CN114891148B - Preparation method of high-strength plastic toughening agent - Google Patents

Preparation method of high-strength plastic toughening agent Download PDF

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CN114891148B
CN114891148B CN202210362420.9A CN202210362420A CN114891148B CN 114891148 B CN114891148 B CN 114891148B CN 202210362420 A CN202210362420 A CN 202210362420A CN 114891148 B CN114891148 B CN 114891148B
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siloxane
acrylic ester
emulsion
strength plastic
modified acrylic
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CN114891148A (en
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顾娇娇
顾法明
李正中
吴旭忠
刘胜成
匡文荣
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JIANGSU HANKUANG INDUSTRIAL CO LTD
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JIANGSU HANKUANG INDUSTRIAL CO LTD
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    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a preparation method of a high-strength plastic toughening agent, belongs to the technical field of plastic toughening, and particularly relates to a preparation method of end-capped acrylamide propyl siloxane by reacting end-aminopropyl siloxane with acryloyl chloride, wherein the end-aminopropyl siloxane is 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane; and (3) adding an initiator into the emulsion containing BA, st, MMA and the end-capped acrylamide propyl siloxane, reacting to generate modified acrylic ester emulsion, and drying to obtain modified acrylic ester, wherein the emulsifying agent used in the emulsion comprises an anionic emulsifying agent and a nonionic emulsifying agent. The modified acrylic ester prepared by the invention can be used for preparing high-strength plastics, the water absorption and tensile strength of the modified acrylic ester adhesive film prepared by the invention are reduced, the prepared high-strength plastics has good impact resistance and the impact strength is 13-20KJ/m 2 。

Description

Preparation method of high-strength plastic toughening agent
Technical Field
The invention belongs to the technical field of plastic toughening, and particularly relates to a preparation method of a high-strength plastic toughening agent.
Background
Polyvinyl chloride (PVC) is a high-general-purpose polymer material used worldwide, and is one of the earliest resins industrialized worldwide. The PVC material has low raw material price, good performances such as insulation, flame retardance, good chemical stability and the like, so that the PVC material is widely applied, and the hard PVC material can be used as plastic building materials (pipes, plates) and packaging products (boxes, bottles, medical packages and the like); the soft PVC material can be used as building materials (wallpaper, waterproof coiled materials, sealing profiles, floors and the like), wires and cables, artificial leather and the like.
PVC is a high polymer formed by polymerizing vinyl chloride monomers through free radicals, and defects such as chloromethyl structure, allyl chloride structure, tertiary chloride structure and the like are caused in PVC by chain transfer reaction and double-radical coupling termination reaction in the polymerization process. The existence of the defects reduces the performance of the PVC material, and a large number of polar bonds C-Cl bonds in the PVC molecular chain cause larger acting force between molecules, so that the material is hard and brittle. The pure PVC material has poor toughness at room temperature and low temperature, has notch sensitivity, is easy to crack when being impacted by external force, is difficult to be used as building materials or structural materials, and limits the application of PVC materials.
The invention aims to provide a toughening agent capable of improving PVC performance.
Disclosure of Invention
The invention aims to provide a preparation method of a high-strength plastic toughening agent for preparing plastics and improving the impact resistance of plastics.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a method for preparing a modified acrylate comprising:
reacting terminal aminopropyl siloxane with acryloyl chloride to prepare terminal acrylamide aminopropyl siloxane, wherein the terminal aminopropyl siloxane is 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane;
and (3) adding an initiator into the emulsion containing BA, st, MMA and the end-capped acrylamide propyl siloxane, reacting to generate modified acrylic ester emulsion, and drying to obtain modified acrylic ester, wherein the emulsifying agent used in the emulsion comprises an anionic emulsifying agent and a nonionic emulsifying agent. According to the invention, propenyl is introduced into siloxane through the reaction of aminopropyl siloxane and acryloyl chloride to obtain end-capped acrylamide propyl siloxane with alkenyl and silicon elements, the end-capped acrylamide propyl siloxane and BA, st, MMA are mixed in emulsion, modified acrylic ester emulsion is prepared under the action of an initiator, and the modified acrylic ester emulsion is dried to obtain modified acrylic ester, so that the obtained modified acrylic ester can be used as a toughening agent for preparing plastics, and the performance of the plastics is improved.
Preferably, the acrylic acid chloride solution is used in an amount such that the molar amount of acrylic acid chloride is 200-300% of the molar amount of the amino terminated propyl siloxane used.
Preferably, the modified acrylic ester emulsion is filtered, added with calcium phytate, mixed and dried to obtain the modified acrylic ester. After the modified acrylic ester emulsion is prepared, large-particle insoluble impurities are removed through filtration, and then the modified acrylic ester is uniformly mixed with calcium phytate to prepare the modified acrylic ester, after the prepared modified acrylic ester is used for preparing plastics, the impact resistance of the plastics can be greatly improved, the modified acrylic ester prepared by end-capped acrylamide propyl siloxane and calcium phytate are used together to have the effect of improving the impact resistance of the plastics, and when the modified acrylic ester prepared by end-capped acrylamide propyl siloxane and calcium phytate are used, the impact resistance of the plastics is improved slightly.
More preferably, the calcium phytate is used in an amount of 2-10wt% of the modified acrylate emulsion.
Preferably, the initiator is APS.
Preferably, in the preparation of the end-capped acrylamide propyl siloxane, the end-aminopropyl siloxane is added into dichloromethane and mixed to obtain an end-aminopropyl siloxane solution, anhydrous potassium carbonate is added, an acryloyl chloride solution is dropwise added at the temperature of 0-5 ℃, after the dropwise addition is finished, the reaction is carried out for 2-8 hours at the temperature of 30-40 ℃, after the reaction is finished, the end-capped acrylamide propyl siloxane is obtained by washing with sodium bicarbonate solution, deionized water and saturated saline solution, drying and spin-evaporating to remove solvent dichloromethane.
More preferably, in the preparation of the end-capped acrylamide propyl siloxane, the end-aminopropyl siloxane is 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane, and the end-aminopropyl siloxane solution contains 50-70wt% of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane.
More preferably, the anhydrous potassium carbonate is used in the preparation of the blocked acrylamide propyl siloxane in an amount of 0.4 to 2wt% of the blocked amino propyl siloxane solution.
More preferably, in the preparation of the end-capped acrylamide propyl siloxane, the acrylic acid chloride solution contains 50-70wt% of acrylic acid chloride, and the acrylic acid chloride solution is used in an amount such that the molar amount of acrylic acid chloride is 200-300% of the molar amount of the end-aminopropyl siloxane used.
More preferably, the preparation of the end-capped acrylamide propyl siloxane comprises 3-8wt% sodium bicarbonate in sodium bicarbonate solution.
Preferably, in the preparation of the modified acrylic ester, an emulsifier is added into deionized water and stirred and mixed, then BA, st, MMA and end-capped acrylamide propyl siloxane are added, the stirred and mixed to obtain a pre-emulsion, the pre-emulsion is subjected to ultrasonic treatment for 10-30min, an APS solution is added at the temperature of 75-85 ℃, the reaction is carried out for 2-8h, after the reaction is completed, the temperature is cooled to 30-40 ℃, the pH value is regulated to 6-8, the filtration is carried out, the modified acrylic ester emulsion is obtained, and the modified acrylic ester is obtained after drying and crushing.
More preferably, in the preparation of the modified acrylic ester, the emulsifier is added into deionized water and stirred and mixed, then BA, st, MMA and end-capped acrylamide propyl siloxane are added, the stirred and mixed to obtain pre-emulsion, ultrasonic treatment is carried out for 10-30min, APS solution is added at the temperature of 75-85 ℃, reaction is carried out for 2-8h, after the reaction is completed, cooling is carried out to 30-40 ℃, the pH value is regulated to 6-8, filtration is carried out, the modified acrylic ester emulsion is obtained, then calcium phytate is added, the stirred and mixed, ultrasonic treatment is carried out for 10-30min, drying and crushing are carried out, and the modified acrylic ester is obtained.
More preferably, in the preparation of the modified acrylate, the emulsifier is mixed by an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is SDS, and the nonionic emulsifier is NP-30.
More preferably, the modified acrylate is prepared with an anionic emulsifier content of 30 to 60wt%.
More preferably, the content of emulsifier in the pre-emulsion is 2-5wt% in the preparation of the modified acrylate.
More preferably, in the preparation of the modified acrylate, the BA content of the pre-emulsion is 20-40wt%.
More preferably, st is used in the preparation of the modified acrylate in an amount of 10 to 20wt% of BA.
More preferably, MMA is used in an amount of 5 to 15wt% of BA in the preparation of the modified acrylate.
More preferably, in the preparation of the modified acrylate, the end-capped acrylamide propyl siloxane is used in an amount of 4 to 16wt% of BA.
More preferably, the modified acrylate is prepared with 2 to 5wt% APS in the APS solution, and the APS solution is used in an amount of 2 to 6wt% of the pre-emulsion.
More preferably, in the preparation of the modified acrylic ester, the calcium phytate is used in an amount of 2-10wt% of the modified acrylic ester emulsion.
The invention discloses modified acrylic ester prepared by the method.
The invention discloses application of the modified acrylic ester in preparation of plastic materials.
A method for preparing high strength plastic, comprising: the preparation method of the modified acrylic ester.
Preferably, the high-strength plastic at least comprises PVC resin, composite lead stabilizer, stearic acid 1801, paraffin, light calcium carbonate and modified acrylic ester.
Preferably, in the preparation of the high-strength plastic, PVC resin, a composite lead stabilizer, stearic acid 1801, paraffin, light calcium carbonate and modified acrylic ester are mixed, added into a high-speed mixer, mixed at the temperature of 90-110 ℃ for 0.5-3h, then in a plasticator, open-rolled at the temperature of 160-180 ℃ to continuously perform triangular wrapping and rolling until the material is uniform in color and luster and the cut section does not show hairiness particles, then the roll gap is adjusted, the roll gap is thinned and communicated for 3-4 times, the high-strength plastic sheet is obtained according to the required thickness, and then the high-strength plastic sheet is subjected to die pressing treatment to obtain the high-strength plastic.
More preferably, in the preparation of the high-strength plastic, the composite lead stabilizer is used in an amount of 3 to 9wt% of the PVC resin.
More preferably, in the preparation of the high strength plastic, stearic acid 1801 is used in an amount of 0.5 to 2wt% of the PVC resin.
More preferably, in the preparation of the high strength plastic, the paraffin wax is used in an amount of 0.4 to 1.6wt% of the PVC resin.
More preferably, in the preparation of the high strength plastic, the light calcium carbonate is used in an amount of 3 to 7wt% of the PVC resin.
More preferably, in the preparation of the high strength plastic, the modified acrylate is used in an amount of 2 to 10wt% of the PVC resin.
More preferably, ethyl cyclopentanecarboxylate may be added to the preparation of the high-strength plastic, with the ethyl cyclopentanecarboxylate being used in an amount of 1-5wt% of the PVC resin. After PVC is used as a main material and the end-capped acrylamide propyl siloxane, the composite lead stabilizer, stearic acid 1801, paraffin and light calcium carbonate auxiliary materials are used for preparing plastics, the shock resistance is improved, and after cyclopentane carboxylic acid ethyl ester is further used, the shock resistance of the prepared high-strength plastics is further improved.
Preferably, in the mould pressing treatment process, the mould is placed on a flat vulcanizing machine for preheating, then the high-strength plastic sheet is placed in the mould, the mould is pre-pressed for 2-6min at the temperature of 170-190 ℃, then the air is exhausted for 10-20 times, after the air exhaust is completed, the mould is treated for 3-8min under the pressure of 8-12MPa, and finally the mould is subjected to pressure maintaining and shaping on a cold press and is cooled to the room temperature.
The invention discloses high-strength plastic prepared by the method.
The end-capped acrylamide propyl siloxane is prepared by adopting the reaction of the end-capped amino propyl siloxane and the acryloyl chloride, and then the end-capped acrylamide propyl siloxane and BA, st, MMA react under the action of the initiator to generate the modified acrylic ester, the modified acrylic ester prepared by the invention can be used as a toughening agent for preparing plastics, and the high-strength plastics are prepared by the modified acrylic ester, the PVC resin and other raw materials, so that the modified acrylic ester has the following beneficial effects: the water absorption rate of the modified acrylic acid ester adhesive film is 4-28%, the tensile strength of the modified acrylic acid ester adhesive film is 0.4-0.8MPa, and the impact strength of the high-strength plastic is 13-20KJ/m < 2 >. Therefore, the invention relates to a preparation method of a high-strength plastic toughening agent for preparing plastics and improving the impact resistance of plastics.
Drawings
FIG. 1 is an infrared spectrum of a blocked acrylamidopropyl siloxane;
FIG. 2 is a graph of water absorption of a film;
FIG. 3 is a graph of tensile strength of a film;
fig. 4 is a graph of impact strength of a high strength plastic.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the specific embodiments and the attached drawings:
the comparative examples in the present invention, which are used to illustrate the effect of changes in the use of a certain component on the product, also constitute embodiments of the present invention.
Example 1:
a preparation method of a high-strength plastic toughening agent,
preparation of end-capped acrylamide propyl siloxane: adding the aminopropyl siloxane into dichloromethane, mixing to obtain an aminopropyl siloxane solution, adding anhydrous potassium carbonate, dropwise adding an acryloyl chloride solution at the temperature of 0 ℃, reacting for 4 hours at the temperature of 35 ℃ after the dropwise adding is finished, washing with a sodium bicarbonate solution, deionized water and saturated saline solution, drying, and removing the solvent dichloromethane by rotary evaporation to obtain the end-capped acrylamide propyl siloxane. The terminal aminopropyl siloxane is 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the terminal aminopropyl siloxane solution contains 60wt% of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the anhydrous potassium carbonate is used in an amount of 1.2wt% of the terminal aminopropyl siloxane solution, the acrylic chloride solution contains 60wt% of acrylic chloride, the acrylic chloride solution is used in an amount such that the molar amount of acrylic chloride is 240% of the molar amount of the terminal aminopropyl siloxane, and the sodium bicarbonate solution contains 5wt% of sodium bicarbonate.
Preparation of modified acrylate: adding an emulsifier into deionized water, stirring and mixing, adding BA, st, MMA and end-capped acrylamide propyl siloxane, stirring and mixing to obtain a pre-emulsion, carrying out ultrasonic treatment for 20min, adding an APS solution at the temperature of 80 ℃, reacting for 5h, cooling to 35 ℃ after the reaction is finished, adjusting the pH value to 7, filtering to obtain a modified acrylic ester emulsion, adding calcium phytate, stirring and mixing, carrying out ultrasonic treatment for 20min, drying, and crushing to obtain the modified acrylic ester. The emulsifier is formed by mixing an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is SDS, the nonionic emulsifier is NP-30, the content of the anionic emulsifier in the emulsifier is 40wt%, the content of the emulsifier in the pre-emulsion is 4wt%, the content of BA in the pre-emulsion is 30wt%, the use amount of St is 15wt% of BA, the use amount of MMA is 10wt% of BA, the use amount of end-capped acrylamide propyl siloxane is 12wt% of BA, the APS solution contains 4wt% of APS, the use amount of the APS solution is 3wt% of the pre-emulsion, and the use amount of calcium phytate is 3wt% of the modified acrylate emulsion.
Example 2:
a preparation method of a high-strength plastic toughening agent,
preparation of end-capped acrylamide propyl siloxane: adding the aminopropyl siloxane into dichloromethane, mixing to obtain an aminopropyl siloxane solution, adding anhydrous potassium carbonate, dropwise adding an acryloyl chloride solution at the temperature of 0 ℃, reacting for 4 hours at the temperature of 35 ℃ after the dropwise adding is finished, washing with a sodium bicarbonate solution, deionized water and saturated saline solution, drying, and removing the solvent dichloromethane by rotary evaporation to obtain the end-capped acrylamide propyl siloxane. The terminal aminopropyl siloxane is 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the terminal aminopropyl siloxane solution contains 60wt% of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the anhydrous potassium carbonate is used in an amount of 1.2wt% of the terminal aminopropyl siloxane solution, the acrylic chloride solution contains 60wt% of acrylic chloride, the acrylic chloride solution is used in an amount such that the molar amount of acrylic chloride is 240% of the molar amount of the terminal aminopropyl siloxane, and the sodium bicarbonate solution contains 5wt% of sodium bicarbonate.
Preparation of modified acrylate: adding an emulsifier into deionized water, stirring and mixing, adding BA, st, MMA and end-capped acrylamide propyl siloxane, stirring and mixing to obtain a pre-emulsion, carrying out ultrasonic treatment for 20min, adding an APS solution at the temperature of 80 ℃, reacting for 5h, cooling to 35 ℃ after the reaction is finished, adjusting the pH value to 7, filtering to obtain a modified acrylic ester emulsion, adding calcium phytate, stirring and mixing, carrying out ultrasonic treatment for 20min, drying, and crushing to obtain the modified acrylic ester. The emulsifier is formed by mixing an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is SDS, the nonionic emulsifier is NP-30, the content of the anionic emulsifier in the emulsifier is 40wt%, the content of the emulsifier in the pre-emulsion is 4wt%, the content of BA in the pre-emulsion is 30wt%, the use amount of St is 15wt% of BA, the use amount of MMA is 10wt% of BA, the use amount of end-capped acrylamide propyl siloxane is 12wt% of BA, the APS solution contains 4wt% of APS, the use amount of the APS solution is 3wt% of the pre-emulsion, and the use amount of calcium phytate is 8wt% of the modified acrylate emulsion.
Example 3:
a preparation method of high-strength plastic,
preparation of end-capped acrylamide propyl siloxane: adding the aminopropyl siloxane into dichloromethane, mixing to obtain an aminopropyl siloxane solution, adding anhydrous potassium carbonate, dropwise adding an acryloyl chloride solution at the temperature of 0 ℃, reacting for 4 hours at the temperature of 35 ℃ after the dropwise adding is finished, washing with a sodium bicarbonate solution, deionized water and saturated saline solution, drying, and removing the solvent dichloromethane by rotary evaporation to obtain the end-capped acrylamide propyl siloxane. The terminal aminopropyl siloxane is 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the terminal aminopropyl siloxane solution contains 60wt% of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the anhydrous potassium carbonate is used in an amount of 1.2wt% of the terminal aminopropyl siloxane solution, the acrylic chloride solution contains 60wt% of acrylic chloride, the acrylic chloride solution is used in an amount such that the molar amount of acrylic chloride is 240% of the molar amount of the terminal aminopropyl siloxane, and the sodium bicarbonate solution contains 5wt% of sodium bicarbonate.
Preparation of modified acrylate: adding an emulsifier into deionized water, stirring and mixing, adding BA, st, MMA and end-capped acrylamide propyl siloxane, stirring and mixing to obtain a pre-emulsion, carrying out ultrasonic treatment for 20min, adding an APS solution at the temperature of 80 ℃, reacting for 5h, cooling to 35 ℃ after the reaction is finished, adjusting the pH value to 7, filtering to obtain a modified acrylic ester emulsion, adding calcium phytate, stirring and mixing, carrying out ultrasonic treatment for 20min, drying, and crushing to obtain the modified acrylic ester. The emulsifier is formed by mixing an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is SDS, the nonionic emulsifier is NP-30, the content of the anionic emulsifier in the emulsifier is 40wt%, the content of the emulsifier in the pre-emulsion is 4wt%, the content of BA in the pre-emulsion is 30wt%, the use amount of St is 15wt% of BA, the use amount of MMA is 10wt% of BA, the use amount of end-capped acrylamide propyl siloxane is 12wt% of BA, the APS solution contains 4wt% of APS, the use amount of the APS solution is 3wt% of the pre-emulsion, and the use amount of calcium phytate is 8wt% of the modified acrylate emulsion.
Preparation of high-strength plastic: mixing PVC resin, a composite lead stabilizer, stearic acid 1801, paraffin, light calcium carbonate and modified acrylic ester, adding into a high-speed mixer, mixing at 100 ℃ for 1.5 hours, then in a plasticator, carrying out open mill at 170 ℃, continuously punching triangular bags and rolling until the material is uniform in color and luster and the cut section does not show hairgrain, adjusting the roll gap, carrying out thin pass for 3 times, adjusting the roll gap according to the required thickness, discharging sheets to obtain high-strength plastic sheets, and carrying out mould pressing treatment on the high-strength plastic sheets to obtain the high-strength plastic. The usage amount of the composite lead stabilizer is 5wt% of the PVC resin, the usage amount of stearic acid 1801 is 0.9wt% of the PVC resin, the usage amount of paraffin is 1.2wt% of the PVC resin, the usage amount of light calcium carbonate is 5wt% of the PVC resin, and the usage amount of modified acrylic ester is 4wt% of the PVC resin.
The mould pressing treatment process comprises the following steps: the method comprises the steps of placing a die on a flat vulcanizing machine for preheating, placing a high-strength plastic sheet in the die, prepressing for 5min at 180 ℃, exhausting for 15 times, treating for 5min at 10MPa after exhausting is completed, and finally keeping pressure on a cold press for shaping and cooling to room temperature.
Example 4:
a preparation method of high-strength plastic,
preparation of end-capped acrylamide propyl siloxane: adding the aminopropyl siloxane into dichloromethane, mixing to obtain an aminopropyl siloxane solution, adding anhydrous potassium carbonate, dropwise adding an acryloyl chloride solution at the temperature of 0 ℃, reacting for 4 hours at the temperature of 35 ℃ after the dropwise adding is finished, washing with a sodium bicarbonate solution, deionized water and saturated saline solution, drying, and removing the solvent dichloromethane by rotary evaporation to obtain the end-capped acrylamide propyl siloxane. The terminal aminopropyl siloxane is 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the terminal aminopropyl siloxane solution contains 60wt% of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the anhydrous potassium carbonate is used in an amount of 1.2wt% of the terminal aminopropyl siloxane solution, the acrylic chloride solution contains 60wt% of acrylic chloride, the acrylic chloride solution is used in an amount such that the molar amount of acrylic chloride is 240% of the molar amount of the terminal aminopropyl siloxane, and the sodium bicarbonate solution contains 5wt% of sodium bicarbonate.
Preparation of modified acrylate: adding an emulsifier into deionized water, stirring and mixing, adding BA, st, MMA and end-capped acrylamide propyl siloxane, stirring and mixing to obtain a pre-emulsion, carrying out ultrasonic treatment for 20min, adding an APS solution at the temperature of 80 ℃, reacting for 5h, cooling to 35 ℃ after the reaction is finished, adjusting the pH value to 7, filtering to obtain a modified acrylic ester emulsion, adding calcium phytate, stirring and mixing, carrying out ultrasonic treatment for 20min, drying, and crushing to obtain the modified acrylic ester. The emulsifier is formed by mixing an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is SDS, the nonionic emulsifier is NP-30, the content of the anionic emulsifier in the emulsifier is 40wt%, the content of the emulsifier in the pre-emulsion is 4wt%, the content of BA in the pre-emulsion is 30wt%, the use amount of St is 15wt% of BA, the use amount of MMA is 10wt% of BA, the use amount of end-capped acrylamide propyl siloxane is 12wt% of BA, the APS solution contains 4wt% of APS, the use amount of the APS solution is 3wt% of the pre-emulsion, and the use amount of calcium phytate is 8wt% of the modified acrylate emulsion.
Preparation of high-strength plastic: mixing PVC resin, a composite lead stabilizer, stearic acid 1801, paraffin, light calcium carbonate and modified acrylic ester, adding into a high-speed mixer, mixing at 100 ℃ for 1.5 hours, then in a plasticator, carrying out open mill at 170 ℃, continuously punching triangular bags and rolling until the material is uniform in color and luster and the cut section does not show hairgrain, adjusting the roll gap, carrying out thin pass for 3 times, adjusting the roll gap according to the required thickness, discharging sheets to obtain high-strength plastic sheets, and carrying out mould pressing treatment on the high-strength plastic sheets to obtain the high-strength plastic. The usage amount of the composite lead stabilizer is 5wt% of the PVC resin, the usage amount of stearic acid 1801 is 0.9wt% of the PVC resin, the usage amount of paraffin is 1.2wt% of the PVC resin, the usage amount of light calcium carbonate is 5wt% of the PVC resin, and the usage amount of modified acrylic ester is 9wt% of the PVC resin.
The mould pressing treatment process comprises the following steps: the method comprises the steps of placing a die on a flat vulcanizing machine for preheating, placing a high-strength plastic sheet in the die, prepressing for 5min at 180 ℃, exhausting for 15 times, treating for 5min at 10MPa after exhausting is completed, and finally keeping pressure on a cold press for shaping and cooling to room temperature.
Example 5:
a preparation method of high-strength plastic,
preparation of end-capped acrylamide propyl siloxane: adding the aminopropyl siloxane into dichloromethane, mixing to obtain an aminopropyl siloxane solution, adding anhydrous potassium carbonate, dropwise adding an acryloyl chloride solution at the temperature of 0 ℃, reacting for 4 hours at the temperature of 35 ℃ after the dropwise adding is finished, washing with a sodium bicarbonate solution, deionized water and saturated saline solution, drying, and removing the solvent dichloromethane by rotary evaporation to obtain the end-capped acrylamide propyl siloxane. The terminal aminopropyl siloxane is 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the terminal aminopropyl siloxane solution contains 60wt% of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the anhydrous potassium carbonate is used in an amount of 1.2wt% of the terminal aminopropyl siloxane solution, the acrylic chloride solution contains 60wt% of acrylic chloride, the acrylic chloride solution is used in an amount such that the molar amount of acrylic chloride is 240% of the molar amount of the terminal aminopropyl siloxane, and the sodium bicarbonate solution contains 5wt% of sodium bicarbonate.
Preparation of modified acrylate: adding an emulsifier into deionized water, stirring and mixing, adding BA, st, MMA and end-capped acrylamide propyl siloxane, stirring and mixing to obtain a pre-emulsion, carrying out ultrasonic treatment for 20min, adding an APS solution at the temperature of 80 ℃, reacting for 5h, cooling to 35 ℃ after the reaction is finished, adjusting the pH value to 7, filtering to obtain a modified acrylic ester emulsion, adding calcium phytate, stirring and mixing, carrying out ultrasonic treatment for 20min, drying, and crushing to obtain the modified acrylic ester. The emulsifier is formed by mixing an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is SDS, the nonionic emulsifier is NP-30, the content of the anionic emulsifier in the emulsifier is 40wt%, the content of the emulsifier in the pre-emulsion is 4wt%, the content of BA in the pre-emulsion is 30wt%, the use amount of St is 15wt% of BA, the use amount of MMA is 10wt% of BA, the use amount of end-capped acrylamide propyl siloxane is 12wt% of BA, the APS solution contains 4wt% of APS, the use amount of the APS solution is 3wt% of the pre-emulsion, and the use amount of calcium phytate is 8wt% of the modified acrylate emulsion.
Preparation of high-strength plastic: mixing PVC resin, a composite lead stabilizer, stearic acid 1801, paraffin, light calcium carbonate, modified acrylic ester and cyclopentane carboxylic acid ethyl ester, adding into a high-speed mixer, mixing at 100 ℃ for 1.5h, then in a plasticator, carrying out open mill at 170 ℃, continuously punching triangular bags and rolling until the materials are uniform in color and luster and the cut section does not show hairgrain, adjusting the roll gap, carrying out thin pass for 3 times, adjusting the roll gap according to the required thickness, discharging sheets to obtain high-strength plastic sheets, and carrying out mould pressing treatment on the high-strength plastic sheets to obtain the high-strength plastic. The usage amount of the composite lead stabilizer is 5wt% of the PVC resin, the usage amount of stearic acid 1801 is 0.9wt% of the PVC resin, the usage amount of paraffin is 1.2wt% of the PVC resin, the usage amount of light calcium carbonate is 5wt% of the PVC resin, the usage amount of modified acrylic ester is 9wt% of the PVC resin, and the usage amount of cyclopentane carboxylic acid ethyl ester is 2wt% of the PVC resin.
The mould pressing treatment process comprises the following steps: the method comprises the steps of placing a die on a flat vulcanizing machine for preheating, placing a high-strength plastic sheet in the die, prepressing for 5min at 180 ℃, exhausting for 15 times, treating for 5min at 10MPa after exhausting is completed, and finally keeping pressure on a cold press for shaping and cooling to room temperature.
Example 6:
a preparation method of high-strength plastic,
preparation of end-capped acrylamide propyl siloxane: adding the aminopropyl siloxane into dichloromethane, mixing to obtain an aminopropyl siloxane solution, adding anhydrous potassium carbonate, dropwise adding an acryloyl chloride solution at the temperature of 0 ℃, reacting for 4 hours at the temperature of 35 ℃ after the dropwise adding is finished, washing with a sodium bicarbonate solution, deionized water and saturated saline solution, drying, and removing the solvent dichloromethane by rotary evaporation to obtain the end-capped acrylamide propyl siloxane. The terminal aminopropyl siloxane is 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the terminal aminopropyl siloxane solution contains 60wt% of 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane, the anhydrous potassium carbonate is used in an amount of 1.2wt% of the terminal aminopropyl siloxane solution, the acrylic chloride solution contains 60wt% of acrylic chloride, the acrylic chloride solution is used in an amount such that the molar amount of acrylic chloride is 240% of the molar amount of the terminal aminopropyl siloxane, and the sodium bicarbonate solution contains 5wt% of sodium bicarbonate.
Preparation of modified acrylate: adding an emulsifier into deionized water, stirring and mixing, adding BA, st, MMA and end-capped acrylamide propyl siloxane, stirring and mixing to obtain a pre-emulsion, carrying out ultrasonic treatment for 20min, adding an APS solution at the temperature of 80 ℃, reacting for 5h, cooling to 35 ℃ after the reaction is finished, adjusting the pH value to 7, filtering to obtain a modified acrylic ester emulsion, adding calcium phytate, stirring and mixing, carrying out ultrasonic treatment for 20min, drying, and crushing to obtain the modified acrylic ester. The emulsifier is formed by mixing an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is SDS, the nonionic emulsifier is NP-30, the content of the anionic emulsifier in the emulsifier is 40wt%, the content of the emulsifier in the pre-emulsion is 4wt%, the content of BA in the pre-emulsion is 30wt%, the use amount of St is 15wt% of BA, the use amount of MMA is 10wt% of BA, the use amount of end-capped acrylamide propyl siloxane is 12wt% of BA, the APS solution contains 4wt% of APS, the use amount of the APS solution is 3wt% of the pre-emulsion, and the use amount of calcium phytate is 8wt% of the modified acrylate emulsion.
Preparation of high-strength plastic: mixing PVC resin, a composite lead stabilizer, stearic acid 1801, paraffin, light calcium carbonate, modified acrylic ester and cyclopentane carboxylic acid ethyl ester, adding into a high-speed mixer, mixing at 100 ℃ for 1.5h, then in a plasticator, carrying out open mill at 170 ℃, continuously punching triangular bags and rolling until the materials are uniform in color and luster and the cut section does not show hairgrain, adjusting the roll gap, carrying out thin pass for 3 times, adjusting the roll gap according to the required thickness, discharging sheets to obtain high-strength plastic sheets, and carrying out mould pressing treatment on the high-strength plastic sheets to obtain the high-strength plastic. The usage amount of the composite lead stabilizer is 5wt% of the PVC resin, the usage amount of stearic acid 1801 is 0.9wt% of the PVC resin, the usage amount of paraffin is 1.2wt% of the PVC resin, the usage amount of light calcium carbonate is 5wt% of the PVC resin, the usage amount of modified acrylic ester is 9wt% of the PVC resin, and the usage amount of cyclopentane carboxylic acid ethyl ester is 4wt% of the PVC resin.
The mould pressing treatment process comprises the following steps: the method comprises the steps of placing a die on a flat vulcanizing machine for preheating, placing a high-strength plastic sheet in the die, prepressing for 5min at 180 ℃, exhausting for 15 times, treating for 5min at 10MPa after exhausting is completed, and finally keeping pressure on a cold press for shaping and cooling to room temperature.
Comparative example 1:
a preparation method of a high-strength plastic toughening agent,
this comparative example differs from example 2 only in that calcium phytate was not used in the preparation of the modified acrylate.
Comparative example 2:
a preparation method of a high-strength plastic toughening agent,
this comparative example differs from example 2 only in that no blocked acrylamidopropyl siloxane was used in the preparation of the modified acrylate.
Comparative example 3:
a preparation method of a high-strength plastic toughening agent,
this comparative example differs from example 2 only in that calcium phytate and end-capped acrylamidopropyl siloxanes are not used in the modified acrylate preparation.
Comparative example 4:
a preparation method of high-strength plastic,
this comparative example differs from example 4 only in that calcium phytate was not used in the preparation of the modified acrylate.
Comparative example 5:
a preparation method of high-strength plastic,
this comparative example differs from example 4 only in that no blocked acrylamidopropyl siloxane was used in the preparation of the modified acrylate.
Comparative example 6:
a preparation method of high-strength plastic,
this comparative example differs from example 4 only in that calcium phytate and end-capped acrylamidopropyl siloxanes are not used in the modified acrylate preparation.
Test example:
1. characterization by Infrared Spectroscopy
Test sample: the end-capped acrylamidopropyl siloxanes prepared in example 1.
The infrared spectrum of the end-capped acrylamide propyl siloxane prepared by the invention is shown in figure 1, wherein an infrared absorption peak of a carbon-oxygen double bond is arranged at 1712cm < -1 >, an infrared absorption peak of a carbon-carbon double bond is arranged at 1628cm < -1 >, a characteristic infrared absorption peak of an amide is arranged at 1551cm < -1 >, an infrared absorption peak of a silicon-carbon bond is arranged at 1252cm < -1 >, and an infrared absorption peak of silicon-oxygen silicon is arranged at 1016cm < -1 >, which shows that the end-capped acrylamide propyl siloxane is obtained.
2. Adhesive film water absorption test
The preparation method of the adhesive film comprises the following steps: pouring the modified acrylic ester emulsion into a mould, drying at room temperature to form a film, then treating at 90 ℃ for 10min, and finally treating at 160 ℃ for 5min to obtain the adhesive film.
Test sample: the modified acrylate emulsions obtained in examples 1-2 and comparative examples 1-3 were prepared into adhesive films according to the preparation method of the adhesive films.
The test sample was dried at 90 ℃ for 2h, weighed, then the test sample was immersed in water for 24h, taken out, blotted to dry the surface moisture, and weighed.
The water absorption is calculated according to the following formula:
water absorption = (wet weight-dry weight)/dry weight x 100%.
The water absorption test results of the adhesive film prepared by the method are shown in fig. 2, wherein A is example 1, B is example 2, C is comparative example 1, D is comparative example 2, E is comparative example 3, the water absorption of the adhesive film prepared by the modified acrylate emulsion in example 1 is 7.16%, the water absorption of the adhesive film prepared by the modified acrylate emulsion in example 2 is 5.28%, the water absorption of the adhesive film prepared by comparative example 3 is 27.64%, and compared with comparative example 3, the water absorption of the adhesive film prepared by the method in example 2 is greatly reduced when the end-capped acrylamide propyl siloxane and the calcium phytate are used together, and the water absorption of the adhesive film prepared by the end-capped acrylamide propyl siloxane and the calcium phytate are used together, so that the effect of reducing the water absorption of the modified acrylate adhesive film is shown; the water absorption of the adhesive film prepared from the modified acrylate emulsion in comparative example 1 was 25.35%, the water absorption of the adhesive film prepared from the modified acrylate emulsion in comparative example 2 was 21.43%, the use of the end-capped acrylamide propyl siloxane together with calcium phytate was shown to be superior to the use of the end-capped acrylamide propyl siloxane alone or calcium phytate in comparison with comparative example 1, the use of the end-capped acrylamide propyl siloxane alone was shown to be superior to the use of calcium phytate in comparison with comparative example 2, and it was found that the use of calcium phytate further had a higher effect of reducing the water absorption of the adhesive film in the use of the end-capped acrylamide propyl siloxane by comparison between example 2 and comparative examples 1 to 3.
The water absorption rate of the adhesive film prepared by the invention is 4-28%.
3. Adhesive film tensile property test
Test sample: the modified acrylate emulsions obtained in examples 1-2 and comparative examples 1-3 were prepared into adhesive films according to the preparation method of the adhesive films.
And the tensile strength of the adhesive film is tested by the test sample by adopting an electronic universal material tester.
The tensile property test results of the adhesive film prepared by the method are shown in fig. 3, wherein A is example 1, B is example 2, C is comparative example 1, D is comparative example 2, E is comparative example 3, the tensile property of the adhesive film prepared by the modified acrylate emulsion in example 1 is 0.48MPa, the tensile property of the adhesive film prepared by the modified acrylate emulsion in example 2 is 0.42 MPa, the tensile property of the adhesive film prepared by comparative example 3 is 0.74 MPa, and compared with comparative example 3, the tensile property of the adhesive film prepared by the method is greatly reduced when the end-capped acrylamide propyl siloxane and the calcium phytate are used together, and the mechanical property of the adhesive film prepared by the end-capped acrylamide propyl siloxane and the calcium phytate is reduced when other components are used together; the tensile properties of the adhesive film prepared from the modified acrylate emulsion in comparative example 1 were 0.64 MPa, the tensile properties of the adhesive film prepared from the modified acrylate emulsion in comparative example 2 were 0.58 MPa, example 2 compared with comparative examples 1-2 showed that the co-use of the end-capped acrylamide propyl siloxane with calcium phytate was superior to the use of the end-capped acrylamide propyl siloxane alone or calcium phytate alone, comparative example 1 compared with comparative example 2 showed that the use of the end-capped acrylamide propyl siloxane alone was superior to the use of calcium phytate alone, and it was found by comparison between example 2 and comparative examples 1-3 that the further use of calcium phytate had a higher effect of reducing the tensile properties of the adhesive film under the use of the end-capped acrylamide propyl siloxane.
The tensile strength of the adhesive film prepared by the invention is 0.4-0.8MPa.
4. Impact performance test
Test sample: high strength plastics prepared by the methods of examples 3-6 and comparative examples 4-6.
The test specimens were cut into bars according to the standard, the dimensions were 80 mm. Times.10 mm. Times.4 mm, the notches were milled, the remaining dimensions of the notches were 8mm, and the impact properties were tested according to the GB/T1043 standard.
The impact property test results of the high-strength plastic prepared by the invention are shown in fig. 4, wherein A is example 3, B is example 4, C is example 5, D is example 6,E, comparative example 4,F is comparative example 5, G is comparative example 6, the impact strength of the high-strength plastic prepared by example 3 is 14.37KJ/m2, the impact strength of the high-strength plastic prepared by example 4 is 16.59KJ/m2, the impact strength of the high-strength plastic prepared by comparative example 6 is 8.21KJ/m2, and compared with comparative example 6, the impact strength of the high-strength plastic prepared by example 4 is greatly improved by using the end-capped acrylamide propyl siloxane and the calcium phytate together, and the impact resistance of the high-strength plastic prepared by using the end-capped acrylamide propyl siloxane and the calcium phytate together as toughening agent and PVC resin and other raw materials is improved; the impact strength of the high-strength plastic prepared in comparative example 4 was 11.32KJ/m2, the impact strength of the high-strength plastic prepared in comparative example 5 was 9.69KJ/m2, example 4 compared with comparative examples 3 to 4, showing that the co-use of the end-capped acrylamide propyl siloxane with calcium phytate was superior to the use of the end-capped acrylamide propyl siloxane or calcium phytate alone, comparative example 3 compared with comparative example 4, showing that the use of the end-capped acrylamide propyl siloxane alone was superior to the use of calcium phytate alone, and through the comparison between example 4 and comparative examples 4 to 6, it was found that the further use of calcium phytate had a higher effect of improving the impact resistance of the high-strength plastic under the use of the end-capped acrylamide propyl siloxane; the impact strength of the high-strength plastic prepared in example 5 was 18.74KJ/m2, the impact strength of the high-strength plastic prepared in example 6 was 19.81KJ/m2, and examples 5 to 6 compared with example 4 show that the use of ethyl cyclopentanecarboxylate can further improve the impact resistance of the high-strength plastic when the high-strength plastic was prepared using the end-capped acrylamide propyl siloxane with calcium phytate and other raw materials.
The high-strength plastic prepared by the invention has good impact resistance and impact strength of 13-20KJ/m < 2 >.
The above embodiments are merely for illustrating the present invention and not for limiting the same, and various changes and modifications may be made by one of ordinary skill in the art without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions are also within the scope of the present invention, which is defined by the claims.

Claims (7)

1. A method for preparing a modified acrylate comprising:
reacting terminal aminopropyl siloxane with acryloyl chloride to prepare terminal acrylamide aminopropyl siloxane, wherein the terminal aminopropyl siloxane is 1, 3-bis (3-aminopropyl) -1, 3-tetramethyl disiloxane; the molar quantity of the acrylic chloride is 200-300% of the molar quantity of the amino-terminated propyl siloxane;
and adding an initiator into an emulsion containing BA, st, MMA and end-capped acrylamide propyl siloxane, reacting to generate modified acrylic ester emulsion, filtering, adding calcium phytate, mixing, and drying to obtain modified acrylic ester, wherein the emulsifying agent used in the emulsion comprises an anionic emulsifying agent and a nonionic emulsifying agent.
2. The method for preparing the modified acrylic ester according to claim 1, which is characterized in that: the use amount of the calcium phytate is 2-10wt% of the modified acrylic ester emulsion.
3. The method for preparing the modified acrylic ester according to claim 1, which is characterized in that: the initiator is APS.
4. A modified acrylate prepared by the process of any one of claims 1-3.
5. Use of the modified acrylates of claim 4 for the preparation of plastics materials.
6. A method for preparing high strength plastic, comprising: mixing PVC resin, a composite lead stabilizer, stearic acid 1801, paraffin, light calcium carbonate and the modified acrylic ester according to claim 4, adding into a high-speed mixer, mixing at 90-110 ℃ for 0.5-3h, then in a plasticator, carrying out open mill at 160-180 ℃, continuously beating triangular bags and rolling until the material has uniform color and luster and no feather particle appears on the cut section, adjusting the roll spacing, thinning for 3-4 times, adjusting the roll spacing according to the required thickness, discharging to obtain a high-strength plastic sheet, and carrying out mould pressing treatment on the high-strength plastic sheet to obtain the high-strength plastic.
7. The high strength plastic produced by the method of claim 6.
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