CN114874382A - Method for preparing acrylate foam material by double-initiation and double-curing through water bath microwave method - Google Patents
Method for preparing acrylate foam material by double-initiation and double-curing through water bath microwave method Download PDFInfo
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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
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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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
- 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
- C08J2333/06—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 only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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Abstract
The invention discloses a method for preparing an acrylate foam material by double-initiation and double-curing through a water bath microwave method, which is prepared from an acrylate monomer, an emulsifier, an oil-soluble initiator, a water-soluble initiator and an electrolyte solution, wherein the preparation method comprises the steps of preparing an oil phase, preparing a water phase, emulsifying, scraping and coating a mold, performing water bath microwave curing, washing and drying; according to the invention, the double initiator is used for effectively initiating the acrylic ester monomer to carry out crosslinking reaction, and then the material is prepared through water bath microwave curing, so that the preparation process is short in time consumption and low in energy consumption, and compared with the traditional single thermal curing method, the preparation method provided by the invention has the advantages of improving the production efficiency, saving energy and reducing emission, and meeting the large production condition; the invention adopts the water-in-oil type emulsion, the polarity of water is strong, microwave is easy to absorb, the curing time is shortened, the water bath microwave method ensures that the temperature of the inner layer and the outer layer of the emulsion is more uniform, the initiation time is more synchronous, the curing state is more uniform, the physical properties such as the toughness of the material are improved, and the water absorption multiple and the absorption speed are also improved.
Description
Technical Field
The invention relates to a method for preparing an acrylate foam material, in particular to a method for preparing an acrylate foam material by double-initiation and double-curing through a water bath microwave method.
Background
The existing methods for preparing the acrylic ester foam material comprise a heat drying method, a water bath method, a steam method and the like, and the principles of the methods are that an external heat source conducts and heats from the outside to the inside through heat radiation, but the preparation methods have the advantages of low energy utilization rate, long curing time, uneven temperature distribution, time and energy consumption, low mass production efficiency, and lower toughness of the synthesized acrylic ester foam material.
The same applicant of the application previously filed a short fiber toughened water-absorbent acrylate polymer material and a preparation method thereof, wherein the publication number is CN113637278A, the preparation method utilizes a water vapor method to cure the material, and the water absorption multiple of the obtained material is less than 15 times, and the longitudinal breaking strength and the transverse breaking strength are only 6.56N/25mm and 3.95N/25 mm. Further, as in the case of the solutions disclosed in patent documents CN113771439A and CN113796621A, the material is cured by the water vapor method, and the obtained product is not satisfactory in the longitudinal rupture strength, transverse rupture strength, and water absorption capacity.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing an acrylate foam material by double-initiated double curing by a water bath microwave method.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing an acrylate foam material by double-initiation and double-curing through a water bath microwave method is prepared from the following raw materials in parts by weight: 2-5 parts of acrylate monomer, 0.3-3 parts of emulsifier, 0.02-0.2 part of oil-soluble initiator, 0.2-2 parts of water-soluble initiator and 89-97.5 parts of electrolyte solution, wherein the acrylate monomer consists of skeleton monomer and crosslinking monomer, and the oil-soluble initiator is dihexyl azodiisobutyrate and comprises the following steps:
(1) preparing an oil phase: heating the oil phase mixing pot to 45-55 ℃, simultaneously putting the acrylic ester monomers, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, starting stirring at the stirring speed of 100-800 revolutions per minute for 15-30 minutes to obtain an oil phase for later use.
(2) And preparing a water phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and stirring at the stirring speed of 30-50 rpm for 15-30 minutes until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And emulsification: transferring the 1/5-1/4 water phase in the step (2) to a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 70-80 ℃, starting stirring at the stirring speed of 500-, and stirring at the stirring speed of 200-300 rpm for standby.
(4) And (3) scraping and coating a die: and (4) blade-coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating for later use.
(5) And water bath microwave curing: transferring and conveying the caterpillar mold with the emulsion in the step (4) to a water bath microwave curing furnace, performing linear curing on the material through water bath and microwave at the same time, controlling the linear speed to control the flowing time to be 2-5 minutes, controlling the microwave power to be 1500-plus 3000GHz, and controlling the water bath temperature to be 75-95 ℃.
(6) And washing: and (3) washing the cured raw material, namely washing the raw material by using deionized water mixed with a surfactant solution, and then washing the raw material by using deionized water to remove residual monomers.
(7) And drying: and transferring the washed raw materials into a negative pressure high temperature drying pot for drying and dehydrating, wherein the pressure and the temperature are conventionally set, and the drying time is 2-4 hours, so as to obtain the acrylic ester foam material.
The synthesis steps of the oil-soluble initiator are as follows:
(1) adding azodiisobutyronitrile hydrazine into a three-neck flask A provided with a stirrer, a gas-guide tube and a thermometer, adding excessive hexanol, stirring to dissolve, introducing chlorine gas under cooling of an ice water bath to obtain a mixture, fully stirring the mixture at the stirring speed of 30-50 revolutions per minute, and carrying out oxidation reaction for 4-5 hours to obtain an intermediate A.
(2) And (2) introducing dry hydrogen chloride gas into the three-neck flask A in the step (1) at 15 ℃, reacting for 18-20h at the temperature after introduction, carrying out a Pinner reaction, and then carrying out suction filtration to obtain an intermediate B.
(3) Adding deionized water into a three-neck flask B, starting stirring at the stirring speed of 30-50 revolutions per minute, placing the three-neck flask B into ice water while stirring for cooling, then adding an intermediate B into the three-neck flask B, raising the temperature to 20 ℃ after adding, stirring for 3-5 hours, hydrolyzing to obtain a reaction mixture after hydrolysis, cooling the reaction mixture until solid is separated out to obtain a corresponding crude product, and recrystallizing the crude product with ethanol and water to obtain a pure product, thus preparing dihexyl azodiisobutyrate, namely the required oil-soluble initiator.
The skeleton monomer is a composition of two or more of methyl methacrylate, ethyl dimethacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, lauryl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, isooctyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, tetradecyl methacrylate, octadecyl methacrylate, isooctyl acrylate, n-decyl acrylate, isodecyl acrylate, tetradecyl acrylate and octadecyl acrylate.
The crosslinking monomer is one or a composition of more than one of 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1, 12-dodecyl dimethacrylate, 1, 14-tetradecanediol dimethacrylate, ethylene glycol dimethacrylate and neopentyl triacrylate.
The water-soluble initiator is any one of sodium persulfate, potassium persulfate and ammonium persulfate.
The emulsifier is a water-in-oil emulsifier, and the HLB value of the emulsifier is 3-6.
The emulsifier is diglycerol isostearate.
The electrolyte solution is calcium chloride solution or sodium chloride solution, and the concentration of the electrolyte solution is 1-4%.
The invention has the beneficial effects that:
1. the invention utilizes the dual initiator to initiate the acrylate to carry out water bath microwave curing to form the composite high polymer material, wherein one initiator, namely the azodiisobutyrate dihexyl ester, is developed and synthesized by the initiator, the dual initiator is used to effectively initiate the acrylate monomer to carry out crosslinking reaction, thereby preventing chain termination reaction from being carried out too early, the residual monomer amount after the reaction is very little, the water bath microwave curing is utilized to prepare the acrylate foam material, the preparation process has short time consumption and little energy consumption, compared with the traditional single heat curing method, the invention improves the production efficiency, has the advantages of energy saving and emission reduction, and meets the large production condition.
2. The water-in-oil type emulsion is adopted, water belongs to a substance with strong polarity, microwaves are easily absorbed, the absorbed microwaves are converted into heat energy, the curing time is greatly shortened through water bath energy storage and energy transfer, the temperature of the inner layer and the outer layer of the emulsion is more uniform through a water bath microwave method, the initiation time is more synchronous, and the curing state is more uniform, so that the physical properties such as toughness and the like of the acrylate foam material obtained after the water bath microwave curing are improved, and the water absorption capacity and the absorption speed are also improved.
Detailed Description
In all the examples of the present invention, the temperature and pressure are not particularly emphasized, and are both normal temperature and normal pressure, and the equipment use is not particularly described, and the equipment can be used according to the conventional setting.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
The method for preparing the acrylic ester foam material comprises a hot baking method, a water bath method, a steam method and the like, and because the methods consume time and energy and have low mass production efficiency, the synthesized acrylic ester foam material has lower toughness. The invention adopts a water bath microwave method to synthesize the acrylic ester foam material by using the dual initiators, the time is short, the energy consumption is less, the prepared acrylic ester foam material has good toughness, the effects of energy conservation and emission reduction are achieved, and the method is a good synthesis method.
Microwaves generally refer to electromagnetic waves having a wavelength in the range of 0.1mm to 1000mm, and the corresponding frequency range is 300MHz to 3000 GHz. The conventional heating methods such as a heat drying method, a water bath method and a steam method have the principle that an external heat source heats the glass substrate through heat radiation from the outside to the inside, so that the energy utilization rate is low and the temperature distribution is uneven. Microwave heating: a heating mode for converting absorbed electromagnetic energy into thermal energy through dielectric molecules belongs to a body heating mode, the temperature is increased quickly, and the temperature inside and outside the heating mode is the same. The microwave with high frequency is selected, and the frequency range is 2000G-3000 GHz.
The invention discloses a preparation method of a water bath microwave dual-initiator acrylate foam material, which comprises the following steps: 2-5 parts of acrylate monomer, 0.3-3 parts of emulsifier, 0.02-0.2 part of oil-soluble initiator (dihexyl azodiisobutyrate), 0.2-2 parts of water-soluble initiator and 89-97.5 parts of electrolyte solution. The invention utilizes the dual initiator to initiate acrylic ester to carry out water bath microwave curing to form the composite high molecular material, wherein, one initiator, namely, the dihexyl azodiisobutyrate is developed and synthesized by the initiator, the dihexyl azodiisobutyrate is a novel oil-soluble azo initiator, the initiator contains polyfunctional groups of active groups, and the product is different from the azodiisobutyronitrile and the azodiisoheptonitrile in that no cyano group is contained, and the decomposition products are nontoxic, so that the nontoxic polymer can be prepared. The use of a diinitiator now effectively initiates the reaction of the acrylate, prevents premature excessive chain termination and leaves a small amount of monomer remaining after the reaction. The microwave curing is utilized, so that not only is energy saved, but also time is saved, the temperature of the emulsion is consistent from inside to outside by the microwave, the microwave is easily absorbed because the emulsion is water-in-oil emulsion, water belongs to a substance with strong polarity, the time required for curing is short because the absorbed microwave is converted into heat energy, and the performance of the material obtained after curing is good.
A method for preparing an acrylate foam material by double-initiation and double-curing through a water bath microwave method is prepared from the following raw materials in parts by weight: 2-5 parts of acrylate monomer, 0.3-3 parts of emulsifier, 0.02-0.2 part of oil-soluble initiator, 0.2-2 parts of water-soluble initiator and 89-97.5 parts of electrolyte solution, wherein the acrylate monomer consists of skeleton monomer and crosslinking monomer, the oil-soluble initiator is dihexyl azodiisobutyrate, and the preparation steps are as follows:
(1) preparing an oil phase: heating the oil phase mixing pot to 45-55 ℃, simultaneously putting the acrylic ester monomers, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, starting stirring at the stirring speed of 100-800 revolutions per minute for 15-30 minutes to obtain an oil phase for later use.
(2) And preparing a water phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and stirring at the stirring speed of 30-50 rpm for 15-30 minutes until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And emulsification: transferring the water phase from 1/5 to 1/4 in the step (2) to a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 70-80 ℃, starting stirring at the stirring speed of 500 plus materials for 800 r/min, then dripping all the oil phases obtained in the step (1) through a flow injector, after the oil phase feeding is finished, reducing the stirring speed to 300 plus materials for 500 r/min, adding the rest water phases from 3/4 to 4/5 through the flow injector, after the water phases are completely added, starting the homogenizing emulsifying machine at the homogenizing head rotation speed of 8000 plus materials for 10000 r/min, and keeping the homogenizing emulsifying time at 5-10 min to form initial emulsion with uniform dispersion and same grade particles, then closing the homogenizing emulsifying machine, starting stirring at the stirring speed of 300 plus materials for 500 r/min, keeping stirring for 5-10 min, obtaining the emulsion, then transferring the emulsion to a storage pot, and stirring at the stirring speed of 200-300 r/min for standby.
(4) And (3) scraping and coating a die: and (4) blade-coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating according to a certain thickness.
(5) And water bath microwave curing: the caterpillar mold with the emulsion is transferred and conveyed to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is simultaneously linearly cured by water bath and microwave. The line speed was controlled so that the flow-through time was controlled at 2-5 minutes. Wherein, the microwave power is controlled at 1500-3000 GHz. The temperature of the water bath is controlled between 75 and 95 ℃.
(6) And washing: and (3) washing the cured raw material, namely washing the raw material by using deionized water mixed with a surfactant solution, and then washing the raw material by using deionized water to remove residual monomers.
(7) And drying: and transferring the washed raw materials into a negative pressure high temperature drying pot for drying and dehydrating, wherein the pressure and the temperature are conventionally set, and the drying time is 2-4 hours, so as to obtain the acrylic ester foam material.
The oil-soluble initiator of the invention, namely the dihexyl azodiisobutyrate is developed and synthesized by itself, the dihexyl azodiisobutyrate is a novel oil-soluble azo initiator, the initiator contains a polyfunctional group of an active group, the dihexyl azodiisobutyrate is different from azodiisobutyronitrile and azodiisoheptonitrile in that no cyano group is contained, and decomposition products are nontoxic, so that a nontoxic polymer can be prepared. The oil-soluble initiator (dihexyl azodiisobutyrate) is synthesized by the following steps:
(1) adding azodiisobutyronitrile hydrazine (HAIBN, chemical formula C) into a three-neck flask A provided with a stirrer, an air guide tube and a thermometer 8 H 12 N 4 ) And adding excessive hexanol (n-hexanol produced by chemical Limited of Tongda in the Jinan century), and stirring to dissolve. Chlorine (generated by reaction with 1mol hydrazo-azobisisobutyronitrile) was bubbled through the ice water bath cooled2mol of HCl) to obtain a mixture, and the mixture is stirred at a stirring speed of 30-50 rpm and allowed to undergo an oxidation reaction for 4-5h to obtain intermediate a.
The reaction equation is as follows:
(2) and (2) introducing dry hydrogen chloride (chemical formula is HCl) gas into the three-neck flask A in the step (1) at 15 ℃, reacting for 18-20h at the temperature after introduction, carrying out a Pinner reaction, and then carrying out suction filtration to obtain an intermediate B.
The reaction equation is as follows:
(3) adding deionized water into a three-neck flask B, starting stirring at the stirring speed of 30-50 revolutions per minute, placing the three-neck flask B into ice water for cooling while stirring, then adding the intermediate B obtained in the step (2) into the three-neck flask B, raising the temperature to 20 ℃ after adding, stirring for 3-5 hours, hydrolyzing to obtain a reaction mixture, then cooling the reaction mixture until solid is separated out to obtain a corresponding crude product, and using ethanol (the chemical formula is C) for the crude product 2 H 6 O) and water are recrystallized to obtain a pure product, and the dihexyl azodiisobutyrate, namely the needed oil-soluble initiator, is prepared.
The reaction equation is as follows:
the skeleton monomer is methyl methacrylate (chemical formula is C) 5 H 8 O 2 ) Ethyl methacrylate (chemical formula C) 6 H 10 O 2 ) Ethyl dimethacrylate (chemical formula is C) 7 H 12 O 2 ) Butyl methacrylate (formula)Is C 8 H 14 O 2 ) Isobutyl methacrylate (chemical formula C) 8 H 14 O 2 ) Hexyl methacrylate (formula C) 10 H 18 O 2 ) Lauryl methacrylate (chemical formula C) 16 H 30 O 2 ) Isobornyl methacrylate (chemical formula C) 14 H 22 O 2 ) Cyclohexyl methacrylate (chemical formula C) 10 H 16 O 2 ) Isooctyl methacrylate (chemical formula C) 12 H 22 O 2 ) N-decyl methacrylate (formula C) 14 H 26 O 2 ) Isodecyl methacrylate (chemical formula C) 14 H 26 O 2 ) Tetradecyl methacrylate (chemical formula C) 18 H 34 O 2 ) Octadecyl methacrylate (chemical formula C) 22 H 43 O 2 ) Isooctyl acrylate (chemical formula is C) 11 H 20 O 2 ) N-decyl acrylate (chemical formula C) 13 H 24 O 2 ) Isodecyl acrylate (chemical formula C) 13 H 24 O 2 ) Tetradecyl acrylate (chemical formula C) 17 H 32 O 2 ) And octadecyl acrylate (formula C) 21 H 40 O 2 ) Two or more of them.
The crosslinking monomer is 1, 6-hexanediol diacrylate (chemical formula is C) 12 H 18 O 4 ) 1, 4-butanediol dimethacrylate (chemical formula C) 12 H 18 O 4 ) Trimethylolpropane triacrylate (chemical formula is C) 15 H 20 O 6 ) Trimethylolpropane trimethacrylate (chemical formula C) 18 H 26 O 6 ) 1, 12-dodecyl dimethacrylate (chemical formula C) 20 H 34 O 4 ) 1, 14-tetradecanediol dimethacrylate (chemical formula C) 22 H 38 O 4 ) Ethylene glycol dimethacrylate (molecular formula C) 10 H 14 O 4 ) And neopentyl triacrylate (chemical formula C) 8 H 14 O 2 ) One or more of the above compositions.
The water-soluble initiator is sodium persulfate (chemical formula is Na) 2 S 2 O 8 ) Potassium persulfate (formula K) 2 S 2 O 8 ) And ammonium persulfate (chemical formula is (NH) 4 ) 2 S 2 O 8 ) Any one of them. The water-soluble initiator initiates the reaction of the acrylate, prevents premature and excessive chain termination, and leaves a small amount of monomer after the reaction.
The emulsifier is a water-in-oil emulsifier, and the HLB value of the emulsifier is 3-6. The emulsifier is diglycerol isostearate (73296-86-2 dispersant from Wuhan daoshi Biotech Co., Ltd.). In the invention, the diglycerol isostearate is adsorbed on the surface of the liquid drop and is directionally arranged around the liquid drop to form a film, so that the interface free energy and the oil-water interface tension are reduced, a firm emulsion film is formed, the liquid drop aggregation is effectively prevented, a stable emulsion is formed, and the energy consumed by emulsion preparation is reduced.
The electrolyte solution is calcium chloride (chemical formula is CaCl) 2 ) The electrolyte solution is a solution or a sodium chloride (chemical formula is NaCl) solution, the solvent adopts distilled water or purified water, and the concentration of the electrolyte solution is 1-4%.
The Pinner reaction refers to a reaction in which a nitrile is converted to an imidate, and then reacted with water or ammonia to produce an ester or amidine. Named under the name of the chemist Adolf Pinner. Alcoholysis of nitriles in chloroform, typically catalyzed by HCl gas, gives the hydrochloride salt of the imidate, also known as the Pinner salt, which reacts with many other nucleophiles, except water and ammonia, as mentioned above, with excess alcohol to give the orthoester, and hydrogen sulfide to give the thioester.
Specific example 1: 3.2 parts of acrylate monomers, 0.5 part of emulsifier, 0.2-1 part of oil-soluble initiator, 0.2-2 parts of water-soluble initiator and 96 parts of electrolyte solution, wherein the acrylate monomers comprise skeleton monomers and crosslinking monomers, the skeleton monomers comprise 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomers comprise 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure of specific example 1 is as follows:
(1) preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously putting the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, starting stirring, wherein the stirring speed is 450 revolutions per minute, and the stirring time is 25 minutes, so as to obtain the oil phase for later use.
(2) And preparing a water phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water phase mixing pot, and stirring at the stirring speed of 40 revolutions per minute for 20 minutes until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And emulsification: and (3) transferring the water phase 1/5 in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 75 ℃, starting stirring at the stirring speed of 650 revolutions per minute, then dripping all the oil phases obtained in the step (1) through a flow injector, reducing the stirring speed to 400 revolutions per minute after the oil phase feeding is finished, adding the rest water phases through the flow injector, starting the homogenizing emulsifying machine after all the water phases are added, enabling the rotation speed of a homogenizing head to be 9000 revolutions per minute, enabling the homogenizing emulsifying time to be 8 minutes, forming primary emulsion with the same grade of uniformly dispersed particles, then closing the homogenizing emulsifying machine, starting stirring at the stirring speed of 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, then transferring the emulsion into a storage pot, and stirring at 250 revolutions per minute for standby.
(4) And (3) scraping and coating a die: and (4) blade-coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating to obtain a raw material.
(5) And water bath microwave curing: the caterpillar mold with the emulsion is transferred and conveyed to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is simultaneously linearly cured by water bath and microwave. The line speed was controlled so that the flow-through time was controlled at 3 minutes. Wherein, the microwave power is controlled at 3000 GHz. The temperature of the water bath was controlled at 85 ℃.
(6) And washing: and (3) washing the cured raw material, namely washing the raw material by using deionized water mixed with a surfactant solution, and then washing the raw material by using deionized water to remove residual monomers.
(7) And drying: and (3) transferring the washed raw materials into a negative-pressure high-temperature drying pot, drying and dehydrating, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, thus obtaining the example 1.
Specific example 2: 3.2 parts of acrylate monomers, 0.5 part of emulsifier, 0.2-1 part of oil-soluble initiator, 0.2-2 parts of water-soluble initiator and 96 parts of electrolyte solution, wherein the acrylate monomers comprise skeleton monomers and crosslinking monomers, the skeleton monomers comprise 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomers comprise 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure of specific example 2 is as follows:
(1) preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously putting the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, starting stirring, wherein the stirring speed is 450 revolutions per minute, and the stirring time is 25 minutes, so as to obtain the oil phase for later use.
(2) And preparing a water phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water phase mixing pot, and stirring at the stirring speed of 40 revolutions per minute for 20 minutes until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And emulsification: and (3) transferring the water phase 1/5 in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 75 ℃, starting stirring at the stirring speed of 650 revolutions per minute, then dripping all the oil phases obtained in the step (1) through a flow injector, reducing the stirring speed to 400 revolutions per minute after the oil phase feeding is finished, adding the rest water phases through the flow injector, starting the homogenizing emulsifying machine after all the water phases are added, enabling the rotation speed of a homogenizing head to be 9000 revolutions per minute, enabling the homogenizing emulsifying time to be 8 minutes, forming primary emulsion with the same grade of uniformly dispersed particles, then closing the homogenizing emulsifying machine, starting stirring at the stirring speed of 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, then transferring the emulsion into a storage pot, and stirring at 250 revolutions per minute for standby.
(4) And (3) scraping and coating a die: and (4) blade-coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating to obtain a raw material.
(5) And curing in a water bath: and (4) transferring the caterpillar mold with the emulsion in the step (4) to a water bath curing furnace, wherein the temperature is 85 ℃, the curing time is 8 minutes, the water bath curing is a known conventional technology, and the rest parameters are set according to the conventional method.
(6) And washing: and (3) washing the cured raw material, namely washing the raw material by using deionized water mixed with a surfactant solution, and then washing the raw material by using deionized water to remove residual monomers.
(7) And drying: and (3) transferring the washed raw materials into a negative-pressure high-temperature drying pot, drying and dehydrating, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, thus obtaining the example 2.
Specific example 3: 3.2 parts of acrylate monomers, 0.5 part of emulsifier, 0.2-1 part of oil-soluble initiator, 0.2-2 parts of water-soluble initiator and 96 parts of electrolyte solution, wherein the acrylate monomers comprise skeleton monomers and crosslinking monomers, the skeleton monomers comprise 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomers comprise 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure of specific example 3 is as follows:
(1) preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously putting the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, starting stirring, wherein the stirring speed is 450 revolutions per minute, and the stirring time is 25 minutes, so as to obtain the oil phase for later use.
(2) And preparing a water phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water phase mixing pot, and stirring at the stirring speed of 40 revolutions per minute for 20 minutes until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And emulsification: and (3) transferring the water phase 1/5 in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 75 ℃, starting stirring at the stirring speed of 650 revolutions per minute, then dripping all the oil phases obtained in the step (1) through a flow injector, reducing the stirring speed to 400 revolutions per minute after the oil phase feeding is finished, adding the rest water phases through the flow injector, starting the homogenizing emulsifying machine after all the water phases are added, enabling the rotation speed of a homogenizing head to be 9000 revolutions per minute, enabling the homogenizing emulsifying time to be 8 minutes, forming primary emulsion with the same grade of uniformly dispersed particles, then closing the homogenizing emulsifying machine, starting stirring at the stirring speed of 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, then transferring the emulsion into a storage pot, and stirring at 250 revolutions per minute for standby.
(4) And (3) scraping and coating a die: and (4) blade-coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating to obtain a raw material.
(5) And water vapor curing: and (4) transferring the caterpillar mold with the emulsion in the step (4) to a steam curing furnace, wherein the curing time is 10 minutes, the steam curing is a known conventional technology, and the rest parameters are set according to the conventional method.
(6) And washing: and (3) washing the cured raw material, namely washing the raw material by using deionized water mixed with a surfactant solution, and then washing the raw material by using deionized water to remove residual monomers.
(7) And drying: and (3) transferring the washed raw materials into a negative-pressure high-temperature drying pot, drying and dehydrating, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, thus obtaining the example 3.
Specific example 4: 3.2 parts of acrylate monomers, 0.5 part of emulsifier, 0.2-2 parts of water-soluble initiator and 96 parts of electrolyte solution, wherein the acrylate monomers consist of skeleton monomers and crosslinking monomers, the skeleton monomers comprise 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomers comprise 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure of specific example 4 is as follows:
(1) preparing an oil phase: and heating the oil phase mixing pot to 50 ℃, simultaneously putting the acrylic ester monomers and the emulsifier in parts by weight into the oil phase mixing pot, and starting stirring at the stirring speed of 450 revolutions per minute for 25 minutes to obtain the oil phase for later use.
(2) And preparing a water phase: adding the electrolyte solution and the water-soluble initiator in parts by weight into a water phase mixing pot, starting stirring at the stirring speed of 40 revolutions per minute for 20(3), and emulsifying: and (3) transferring the water phase 1/5 in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 75 ℃, starting stirring at the stirring speed of 650 revolutions per minute, then dripping all the oil phases obtained in the step (1) through a flow injector, reducing the stirring speed to 400 revolutions per minute after the oil phase feeding is finished, adding the rest water phases through the flow injector, starting the homogenizing emulsifying machine after all the water phases are added, enabling the rotation speed of a homogenizing head to be 9000 revolutions per minute, enabling the homogenizing emulsifying time to be 8 minutes, forming primary emulsion with the same grade of uniformly dispersed particles, then closing the homogenizing emulsifying machine, starting stirring at the stirring speed of 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, then transferring the emulsion into a storage pot, and stirring at 250 revolutions per minute for standby.
(4) And (3) scraping and coating a die: and (4) coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating to obtain a raw material.
(5) And water bath microwave curing: the caterpillar mold with the emulsion is transferred and conveyed to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is simultaneously linearly cured by water bath and microwave. The line speed was controlled so that the flow-through time was controlled at 4 minutes. Wherein, the microwave power is controlled at 3000 GHz. The temperature of the water bath was controlled at 85 ℃.
(6) And washing: and (3) washing the cured raw material, namely washing the raw material by using deionized water mixed with a surfactant solution, and then washing the raw material by using deionized water to remove residual monomers.
(7) And drying: and (3) transferring the washed raw materials into a negative-pressure high-temperature drying pot, drying and dehydrating, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, thus obtaining the example 4.
Specific example 5: 3.2 parts of acrylate monomers, 0.5 part of emulsifier, 0.2-1 part of oil-soluble initiator, 0.2-2 parts of water-soluble initiator and 96 parts of electrolyte solution, wherein the acrylate monomers comprise skeleton monomers and crosslinking monomers, the skeleton monomers comprise 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomers comprise 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure of specific example 5 was as follows:
(1) preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously putting the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, starting stirring, wherein the stirring speed is 450 revolutions per minute, and the stirring time is 25 minutes, so as to obtain the oil phase for later use.
(2) And preparing a water phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water phase mixing pot, and stirring at the stirring speed of 40 revolutions per minute for 20 minutes until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And emulsification: and (3) transferring the water phase 1/5 in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 75 ℃, starting stirring at the stirring speed of 650 revolutions per minute, then dripping all the oil phases obtained in the step (1) through a flow injector, reducing the stirring speed to 400 revolutions per minute after the oil phase feeding is finished, adding the rest water phases through the flow injector, starting the homogenizing emulsifying machine after all the water phases are added, enabling the rotation speed of a homogenizing head to be 9000 revolutions per minute, enabling the homogenizing emulsifying time to be 8 minutes, forming primary emulsion with the same grade of uniformly dispersed particles, then closing the homogenizing emulsifying machine, starting stirring at the stirring speed of 400 revolutions per minute, keeping stirring for 3 minutes to obtain emulsion, then transferring the emulsion into a storage pot, and stirring at 250 revolutions per minute for standby.
(4) And (3) scraping and coating a die: and (4) blade-coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating to obtain a raw material.
(5) And water bath microwave curing: the caterpillar mold with the emulsion is transferred and conveyed to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is simultaneously linearly cured by water bath and microwave. The line speed was controlled so that the flow-through time was controlled at 3 minutes. Wherein, the microwave power is controlled at 3000 GHz. The temperature of the water bath was controlled at 85 ℃.
(6) And washing: and (3) washing the cured raw material, namely washing the raw material by using deionized water mixed with a surfactant solution, and then washing the raw material by using deionized water to remove residual monomers.
(7) And drying: and (3) transferring the washed raw materials into a negative-pressure high-temperature drying pot, drying and dehydrating, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, thus obtaining the example 5.
Specific example 6: 3.2 parts of acrylate monomers, 0.5 part of emulsifier, 0.2-1 part of oil-soluble initiator, 0.2-2 parts of water-soluble initiator and 96 parts of electrolyte solution, wherein the acrylate monomers comprise skeleton monomers and crosslinking monomers, the skeleton monomers comprise 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomers comprise 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure of specific example 6 was as follows:
(1) preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously putting the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, starting stirring, wherein the stirring speed is 450 revolutions per minute, and the stirring time is 25 minutes, so as to obtain the oil phase for later use.
(2) And preparing a water phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water phase mixing pot, and stirring at the stirring speed of 40 revolutions per minute for 20 minutes until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And (3) emulsification: and (3) transferring the water phase 1/5 in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 75 ℃, starting stirring at the stirring speed of 650 revolutions per minute, then dripping all the oil phases obtained in the step (1) through a flow injector, reducing the stirring speed to 400 revolutions per minute after the oil phase feeding is finished, adding the rest water phases through the flow injector, starting the homogenizing emulsifying machine after all the water phases are added, enabling the rotation speed of a homogenizing head to be 9000 revolutions per minute, enabling the homogenizing emulsifying time to be 8 minutes, forming primary emulsion with the same grade of uniformly dispersed particles, then closing the homogenizing emulsifying machine, starting stirring at the stirring speed of 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, then transferring the emulsion into a storage pot, and stirring at 250 revolutions per minute for standby.
(4) And (3) scraping and coating a die: and (4) blade-coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating to obtain a raw material.
(5) And water bath microwave curing: the caterpillar mold with the emulsion is transferred and conveyed to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is simultaneously linearly cured by water bath and microwave. The line speed was controlled so that the flow-through time was controlled at 4 minutes. Wherein, the microwave power is controlled at 3000 GHz. The temperature of the water bath was controlled at 85 ℃.
(6) And washing: and (3) washing the cured raw material, namely washing the raw material by using deionized water mixed with a surfactant solution, and then washing the raw material by using deionized water to remove residual monomers.
(7) And drying: and (3) transferring the washed raw materials into a negative-pressure high-temperature drying pot, drying and dehydrating, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, thus obtaining the example 6.
Specific example 7: 3.2 parts of acrylate monomers, 0.5 part of emulsifier, 0.2-1 part of oil-soluble initiator, 0.2-2 parts of water-soluble initiator and 96 parts of electrolyte solution, wherein the acrylate monomers comprise skeleton monomers and crosslinking monomers, the skeleton monomers comprise 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomers comprise 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure of specific example 7 was as follows:
(1) preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously putting the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, starting stirring, wherein the stirring speed is 450 revolutions per minute, and the stirring time is 25 minutes, so as to obtain the oil phase for later use.
(2) And preparing a water phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water phase mixing pot, and stirring at the stirring speed of 40 revolutions per minute for 20 minutes until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And emulsification: and (3) transferring the water phase 1/5 in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 75 ℃, starting stirring at the stirring speed of 650 revolutions per minute, then dripping all the oil phases obtained in the step (1) through a flow injector, reducing the stirring speed to 400 revolutions per minute after the oil phase feeding is finished, adding the rest water phases through the flow injector, starting the homogenizing emulsifying machine after all the water phases are added, enabling the rotation speed of a homogenizing head to be 9000 revolutions per minute, enabling the homogenizing emulsifying time to be 8 minutes, forming primary emulsion with the same grade of uniformly dispersed particles, then closing the homogenizing emulsifying machine, starting stirring at the stirring speed of 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, then transferring the emulsion into a storage pot, and stirring at 250 revolutions per minute for standby.
(4) And (3) scraping and coating a die: and (4) blade-coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating to obtain a raw material.
(5) And water bath microwave curing: the caterpillar mold with the emulsion is transferred and conveyed to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is simultaneously linearly cured by water bath and microwave. The line speed was controlled so that the flow-through time was controlled at 5 minutes. Wherein, the microwave power is controlled at 3000 GHz. The temperature of the water bath was controlled at 85 ℃.
(6) And washing: and (3) washing the cured raw material, namely washing the raw material by using deionized water mixed with a surfactant solution, and then washing the raw material by using deionized water to remove residual monomers.
(7) And drying: and (3) transferring the washed raw materials into a negative-pressure high-temperature drying pot, drying and dehydrating, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, thus obtaining the example 7.
Specific example 8: 3.2 parts of acrylate monomers, 0.5 part of emulsifier, 0.2-1 part of oil-soluble initiator, 0.2-2 parts of water-soluble initiator and 96 parts of electrolyte solution, wherein the acrylate monomers comprise skeleton monomers and crosslinking monomers, the skeleton monomers comprise 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomers comprise 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure of specific example 8 was as follows:
(1) preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously putting the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, starting stirring, wherein the stirring speed is 450 revolutions per minute, and the stirring time is 25 minutes, so as to obtain the oil phase for later use.
(2) And preparing a water phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water phase mixing pot, and stirring at the stirring speed of 40 revolutions per minute for 20 minutes until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And emulsification: and (3) transferring the water phase 1/5 in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 75 ℃, starting stirring at the stirring speed of 650 revolutions per minute, then dripping all the oil phases obtained in the step (1) through a flow injector, reducing the stirring speed to 400 revolutions per minute after the oil phase feeding is finished, adding the rest water phases through the flow injector, starting the homogenizing emulsifying machine after all the water phases are added, enabling the rotation speed of a homogenizing head to be 9000 revolutions per minute, enabling the homogenizing emulsifying time to be 8 minutes, forming primary emulsion with the same grade of uniformly dispersed particles, then closing the homogenizing emulsifying machine, starting stirring at the stirring speed of 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, then transferring the emulsion into a storage pot, and stirring at 250 revolutions per minute for standby.
(4) And (3) scraping and coating a die: and (4) blade-coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating to obtain a raw material.
(5) And water vapor curing: and (3) transferring the crawler mold with the emulsion in the step (4) to a steam curing furnace, wherein the curing time is 3 minutes, the steam curing is a known conventional technology, and the rest parameters are set according to the conventional method, so that the obtained example 8 cannot be molded due to too short curing time, and the steps (6) and (7) cannot be carried out.
Specific embodiments are shown in the following table:
the following are specifically mentioned: the curing time and the flowing time in the preparation step (5) refer to the time required by the material to be cured, and the flowing time in the step (5) is the concept of process control, namely the shortest time required by the material to be cured is confirmed, the material performance at the time is confirmed to reach the standard, and then the process guides the operation control. Examples 6, 7, and 8 were also provided to demonstrate the accuracy of the cure time.
The applicant has tested the main properties of the acrylate foams of the specific examples 1 to 8, with the following results:
from the data analysis, compared with a water bath curing technology and a water vapor curing technology, the curing time is greatly shortened by using water bath microwave curing, the production efficiency is greatly improved, and the obtained acrylic ester foam material has relatively good performance; and when the water bath microwave curing is also used, when the oily emulsifier of the azodiisobutyrate dihexyl ester is used for synthesizing the acrylate foam material, the product performance is relatively better, and the optimal using amount is 0.05 part.
By comparison with the prior application (publication No. CN113637278A), the absorption times of the materials prepared by the method of the application exceed 15 times, and the longitudinal breaking strength and the transverse breaking strength are greatly improved.
Experimental data show that the performance of the produced product is not changed greatly by increasing the dosage of the dihexyl azodiisobutyrate; and when the water absorption capacity, the longitudinal breaking strength and the transverse breaking strength of the product are reduced along with the reduction of the dosage of the dihexyl azodiisobutyrate, the absorption speed of the synthetic liquid is reduced.
The test results for examples 6 and 7 are very similar to those for example 1, as can be seen by comparing the properties of examples 1,6 and 7, indicating that the material has met the requirements when microwave cured in a water bath for 3 minutes. By comparing examples 3 and 8, the material could not be shaped within 3 minutes by curing with water vapor under otherwise unchanged conditions. In conclusion, the water bath microwave curing time is short and effective.
The above embodiments do not limit the scope of the present invention, and those skilled in the art can make equivalent modifications and variations without departing from the overall concept of the present invention.
Claims (8)
1. A method for preparing an acrylate foam material by double-initiation and double-curing through a water bath microwave method is prepared from the following raw materials in parts by weight: 2-5 parts of acrylate monomer, 0.3-3 parts of emulsifier, 0.02-0.2 part of oil-soluble initiator, 0.2-2 parts of water-soluble initiator and 89-97.5 parts of electrolyte solution, wherein the acrylate monomer consists of skeleton monomer and crosslinking monomer, and the oil-soluble initiator is dihexyl azodiisobutyrate and is characterized by comprising the following steps:
(1) preparing an oil phase: heating the oil phase mixing pot to 45-55 ℃, simultaneously putting the acrylic ester monomers, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, starting stirring at the stirring speed of 100-;
(2) and preparing a water phase: adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and starting stirring at the stirring speed of 30-50 revolutions per minute for 15-30 minutes until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use;
(3) and emulsification: transferring the water phase from 1/5 to 1/4 in the step (2) to a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 70-80 ℃, starting stirring at the stirring speed of 500-, stirring at the stirring speed of 200-300 r/min for standby;
(4) and (3) scraping and coating a die: coating the emulsion obtained in the step (3) into a caterpillar mold with an anti-sticking coating in a scraping mode for later use;
(5) and water bath microwave curing: transferring and conveying the caterpillar mold with the emulsion in the step (4) to a water bath microwave curing furnace, performing linear curing on the material through water bath and microwave at the same time, controlling the linear speed to control the flowing time to be 2-5 minutes, controlling the microwave power to be 1500-plus 3000GHz, and controlling the water bath temperature to be 75-95 ℃;
(6) and washing: washing the cured raw material, namely washing the raw material by using deionized water mixed with a surfactant solution, and then washing the raw material by using deionized water to remove residual monomers;
(7) and drying: and transferring the washed raw materials into a negative pressure high temperature drying pot for drying and dehydrating, wherein the pressure and the temperature are conventionally set, and the drying time is 2-4 hours, so as to obtain the acrylic ester foam material.
2. The method according to claim 1, characterized in that the oil-soluble initiator is synthesized by the following steps:
(1) adding azodiisobutyronitrile hydrazine into a three-neck flask A provided with a stirrer, a gas-guide tube and a thermometer, adding excessive hexanol, stirring to dissolve, introducing chlorine gas under cooling of an ice water bath to obtain a mixture, fully stirring the mixture at a stirring speed of 30-50 revolutions per minute, and carrying out oxidation reaction for 4-5 hours to obtain an intermediate A;
(2) introducing dry hydrogen chloride gas into the three-neck flask A in the step (1) at 15 ℃, reacting for 18-20h at the temperature, carrying out a Pinner reaction, and then carrying out suction filtration to obtain an intermediate B;
(3) adding deionized water into a three-neck flask B, starting stirring at the stirring speed of 30-50 revolutions per minute, placing the three-neck flask B into ice water while stirring for cooling, then adding an intermediate B into the three-neck flask B, raising the temperature to 20 ℃ after adding, stirring for 3-5 hours, hydrolyzing to obtain a reaction mixture after hydrolysis, cooling the reaction mixture until solid is separated out to obtain a corresponding crude product, and recrystallizing the crude product with ethanol and water to obtain a pure product, thus preparing dihexyl azodiisobutyrate, namely the required oil-soluble initiator.
3. The method according to claim 1, wherein the skeletal monomer is a combination of two or more of methyl methacrylate, ethyl dimethacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, lauryl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, isooctyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, tetradecyl methacrylate, octadecyl methacrylate, isooctyl acrylate, n-decyl acrylate, isodecyl acrylate, tetradecyl acrylate, and octadecyl acrylate.
4. The method according to claim 1, wherein the crosslinking monomer is one or more selected from the group consisting of 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1, 12-dodecyl dimethacrylate, 1, 14-tetradecanediol dimethacrylate, ethylene glycol dimethacrylate and neopentyl triacrylate.
5. The method according to claim 1, characterized in that the water-soluble initiator is any one of sodium persulfate, potassium persulfate and ammonium persulfate.
6. The method according to claim 1, wherein the emulsifier is a water-in-oil emulsifier, and the emulsifier has an HLB value of 3 to 6.
7. The method according to claim 6, characterized in that the emulsifier is diglycerol isostearate.
8. The method according to claim 1, wherein the electrolyte solution is a calcium chloride solution or a sodium chloride solution, and the concentration of the electrolyte solution is 1-4%.
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| CN1317033A (en) * | 1998-07-31 | 2001-10-10 | 3M创新有限公司 | Articles that include polymer foam and method for preparing same |
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