g of toluene are added into a three-neck flask protected by nitrogen gas for stirring, 44.4g of 50wt% isophorone diisocyanate toluene solution is dropwise added into the three-neck flask at room temperature, the reaction is carried out for 2.5 hours after the dropwise addition, 17.2g of 50wt% ethylene-vinyl acetate toluene solution is dropwise added into the three-neck flask after the dropwise addition, the reaction is carried out for 2.5 hours after the dropwise addition, the temperature of the three-neck flask is increased to 80 ℃, and toluene is distilled off under reduced pressure to obtain an intermediate I;
weighing: 30g of intermediate I, 20g of 3-chloropropene, 30g of n-decene and 80ml of toluene are added into a polymerization reaction kettle for stirring, the temperature of the polymerization reaction kettle is increased to 55 ℃, then 1g of sodium persulfate is added into the polymerization reaction kettle for negative pressure reaction for 2.5h, 50ml of purified water is added into a three-neck flask for stirring for 13min, standing and separating liquid are carried out, an organic phase is transferred into a rotary evaporator with the temperature of 75 ℃, and the solvent is removed by reduced pressure evaporation, thus obtaining modified resin;
step four, preparing a film
Weighing: 200g of composite glass fiber, 150g of modified calcium carbonate, 1200g of modified resin, 10g of dibutyl phthalate, 20g of zinc stearate, 10g of microcrystalline paraffin, 10g of antioxidant PPD, 10g of sodium p-nonylphenoxy propyl sulfonate and 20g of p-phenylene diisocyanate are added into a screw extruder, the temperature of 6 temperature ranges from a feeding end to a discharging end of the twin-screw extruder is sequentially set to 210 ℃, 220 ℃ and 225 ℃, the main shaft rotating speed of the twin-screw extruder is 12r/min, and after melt extrusion, the mixture is transferred into a blow molding machine for blow molding, so as to obtain a film finished product.
Example 3
The preparation process of the high wear-resistant film material based on the glass fiber comprises the following steps:
step one, preparing composite glass fiber
68wt% sulfuric acid, hexadecyl trimethyl ammonium sulfate and 15wt% hydrogen peroxide are added into a flask according to the dosage ratio of 10ml to 2g to 5ml, and the mixture is uniformly mixed to obtain an activated liquid;
washing glass fiber with clear water, removing surface stains, draining, immersing the glass fiber in a beaker filled with an activating solution, raising the temperature of the flask to 75 ℃, carrying out ultrasonic treatment for 50min, reducing the temperature of the beaker to room temperature, carrying out suction filtration, washing a filter cake with purified water to be neutral, transferring to a drying box with the temperature of 75 ℃, and drying to constant weight to obtain pretreated glass fiber;
weighing: adding 5g of nanometer boron nitride, 3g of nanometer aluminum oxide and 300ml of 65vt percent ethanol water solution into a beaker, increasing the temperature of the beaker to 55 ℃, carrying out ultrasonic dispersion for 50min, adding 50g of pretreated glass fiber into a three-neck flask, carrying out heat preservation and ultrasonic treatment for 6h, reducing the temperature of the beaker to room temperature, carrying out suction filtration, washing a filter cake with purified water for three times, carrying out suction drying, transferring the filter cake into a drying box with the temperature of 65 ℃, and carrying out drying to constant weight to obtain modified glass fiber;
tween-80, OP-10, hexadecyldimethylamine and purified water were mixed in an amount of 5g:2g:6g:88ml of the mixture is added into a beaker and stirred uniformly to obtain emulsion;
methyl 2-nonenoate, butyl methacrylate, oleylamine and emulsion are mixed according to the dosage ratio of 1g:5g:4.5g: adding 6ml into a beaker, and uniformly mixing to obtain a first mixed solution;
methyl acrylate, acrylic acid, styrene, ammonium persulfate and emulsion are mixed according to the dosage ratio of 1g:1.6g:3.6g:0.1g: adding 4ml into a beaker, and uniformly mixing to obtain a mixed solution II;
weighing: adding 100ml of emulsion, 1g of ammonium persulfate and 5g of ammonium bicarbonate into a three-neck flask, stirring, raising the temperature of the three-neck flask to 85 ℃, dropwise adding 50ml of mixed solution I into the three-neck flask, carrying out heat preservation reaction for 3 hours after dropwise adding, dropwise adding 50ml of mixed solution II into the three-neck flask, carrying out heat preservation reaction for 6 hours after dropwise adding, and reducing the temperature of the three-neck flask to room temperature to obtain impregnating solution;
and (3) completely immersing the modified glass fiber in a beaker filled with an impregnating solution, stirring at room temperature for 50min, carrying out suction filtration, transferring a filter cake into a drying oven with the temperature of 70 ℃ for drying for 50min, washing the filter cake with purified water and absolute ethyl alcohol for 3 times in sequence, transferring the filter cake into a drying oven with the temperature of 75 ℃, and drying the filter cake to constant weight to obtain the composite glass fiber.
Step two, preparing modified calcium carbonate
Weighing: 20g of Z-dihydro-5-methyl-5- (3-hexenyl) -2 (3H) -furanone and 57.1g of N-ethyl-N- (2-hydroxyethyl) perfluoro octyl sulfonamide and 150ml of toluene are added into a three-neck beaker to be stirred, the temperature of the three-neck flask is increased to 100 ℃, the temperature of the three-neck flask is kept for 6 hours, the temperature of the three-neck flask is kept at 100 ℃, and the solvent is distilled off under reduced pressure to obtain an intermediate I;
weighing: 50g of nano calcium carbonate and 500ml of acetone are added into a three-neck flask to be stirred, 5g of intermediate I, 15g of crotonamine and 10g of allyl alcohol are added into the three-neck flask at room temperature, the temperature of the three-neck flask is increased to 55 ℃, 0.5g of azodiisobutyronitrile is added into the three-neck flask to react for 3 hours under heat preservation, the acetone is distilled off under reduced pressure, the temperature of the three-neck flask is reduced to room temperature, the three-neck flask is crushed, and a 200-mesh screen is adopted to obtain the modified calcium carbonate.
Step three, preparing modified resin
Weighing: adding 27.8g of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and 83.4g of toluene into a three-neck flask protected by nitrogen, stirring, dropwise adding 44.4g of 50wt% isophorone diisocyanate toluene solution into the three-neck flask at room temperature, carrying out heat preservation reaction for 3 hours after the dropwise addition, then dropwise adding 17.2g of 50wt% vinylacetate toluene solution into the three-neck flask, carrying out heat preservation reaction for 3 hours after the dropwise addition, and raising the temperature of the three-neck flask to 75-85 ℃, and evaporating toluene under reduced pressure to obtain an intermediate I;
weighing: 30g of intermediate I, 20g of 3-chloropropene, 30g of n-decene and 80ml of toluene are added into a polymerization reaction kettle for stirring, the temperature of the polymerization reaction kettle is increased to 60 ℃, then 1g of potassium persulfate is added into the polymerization reaction kettle for negative pressure reaction for 3 hours, 50ml of purified water is added into a three-neck flask for stirring for 15 minutes, standing and liquid separation are carried out, an organic phase is transferred into a rotary evaporator with the temperature of 80 ℃, and the solvent is distilled off under reduced pressure, so that modified resin is obtained;
step four, preparing a film
Weighing: 200g of composite glass fiber, 150g of modified calcium carbonate, 1200g of modified resin, 10g of diisodecyl phthalate, 20g of oleamide, 10g of lubricant, 10g of anti-aging agent H, 10g of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and 20g of terephthalyl diisocyanate are added into a screw extruder, the temperature of 6 temperature intervals from a feed end to a discharge end of the twin-screw extruder is set to 210 ℃, 220 ℃ and 225 ℃ in sequence, the main shaft rotating speed of the twin-screw extruder is 12r/min, and after melt extrusion, the mixture is transferred into a blow molding machine for blow molding, so as to obtain a film finished product.
Comparative example 1
The comparative example differs from example 3 in that the composite glass fiber in step four was replaced with the modified glass fiber in step one in equal amount.
Comparative example 2
The comparative example differs from example 3 in that step one was omitted and the composite glass fiber in step four was replaced with the same amount of glass fiber after washing.
Comparative example 3
The difference between this comparative example and example 3 is that step two was omitted and the modified calcium carbonate in step four was replaced with an equivalent amount of nano calcium carbonate.
Comparative example 4
The difference between this comparative example and example 3 is that step three was omitted and the modified resin in step four was replaced with commercially available PVC.
Performance test:
the mechanical properties, wear resistance and ageing resistance of the film finished products prepared in examples 1-3 and comparative examples 1-3 are tested, wherein the mechanical properties refer to the tensile strength, the 120 ℃ heat shrinkage and the fracture nominal strain of the standard GB/T26690-2011 acrylic acid coated biaxially oriented polypropylene film, and the wear resistance refers to the method A-observation method in the standard GB/T31727-2015 transparent film grinding degree test method; the aging resistance is that a sample is placed in an irradiation chamber with the temperature of 80 ℃ for ultraviolet irradiation for 100 hours, the ultraviolet irradiation intensity is set to 1500 mu W/cm, the mechanical properties of the irradiated sample are measured, and the specific test results are shown in the following table:
data analysis:
analysis of the data of examples 1-3 and comparative examples 1-4 shows that the films prepared by the invention have good mechanical properties, ageing resistance and wear resistance;
analysis and comparison of the data of the comparative examples 1-2 and the data of the examples 1-3 show that the mechanical property and the ageing resistance of the comparative examples 1-2 are lower than those of the detection data of the examples 1-3, and the mechanical property, the ageing resistance and the wear resistance of the comparative example 2 are lower than those of the detection data of the comparative example 1, and the fact that the glass fiber is modified is helpful to improve the crosslinking degree of the modified glass fiber in the modified resin and the modified resin, and the modified glass fiber is further modified and compounded, so that the dispersibility of the glass fiber in the modified resin, the heat conduction and heat dissipation performance of the film and the ageing resistance of the film are improved.
The comparative analysis of the data of comparative example 3 and examples 1-3 shows that the mechanical property, ageing resistance and wear resistance of comparative example 3 are lower than those of examples 1-3, and it is shown that the dispersibility of calcium carbonate in the film can be improved by modifying the calcium carbonate, so that the mechanical property, heat dissipation and wear resistance of the film are improved, and as the heat dissipation of the film is improved, the ageing resistance of the film is further improved, and the calcium carbonate is uniformly distributed in the film, so that the flame retardance of the film is also effectively improved;
the comparison analysis of the data of the comparative example 4 and the data of the examples 1-3 shows that the various detection data of the invention are improved compared with the data of the comparative example 4, which shows that the compounding effect of the modified resin prepared by the invention and the composite glass fiber, the modified calcium carbonate and the additive is better than the compounding effect of the commercial PVC and the composite glass fiber, the modified calcium carbonate and the additive, and the performance of the modified resin is more suitable for being applied in the invention.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.

Claims (9)

1. The high wear-resistant film material based on the glass fiber is characterized by being obtained by uniformly mixing composite glass fiber, modified calcium carbonate, modified resin, an additive and terephthalyl diisocyanate, performing melt extrusion by a double-screw extruder, and transferring into a blow molding machine for blow molding;
the composite glass fiber is prepared by washing glass fiber, immersing and modifying the glass fiber by an activating solution, performing ultrasonic dispersion on the glass fiber, nano boron nitride and nano aluminum oxide to prepare modified glass fiber, and coating a polyolefin layer outside the modified glass fiber, wherein the activating solution consists of 68wt% sulfuric acid, hexadecyl trimethyl ammonium sulfate and 15wt% hydrogen peroxide according to the dosage ratio of 10ml to 2g to 5 ml;
the modified calcium carbonate is obtained by using Z-dihydro-5-methyl-5- (3-hexenyl) -2 (3H) -furanone, N-ethyl-N- (2-hydroxyethyl) perfluoro octyl sulfonamide and toluene to generate an intermediate I through esterification reaction under the high temperature effect, and then carrying out free radical polymerization reaction on the intermediate I, crotonamine and allyl alcohol in the catalyst environment to generate polycondensate to cover the outside of nano calcium carbonate;
the modified resin is prepared by reacting carboxyl on 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid with isophorone diisocyanate and then reacting with carboxyl on vinyl acetic acid to generate an intermediate I, and carrying out free radical polymerization reaction on the intermediate I, 3-chloropropene and n-decene under the action of an initiator.
2. The high wear-resistant film material based on glass fiber according to claim 1, wherein the high wear-resistant film material is prepared from composite glass fiber, modified calcium carbonate, modified resin, additives and terephthalyl diisocyanate according to the dosage ratio of 2g to 1.5g to 12g to 0.6g to 0.2g, and the diameter of the glass fiber is 2-3 μm.
3. The preparation process of the high wear-resistant film material based on the glass fiber is characterized by comprising the following steps of:
step one, adding the emulsion, an initiator and ammonium bicarbonate into a three-neck flask, stirring, raising the temperature of the three-neck flask to 75-85 ℃, dropwise adding a first mixed solution into the three-neck flask, carrying out heat preservation reaction for 2-3h after dropwise adding, dropwise adding a second mixed solution into the three-neck flask, carrying out heat preservation reaction for 4-6h after dropwise adding, and reducing the temperature of the three-neck flask to room temperature to obtain an impregnating solution, wherein the first mixed solution comprises methyl 2-nonenoate, butyl methacrylate, oleylamine and the emulsion according to the dosage ratio of 1g:5g:4.5g:6 ml; the mixed solution II is prepared from methyl acrylate, acrylic acid, styrene, an initiator and an emulsion according to the dosage ratio of 1g:1.6g:3.6g:0.1g:4 ml;
step two, completely dipping the modified glass fiber into a beaker filled with dipping liquid, stirring for 30-50min at room temperature, carrying out suction filtration, transferring a filter cake into a drying oven with the temperature of 60-70 ℃ for drying for 30-50min, washing the filter cake with purified water and absolute ethyl alcohol for 3 times in sequence, transferring the filter cake into a drying oven with the temperature of 65-75 ℃ for drying to constant weight, and obtaining the composite glass fiber;
adding 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid and toluene into a three-neck flask protected by nitrogen, stirring, dropwise adding 50wt% of isophorone diisocyanate toluene solution into the three-neck flask at room temperature, carrying out heat preservation reaction for 2-3h after the dropwise addition is finished, dropwise adding 50wt% of vinylacetate toluene solution into the three-neck flask after the dropwise addition is finished, carrying out heat preservation reaction for 2-3h, and carrying out aftertreatment to obtain an intermediate I;
step four, adding the intermediate I, 3-chloropropene, n-decene and toluene into a polymerization reaction kettle, stirring, increasing the temperature of the polymerization reaction kettle to 50-60 ℃, adding an initiator into the polymerization reaction kettle, carrying out negative pressure reaction for 2-3h, and carrying out post treatment to obtain modified resin;
and fifthly, adding the composite glass fiber, the modified calcium carbonate, the modified resin, the additive and the terephthalyl diisocyanate into a double-screw extruder, and transferring the mixture into a blow molding machine for blow molding after melt extrusion to obtain a film finished product.
4. The process for preparing the high wear-resistant film material based on glass fibers according to claim 3, wherein the modified glass fibers are processed by the following steps:
a1, washing glass fiber with clear water, removing surface stains, draining, immersing the glass fiber in a beaker filled with an activating solution, raising the temperature of the flask to 65-75 ℃, performing ultrasonic treatment for 30-50min, and performing post-treatment to obtain pretreated glass fiber;
a2, adding nano boron nitride, nano aluminum oxide and 65vt percent ethanol water solution into a beaker, increasing the temperature of the beaker to 50-55 ℃, performing ultrasonic dispersion for 30-50min, adding pretreatment glass fiber into a three-neck flask, performing heat preservation and ultrasonic treatment for 4-6h, and performing post-treatment to obtain modified glass fiber, wherein the dosage ratio of the nano boron nitride, the nano aluminum oxide, the 65vt percent ethanol water solution to the pretreatment glass fiber is 1g:0.6g:60ml:10g.
5. A process for preparing a highly abrasion-resistant film material based on glass fibers according to claim 3, wherein the emulsion in the first step is prepared from tween-80, OP-10, hexadecyldimethylamine and purified water in an amount ratio of 5g:2g:6g:88ml of the mixture is added into a beaker and stirred uniformly to obtain the product; the dosage ratio of the emulsion, the initiator, the ammonium bicarbonate, the first mixed solution and the second mixed solution is 10ml:0.1g:0.5g:5ml:5ml, wherein the initiator is ammonium persulfate.
6. A process for preparing a high abrasion resistant film material based on glass fibers according to claim 3, wherein the modified calcium carbonate is processed by the steps of:
b1, adding Z-dihydro-5-methyl-5- (3-hexenyl) -2 (3H) -furanone, N-ethyl-N- (2-hydroxyethyl) perfluorooctyl sulfonamide and toluene into a three-mouth beaker, stirring, heating the three-mouth flask to 90-100 ℃, preserving heat, reacting for 4-6H, and post-treating to obtain an intermediate I;
and B2, adding nano calcium carbonate and acetone into a three-necked flask, stirring, adding the intermediate I, crotonamine and allyl alcohol into the three-necked flask at room temperature, raising the temperature of the three-necked flask to 50-55 ℃, adding a catalyst into the three-necked flask, carrying out heat preservation reaction for 2-3h, and carrying out post treatment to obtain the modified calcium carbonate.
7. The process for preparing a highly abrasion-resistant film material based on glass fibers according to claim 6, wherein the dosage ratio of Z-dihydro-5-methyl-5- (3-hexenyl) -2 (3H) -furanone, N-ethyl-N- (2-hydroxyethyl) perfluorooctyl sulfonamide in step B1 is 1.1mol:1mol; in the step B2, the dosage ratio of nano calcium carbonate, acetone, an intermediate I, crotyl amine, propylene alcohol and a catalyst is 10g:100ml:1g:3g:2g:0.1g.
8. A process for the preparation of a highly abrasion resistant film material based on glass fibers according to claim 3, characterized in that in step three the ratio of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, isophorone diisocyanate and vinylacetic acid is 1mol:1mol:1mol, wherein the dosage of toluene is 3 times of the weight of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid; in the fourth step, the dosage ratio of the intermediate I, 3-chloropropene, n-decene, toluene and the initiator is 3g to 2g to 3g to 8ml to 0.1g, and the initiator is potassium persulfate or sodium persulfate.
9. The preparation process of the high wear-resistant film material based on glass fibers according to claim 3, wherein in the fifth step, the additive consists of a plasticizer, a dispersing agent, a lubricant, an anti-aging agent and an antistatic agent according to the dosage ratio of 1g to 2g to 1g, wherein the plasticizer is one or more of dioctyl phthalate, dibutyl phthalate, diisodecyl phthalate and tricresyl phosphate, the dispersing agent is one or more of calcium stearate, zinc stearate, magnesium stearate and cadmium stearate, the lubricant oleamide and microcrystalline paraffin, the anti-aging agent is one or two of an anti-aging agent DPPD, an anti-aging agent PPD and an anti-aging agent H, and is any one of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and sodium p-nonylphenoxy propyl sulfonate.
CN202311173951.4A 2023-09-12 2023-09-12 High-wear-resistance film material based on glass fiber and preparation process thereof Pending CN116903980A (en)

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CN108410093A (en) * 2018-04-10 2018-08-17 郑州智锦电子科技有限公司 A kind of high strength glass fiber modified polyvinyl chloride material and preparation method thereof
CN112409695A (en) * 2020-12-10 2021-02-26 韦金毅 Low-warpage polypropylene modified plastic and preparation method thereof

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