CN114874382B - Method for preparing acrylic ester foam material by double-initiation and double-solidification through water bath microwave method - Google Patents
Method for preparing acrylic ester foam material by double-initiation and double-solidification through water bath microwave method Download PDFInfo
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- 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
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Abstract
The invention discloses a method for preparing an acrylic ester foam material by double initiation and double solidification of a water bath microwave method, which is prepared from acrylic ester monomers, an emulsifying agent, 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 die, carrying out water bath microwave solidification, washing and drying; the preparation method effectively initiates the acrylic ester monomer to carry out the crosslinking reaction by using the double initiator, and then prepares the material by microwave curing in water bath, so that the preparation process is short in time consumption and less in energy consumption, and compared with the traditional single thermal curing method, the preparation method improves the production efficiency, has the advantages of energy conservation and emission reduction, and meets the condition of mass production; the invention adopts the water-in-oil emulsion, the polarity of water is strong, microwaves are easy to absorb, the curing time is shortened, 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 by a water bath microwave method, the physical properties of the material such as toughness and the like are improved, and the water absorption multiple and the absorption speed are also improved.
Description
Technical Field
The application relates to a method for preparing an acrylic ester foam material, in particular to a method for preparing an acrylic ester foam material by double-initiation and double-solidification through a water bath microwave method.
Background
The existing methods for preparing the acrylic ester foam materials comprise a hot baking method, a water bath method, a steam method and the like, and the principles of the method are that an external heat source conducts and heats from the outside to the inside through thermal radiation, but the preparation methods are low in energy utilization rate, long in curing time, uneven in temperature distribution, time-consuming, energy-consuming, low in mass production efficiency and low in toughness of the synthesized acrylic ester foam materials.
The same applicant of the application applies for a short fiber toughened water-absorbing acrylic ester polymer material and a preparation method thereof, wherein the publication number is CN113637278A, the material is solidified by a water vapor method in the preparation method, the water absorption multiple of the obtained material is less than 15 times, and the longitudinal fracture strength and the transverse fracture strength are only 6.56N/25mm and 3.95N/25mm. In addition, as in the case of the technology described in patent document CN113771439A, CN113796621a, the material is cured by the steam method, and the obtained product is not satisfactory in terms of the longitudinal fracture strength, the transverse fracture strength, and the water absorption capacity.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing an acrylic ester foam material by double-initiation and double-solidification through a water bath microwave method.
The technical scheme adopted for solving the technical problems is as follows:
a method for preparing an acrylic ester foam material by double initiation and double solidification through a water bath microwave method comprises the following raw materials in parts by weight: 2-5 parts of acrylic ester 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 acrylic ester monomer consists of a framework monomer and a 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 adding the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 100-800 rpm, and the stirring time is 15-30 minutes, so as to obtain an oil phase for later use.
(2) Preparing an aqueous phase: adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and starting stirring at a stirring speed of 30-50 r/min for 15-30 min until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And (3) emulsification: transferring 1/5 to 1/4 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 70-80 ℃ and starting stirring, wherein the stirring speed is 500-800 rpm, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, reducing the stirring speed to 300-500 rpm after the oil phase is fed, adding the rest water phase through the flow liquid injector, starting a homogenizing emulsifying machine after the water phase is fully fed, starting the homogenizing head at 8000-10000 rpm, homogenizing and emulsifying for 5-10 minutes to form primary emulsion with uniform dispersion and particle level, then closing the homogenizing emulsifying machine, starting stirring, maintaining the stirring speed for 5-10 minutes, obtaining emulsion, transferring the emulsion into a storage pot, and stirring at the stirring speed of 200-300 rpm for standby.
(4) And (3) a blade coating die: and (3) doctor-coating the emulsion obtained in the step (3) into a crawler belt die with a release coating for standby application.
(5) And (3) carrying out microwave curing in a water bath: transferring the caterpillar band mold with the emulsion in the step (4) to a water bath microwave curing oven, carrying out linear curing on the material through water bath and microwaves at the same time, controlling the linear speed to control the flowing time to be 2-5 minutes, controlling the microwave power to be 1500-3000GHz, and controlling the temperature of the water bath to be 75-95 ℃.
(6) Washing: washing the solidified raw materials, firstly washing by mixing deionized water with a surfactant solution, and then washing by using deionized water to remove residual monomers.
(7) And (3) drying: and transferring the washed raw materials into a negative pressure high temperature drying pot for drying and dewatering, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 2-4 hours, so that the acrylic ester foam material is obtained.
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, an air duct and a thermometer, adding excessive hexanol, stirring to dissolve the azodiisobutyronitrile hydrazine, cooling with ice water bath, introducing chlorine to obtain a mixture, fully stirring the mixture at a stirring speed of 30-50 r/min, and carrying out oxidation reaction for 4-5h to obtain an intermediate A.
(2) And (3) 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 introducing, carrying out a Pinner reaction, and carrying out suction filtration to obtain an intermediate B.
(3) Adding deionized water into a three-neck flask B, starting stirring at a stirring speed of 30-50 r/min, placing the three-neck flask B into ice water while stirring, cooling, adding an intermediate B into the three-neck flask B, heating to 20 ℃, stirring for 3-5 hours, hydrolyzing to obtain a reaction mixture, cooling the reaction mixture until solids are separated out to obtain a corresponding crude product, recrystallizing the crude product with ethanol and water to obtain a pure product, and obtaining the azobisisobutyrate dihexyl ester, namely the required oil-soluble initiator.
The skeleton monomer is 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 more than one of 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1, 12-dodecane 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 type 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 beneficial effects of the invention are as follows:
1. the invention utilizes the double initiator to initiate acrylic ester to carry out water bath microwave curing to form the composite polymer material, wherein the azo-diisobutyrate dihexyl ester serving as an initiator is self-developed and synthesized, the double initiator is used for effectively initiating acrylic ester monomers to carry out crosslinking reaction, premature excessive chain termination reaction is prevented, the residual monomer amount after the reaction is small, the water bath microwave curing is utilized to prepare the acrylic ester foam material, the preparation process is short in time consumption and low in energy consumption, and compared with the traditional single thermal curing method, the invention improves the production efficiency, has the advantages of energy conservation and emission reduction, and meets the mass production condition.
2. The invention adopts the water-in-oil emulsion, water belongs to substances with strong polarity, microwaves are easy to absorb, the absorbed microwaves are converted into heat energy, and simultaneously, the curing time is greatly shortened through water bath energy storage and energy transmission, 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, and therefore, 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 multiple and the absorption speed are also improved.
Detailed Description
In all the embodiments of the present invention, the temperature and the pressure are not particularly emphasized, and are normal temperature and normal pressure, and the use of the device is not particularly described, and the device can be used according to the conventional arrangement.
The present invention will be further described in detail with reference to the following embodiments, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be noted that, without conflict, the embodiments of the present invention and features in the embodiments may be combined with each other.
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 the method is time-consuming and energy-consuming, has low mass production efficiency and has low toughness of the synthesized acrylic ester foam material. The invention synthesizes the acrylic ester foam material by using the double initiator through the water bath microwave method, the time is shorter, the energy consumption is lower, the toughness of the prepared acrylic ester foam material is better, the effects of energy conservation and emission reduction are achieved, and the invention is a better synthesis method.
Microwaves generally refer to electromagnetic waves having a wavelength in the range of 0.1mm-1000mm, with a corresponding frequency in the range of 300MHz-3000GHz. The traditional heating modes such as a hot baking method, a water bath method and a steam method are all based on the principle that an external heat source is heated by conduction from the outside to the inside through thermal radiation, 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 heat energy through dielectric molecules belongs to a body heating mode, and the temperature is quickly increased and the inside and outside temperatures are the same. We choose the microwave with high frequency, the frequency range is 2000G-3000GHz.
The invention discloses a preparation method of a water bath microwave method dual-initiator acrylic ester foam material, which comprises the following steps: 2-5 parts of acrylic ester 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, and the preparation process comprises the steps of preparing an oil phase and a water phase, emulsifying, doctor-blading a die, carrying out microwave curing in a water bath, washing and drying. The invention utilizes double initiator to initiate acrylic ester to carry out water bath microwave curing to form composite high polymer material, wherein, one initiator of the azo-diisobutyrate dihexyl ester is self-developed and synthesized, the azo-diisobutyrate dihexyl ester is a novel oil-soluble azo initiator, the initiator contains multi-functional groups of active groups, the difference between the product and azo-diisobutyronitrile and azo-diisoheptonitrile is that the product does not contain cyano groups, and the decomposition product is nontoxic, so that the nontoxic polymer can be prepared. The use of a dual initiator now effectively initiates the acrylate reaction, prevents premature and excessive chain termination reactions, and results in a small amount of monomer remaining after the reaction. The microwave curing saves energy and time, and the temperature of the emulsion is consistent from inside to outside by the microwave, so that the microwave is easy to be absorbed because the emulsion is water-in-oil emulsion and water belongs to substances with very strong polarities, the time required for curing by converting the absorbed microwave into heat energy is relatively short, and the material performance obtained after curing is relatively good.
A method for preparing an acrylic ester foam material by double initiation and double solidification through a water bath microwave method comprises the following raw materials in parts by weight: 2-5 parts of acrylic ester 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 acrylic ester monomer consists of a framework monomer and a crosslinking monomer, and 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 adding the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 100-800 rpm, and the stirring time is 15-30 minutes, so as to obtain an oil phase for later use.
(2) Preparing an aqueous phase: adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and starting stirring at a stirring speed of 30-50 r/min for 15-30 min until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use.
(3) And (3) emulsification: transferring 1/5 to 1/4 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 70-80 ℃ and starting stirring, wherein the stirring speed is 500-800 rpm, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, reducing the stirring speed to 300-500 rpm after the oil phase is fed, adding the rest (3/4 to 4/5) of the water phase through the flow liquid injector, starting a homogenizing emulsifying machine after the water phase is fully fed, wherein the rotating speed of a homogenizing head is 8000-10000 rpm, the homogenizing emulsifying time is 5-10 min, forming primary emulsion with uniform dispersion and particle level, then switching off the homogenizing emulsifying machine, starting stirring, keeping stirring for 5-10 min at the stirring speed of 300-500 rpm, obtaining emulsion, transferring the emulsion into a storage pot, and stirring for standby at the stirring speed of 200-300 rpm.
(4) And (3) a blade coating die: and (3) doctor-coating the emulsion obtained in the step (3) into a crawler belt mould with a release coating according to a certain thickness.
(5) And (3) carrying out microwave curing in a water bath: the caterpillar mold with emulsion is transferred to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is subjected to linear curing simultaneously by water bath and microwaves. The line speed was controlled so that the flow-through time was controlled to 2-5 minutes. Wherein the microwave power is controlled at 1500-3000GHz. The temperature of the water bath is controlled between 75 and 95 ℃.
(6) Washing: washing the solidified raw materials, firstly washing by mixing deionized water with a surfactant solution, and then washing by using deionized water to remove residual monomers.
(7) And (3) drying: and transferring the washed raw materials into a negative pressure high temperature drying pot for drying and dewatering, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 2-4 hours, so that the acrylic ester foam material is obtained.
The oil-soluble initiator of the invention is the dihexyl azo diisobutyrate which is self-developed and synthesized, the dihexyl azo diisobutyrate is a novel oil-soluble azo initiator, the initiator contains a multi-functional group of active groups, and the dihexyl azo diisobutyrate, the azobisisobutyronitrile and the azobisisoheptonitrile are different in that the initiator does not contain cyano groups, and the decomposition products are nontoxic, so that the nontoxic polymer can be prepared. The synthesis procedure of the oil-soluble initiator (dihexyl azodiisobutyrate) is as follows:
(1) Adding azobisisobutyronitrile hydrazine (HAIBN, chemical formula C) into three-neck flask A with stirrer, air duct and thermometer 8 H 12 N 4 ) Then, excess hexanol (selected from n-hexanol produced by Jinan century chemical industry Co., ltd.) was added and dissolved by stirring. Chlorine gas (2 mol of HCl is generated by reaction with 1mol of hydrogenated azo-bis-isobutyronitrile hydrazine) is introduced under cooling in an ice water bath to obtain a mixture, and the mixture is stirred at a stirring speed of 30-50 rpm and is subjected to oxidation reaction for 4-5h to obtain an intermediate A.
The reaction equation is as follows:
(2) And (3) introducing dry hydrogen chloride (with a chemical formula of HCl) gas into the three-neck flask A in the step (1) at 15 ℃, reacting for 18-20h at the temperature after introducing, carrying out a Pinner reaction, and 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 a stirring speed of 30-50 r/min, cooling the three-neck flask B in ice water while stirring, adding the intermediate B obtained in the step (2) into the three-neck flask B, heating to 20 ℃, stirring for 3-5 hours, hydrolyzing to obtain a reaction mixture, cooling the reaction mixture until solids are separated out to obtain a corresponding crude product, and using ethanol (the chemical formula is C 2 H 6 And O) and water are recrystallized to obtain a pure product, and the dihexyl azodiisobutyrate, namely the required 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 C 7 H 12 O 2 ) Butyl methacrylate (chemical formula C 8 H 14 O 2 ) Isobutyl methacrylate (chemical formula C 8 H 14 O 2 ) Hexyl methacrylate (chemical 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 (chemical 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 ) Stearyl methacrylate (chemical formula C) 22 H 43 O 2 ) C, CIsooctyl enolate (chemical formula 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 stearyl acrylate (chemical formula C 21 H 40 O 2 ) Two or more of the above.
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 ) Trimethylol propyl triacrylate (chemical formula 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 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 (NH) 4 ) 2 S 2 O 8 ) Any one of the following. The water-soluble initiator can initiate the acrylate to react, so that the premature excessive chain termination reaction is prevented, and the residual monomer amount after the reaction is small.
The emulsifier is a water-in-oil type emulsifier, and the HLB value of the emulsifier is 3-6. The emulsifier is diglycerol isostearate (73296-86-2 dispersant manufactured by Wu Hanshu mol Biotechnology 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 interfacial free energy and the oil-water interfacial tension are reduced, a firm emulsion film is formed, the aggregation of the liquid drop is effectively prevented, a stable emulsion is formed, and the energy consumed by emulsion preparation is reduced.
The electrolyte solution is calcium chloride (with a chemical formula of CaCl 2 ) The solution or sodium chloride (the chemical formula is NaCl) solution, distilled water or purified water is adopted as the solvent, 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 iminoester, which is then reacted with water or ammonia to produce an ester or amidine. Named after the name of the chemist Adolf Pinner. The alcoholysis of nitriles in chloroform, typically under the catalysis of HCl gas, gives the hydrogen chloride salt of an iminoester, also known as the Pinner salt, which can be reacted with a number of other nucleophiles, in addition to the water and ammonia mentioned above, with an excess of alcohol to give orthoesters and hydrogen sulfide to give thioesters.
Specific example 1: 3.2 parts of acrylic ester monomer, 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 acrylic ester monomer consists of a framework monomer and a crosslinking monomer, the framework monomer consists of 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomer consists of 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 adding the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 450 r/min, and the stirring time is 25 min, so as to obtain an oil phase for later use.
(2) Preparing an aqueous phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and starting stirring at a stirring speed of 40 rpm 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: transferring 1/5 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously, heating the high-speed homogenizing emulsifying pot to 75 ℃ and starting stirring, wherein the stirring speed is 650 revolutions per minute, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, after the oil phase is fed, reducing the stirring speed to 400 revolutions per minute, adding the rest water phase through the flow liquid injector, after the water phase is completely added, starting a homogenizing emulsifying machine, wherein the rotating speed of a homogenizing head is 9000 revolutions per minute, the homogenizing emulsifying time is 8 minutes, forming primary emulsion with uniform dispersion and particle level, then closing the homogenizing emulsifying machine, starting stirring, the stirring speed is 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, transferring the emulsion to a storage pot, and stirring for standby at 250 revolutions per minute.
(4) And (3) a blade coating die: and (3) doctor-coating the emulsion obtained in the step (3) into a crawler belt die with a release coating to obtain a raw material.
(5) And (3) carrying out microwave curing in a water bath: the caterpillar mold with emulsion is transferred to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is subjected to linear curing simultaneously by water bath and microwaves. The line speed was controlled so that the flow-through time was controlled at 3 minutes. Wherein the microwave power is controlled at 3000GHz. The water bath temperature was controlled at 85 ℃.
(6) Washing: washing the solidified raw materials, firstly washing by mixing deionized water with a surfactant solution, and then washing by using deionized water to remove residual monomers.
(7) And (3) drying: and (3) transferring the washed raw materials into a negative pressure high temperature drying pot for drying and dewatering, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, so that the example 1 is obtained.
Specific example 2: 3.2 parts of acrylic ester monomer, 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 acrylic ester monomer consists of a framework monomer and a crosslinking monomer, the framework monomer consists of 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomer consists of 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 adding the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 450 r/min, and the stirring time is 25 min, so as to obtain an oil phase for later use.
(2) Preparing an aqueous phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and starting stirring at a stirring speed of 40 rpm 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: transferring 1/5 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously, heating the high-speed homogenizing emulsifying pot to 75 ℃ and starting stirring, wherein the stirring speed is 650 revolutions per minute, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, after the oil phase is fed, reducing the stirring speed to 400 revolutions per minute, adding the rest water phase through the flow liquid injector, after the water phase is completely added, starting a homogenizing emulsifying machine, wherein the rotating speed of a homogenizing head is 9000 revolutions per minute, the homogenizing emulsifying time is 8 minutes, forming primary emulsion with uniform dispersion and particle level, then closing the homogenizing emulsifying machine, starting stirring, the stirring speed is 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, transferring the emulsion to a storage pot, and stirring for standby at 250 revolutions per minute.
(4) And (3) a blade coating die: and (3) doctor-coating the emulsion obtained in the step (3) into a crawler belt die with a release coating to obtain a raw material.
(5) And (3) water bath curing: transferring the caterpillar band 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) Washing: washing the solidified raw materials, firstly washing by mixing deionized water with a surfactant solution, and then washing by using deionized water to remove residual monomers.
(7) And (3) drying: and (3) transferring the washed raw materials into a negative pressure high temperature drying pot for drying and dewatering, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, so that the example 2 is obtained.
Specific example 3: 3.2 parts of acrylic ester monomer, 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 acrylic ester monomer consists of a framework monomer and a crosslinking monomer, the framework monomer consists of 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomer consists of 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 adding the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 450 r/min, and the stirring time is 25 min, so as to obtain an oil phase for later use.
(2) Preparing an aqueous phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and starting stirring at a stirring speed of 40 rpm 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: transferring 1/5 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously, heating the high-speed homogenizing emulsifying pot to 75 ℃ and starting stirring, wherein the stirring speed is 650 revolutions per minute, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, after the oil phase is fed, reducing the stirring speed to 400 revolutions per minute, adding the rest water phase through the flow liquid injector, after the water phase is completely added, starting a homogenizing emulsifying machine, wherein the rotating speed of a homogenizing head is 9000 revolutions per minute, the homogenizing emulsifying time is 8 minutes, forming primary emulsion with uniform dispersion and particle level, then closing the homogenizing emulsifying machine, starting stirring, the stirring speed is 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, transferring the emulsion to a storage pot, and stirring for standby at 250 revolutions per minute.
(4) And (3) a blade coating die: and (3) doctor-coating the emulsion obtained in the step (3) into a crawler belt die with a release coating to obtain a raw material.
(5) Curing by water vapor: 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) Washing: washing the solidified raw materials, firstly washing by mixing deionized water with a surfactant solution, and then washing by using deionized water to remove residual monomers.
(7) And (3) drying: and (3) transferring the washed raw materials into a negative pressure high temperature drying pot for drying and dewatering, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, so that the example 3 is obtained.
Specific example 4: 3.2 parts of acrylic ester monomer, 0.5 part of emulsifier, 0.2-2 parts of water-soluble initiator and 96 parts of electrolyte solution, wherein the acrylic ester monomer consists of a framework monomer and a crosslinking monomer, the framework monomer consists of 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomer consists of 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: heating the oil phase mixing pot to 50 ℃, simultaneously adding the acrylic ester monomer and the emulsifier in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 450 r/min, and the stirring time is 25 min, so as to obtain an oil phase for later use.
(2) Preparing an aqueous phase: adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, starting stirring, wherein the stirring speed is 40 rpm, the stirring time is 20 (3), and emulsifying: transferring 1/5 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously, heating the high-speed homogenizing emulsifying pot to 75 ℃ and starting stirring, wherein the stirring speed is 650 revolutions per minute, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, after the oil phase is fed, reducing the stirring speed to 400 revolutions per minute, adding the rest water phase through the flow liquid injector, after the water phase is completely added, starting a homogenizing emulsifying machine, wherein the rotating speed of a homogenizing head is 9000 revolutions per minute, the homogenizing emulsifying time is 8 minutes, forming primary emulsion with uniform dispersion and particle level, then closing the homogenizing emulsifying machine, starting stirring, the stirring speed is 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, transferring the emulsion to a storage pot, and stirring for standby at 250 revolutions per minute.
(4) And (3) a blade coating die: and (3) doctor-coating the emulsion obtained in the step (3) into a crawler belt die with a release coating to obtain a raw material.
(5) And (3) carrying out microwave curing in a water bath: the caterpillar mold with emulsion is transferred to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is subjected to linear curing simultaneously by water bath and microwaves. The line speed was controlled so that the flow-through time was controlled at 4 minutes. Wherein the microwave power is controlled at 3000GHz. The water bath temperature was controlled at 85 ℃.
(6) Washing: washing the solidified raw materials, firstly washing by mixing deionized water with a surfactant solution, and then washing by using deionized water to remove residual monomers.
(7) And (3) drying: the washed raw materials are transferred into a negative pressure high temperature drying pot for drying and dehydration, the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, so that the example 4 is obtained.
Specific example 5: 3.2 parts of acrylic ester monomer, 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 acrylic ester monomer consists of a framework monomer and a crosslinking monomer, the framework monomer consists of 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomer consists of 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure of specific example 5 is as follows:
(1) Preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously adding the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 450 r/min, and the stirring time is 25 min, so as to obtain an oil phase for later use.
(2) Preparing an aqueous phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and starting stirring at a stirring speed of 40 rpm 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: transferring 1/5 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously, heating the high-speed homogenizing emulsifying pot to 75 ℃ and starting stirring, wherein the stirring speed is 650 revolutions per minute, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, after the oil phase is fed, reducing the stirring speed to 400 revolutions per minute, adding the rest water phase through the flow liquid injector, after the water phase is completely added, starting a homogenizing emulsifying machine, wherein the rotating speed of a homogenizing head is 9000 revolutions per minute, the homogenizing emulsifying time is 8 minutes, forming primary emulsion with uniform dispersion and particle level, then closing the homogenizing emulsifying machine, starting stirring, the stirring speed is 400 revolutions per minute, keeping stirring for 3 minutes, obtaining emulsion, transferring the emulsion to a storage pot, and stirring for standby at 250 revolutions per minute.
(4) And (3) a blade coating die: and (3) doctor-coating the emulsion obtained in the step (3) into a crawler belt die with a release coating to obtain a raw material.
(5) And (3) carrying out microwave curing in a water bath: the caterpillar mold with emulsion is transferred to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is subjected to linear curing simultaneously by water bath and microwaves. The line speed was controlled so that the flow-through time was controlled at 3 minutes. Wherein the microwave power is controlled at 3000GHz. The water bath temperature was controlled at 85 ℃.
(6) Washing: washing the solidified raw materials, firstly washing by mixing deionized water with a surfactant solution, and then washing by using deionized water to remove residual monomers.
(7) And (3) drying: the washed raw materials are transferred into a negative pressure high temperature drying pot for drying and dehydration, the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, so that the example 5 is obtained.
Specific example 6: 3.2 parts of acrylic ester monomer, 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 acrylic ester monomer consists of a framework monomer and a crosslinking monomer, the framework monomer consists of 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomer consists of 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure of specific example 6 is as follows:
(1) Preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously adding the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 450 r/min, and the stirring time is 25 min, so as to obtain an oil phase for later use.
(2) Preparing an aqueous phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and starting stirring at a stirring speed of 40 rpm 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: transferring 1/5 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously, heating the high-speed homogenizing emulsifying pot to 75 ℃ and starting stirring, wherein the stirring speed is 650 revolutions per minute, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, after the oil phase is fed, reducing the stirring speed to 400 revolutions per minute, adding the rest water phase through the flow liquid injector, after the water phase is completely added, starting a homogenizing emulsifying machine, wherein the rotating speed of a homogenizing head is 9000 revolutions per minute, the homogenizing emulsifying time is 8 minutes, forming primary emulsion with uniform dispersion and particle level, then closing the homogenizing emulsifying machine, starting stirring, the stirring speed is 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, transferring the emulsion to a storage pot, and stirring for standby at 250 revolutions per minute.
(4) And (3) a blade coating die: and (3) doctor-coating the emulsion obtained in the step (3) into a crawler belt die with a release coating to obtain a raw material.
(5) And (3) carrying out microwave curing in a water bath: the caterpillar mold with emulsion is transferred to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is subjected to linear curing simultaneously by water bath and microwaves. The line speed was controlled so that the flow-through time was controlled at 4 minutes. Wherein the microwave power is controlled at 3000GHz. The water bath temperature was controlled at 85 ℃.
(6) Washing: washing the solidified raw materials, firstly washing by mixing deionized water with a surfactant solution, and then washing by using deionized water to remove residual monomers.
(7) And (3) drying: the washed raw materials are transferred into a negative pressure high temperature drying pot for drying and dehydration, the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, so that the example 6 is obtained.
Specific example 7: 3.2 parts of acrylic ester monomer, 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 acrylic ester monomer consists of a framework monomer and a crosslinking monomer, the framework monomer consists of 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomer consists of 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure for specific example 7 is as follows:
(1) Preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously adding the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 450 r/min, and the stirring time is 25 min, so as to obtain an oil phase for later use.
(2) Preparing an aqueous phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and starting stirring at a stirring speed of 40 rpm 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: transferring 1/5 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously, heating the high-speed homogenizing emulsifying pot to 75 ℃ and starting stirring, wherein the stirring speed is 650 revolutions per minute, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, after the oil phase is fed, reducing the stirring speed to 400 revolutions per minute, adding the rest water phase through the flow liquid injector, after the water phase is completely added, starting a homogenizing emulsifying machine, wherein the rotating speed of a homogenizing head is 9000 revolutions per minute, the homogenizing emulsifying time is 8 minutes, forming primary emulsion with uniform dispersion and particle level, then closing the homogenizing emulsifying machine, starting stirring, the stirring speed is 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, transferring the emulsion to a storage pot, and stirring for standby at 250 revolutions per minute.
(4) And (3) a blade coating die: and (3) doctor-coating the emulsion obtained in the step (3) into a crawler belt die with a release coating to obtain a raw material.
(5) And (3) carrying out microwave curing in a water bath: the caterpillar mold with emulsion is transferred to a water bath microwave curing oven, and flows through the curing oven at a certain linear speed, and the material is subjected to linear curing simultaneously by water bath and microwaves. The line speed was controlled so that the flow-through time was controlled at 5 minutes. Wherein the microwave power is controlled at 3000GHz. The water bath temperature was controlled at 85 ℃.
(6) Washing: washing the solidified raw materials, firstly washing by mixing deionized water with a surfactant solution, and then washing by using deionized water to remove residual monomers.
(7) And (3) drying: the washed raw materials are transferred into a negative pressure high temperature drying pot for drying and dehydration, the pressure and the temperature are set according to the conventional method, and the drying time is 3 hours, so that the example 7 is obtained.
Specific example 8: 3.2 parts of acrylic ester monomer, 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 acrylic ester monomer consists of a framework monomer and a crosslinking monomer, the framework monomer consists of 1.2 parts of isooctyl acrylate and 0.7 part of isooctyl methacrylate, and the crosslinking monomer consists of 0.8 part of 1, 4-butanediol dimethacrylate and 0.5 part of 1, 6-hexanediol diacrylate.
The preparation procedure for specific example 8 is as follows:
(1) Preparing an oil phase: heating the oil phase mixing pot to 50 ℃, simultaneously adding the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 450 r/min, and the stirring time is 25 min, so as to obtain an oil phase for later use.
(2) Preparing an aqueous phase: and adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, and starting stirring at a stirring speed of 40 rpm 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: transferring 1/5 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously, heating the high-speed homogenizing emulsifying pot to 75 ℃ and starting stirring, wherein the stirring speed is 650 revolutions per minute, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, after the oil phase is fed, reducing the stirring speed to 400 revolutions per minute, adding the rest water phase through the flow liquid injector, after the water phase is completely added, starting a homogenizing emulsifying machine, wherein the rotating speed of a homogenizing head is 9000 revolutions per minute, the homogenizing emulsifying time is 8 minutes, forming primary emulsion with uniform dispersion and particle level, then closing the homogenizing emulsifying machine, starting stirring, the stirring speed is 400 revolutions per minute, keeping stirring for 8 minutes, obtaining emulsion, transferring the emulsion to a storage pot, and stirring for standby at 250 revolutions per minute.
(4) And (3) a blade coating die: and (3) doctor-coating the emulsion obtained in the step (3) into a crawler belt die with a release coating to obtain a raw material.
(5) Curing by water vapor: transferring the track mold with the emulsion in the step (4) to a steam curing furnace, wherein the curing time is 3 minutes, steam curing is a known conventional technology, other parameters are set according to the conventional technology, and the obtained example 8 cannot be molded and cannot be subjected to the steps (6) and (7) because the curing time is too short.
Specific embodiments are shown in the following table:
what needs to be specifically stated is: the curing time and the flowing time in the preparation step (5) refer to the time required by the curing of the material, and the flowing time in the step (5) is the concept of process control, namely the shortest time required by the curing of the material is confirmed, the material performance at the time is confirmed to reach the standard, and then the process is guided to operate and control. Examples 6, 7, 8 were also set up to demonstrate the accuracy of the cure time.
The applicant tested the main properties of the acrylate foams of specific examples 1-8, as follows:
as can be seen from the analysis of the data, compared with the water bath curing technology and the steam curing technology, the curing time is greatly shortened by utilizing the water bath microwave curing, the production efficiency is greatly improved, and the performance of the obtained acrylic ester foam material is relatively good; and the same water bath microwave curing is adopted, when the oily emulsifier dihexyl azodiisobutyrate is used for synthesizing the acrylic ester foam material, the performance of the obtained product is relatively better, and the optimal dosage of the product is 0.05 part.
Compared with the prior application document (publication No. CN 113637278A), the material prepared by the method has the absorption times of more than 15 times, and the longitudinal fracture strength and the transverse fracture strength are also greatly improved.
Experimental data shows that the performance of the produced product is not greatly changed by increasing the dosage of the dihexyl azodiisobutyrate; and when the dosage of the dihexyl azodiisobutyrate is reduced, the water absorption multiple, the longitudinal fracture strength and the transverse fracture strength of the product are reduced, and the absorption speed of the synthetic liquid is reduced.
As can be seen by comparing the properties of examples 1, 6, 7, the test results of examples 6 and 7 are very close to example 1, indicating that the material has reached the demand at 3 minutes of microwave curing in a water bath. By comparing examples 3 and 8, the material could not be molded within 3 minutes by curing with steam under the remaining conditions. In conclusion, the microwave curing time in the water bath is short and effective.
The above embodiments do not limit the protection scope of the application, and those skilled in the art can make equivalent modifications and variations without departing from the whole inventive concept, and they still fall within the scope of the application.
Claims (8)
1. A method for preparing an acrylic ester foam material by double initiation and double solidification through a water bath microwave method comprises the following raw materials in parts by weight: 2-5 parts of acrylic ester 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 acrylic ester monomer consists of a framework monomer and a crosslinking monomer, and the oil-soluble initiator is dihexyl azo diisobutyrate, and is characterized by comprising the following steps:
(1) Preparing an oil phase: heating the oil phase mixing pot to 45-55 ℃, simultaneously adding the acrylic ester monomer, the emulsifier and the oil-soluble initiator in parts by weight into the oil phase mixing pot, and starting stirring, wherein the stirring speed is 100-800 rpm, and the stirring time is 15-30 minutes, so as to obtain an oil phase for later use;
(2) Preparing an aqueous phase: adding the electrolyte solution and the water-soluble initiator in parts by weight into a water-phase mixing pot, starting stirring at a stirring speed of 30-50 r/min for 15-30 min until the electrolyte solution and the water-soluble initiator are fully dissolved to obtain a water phase for later use;
(3) And (3) emulsification: transferring 1/5 to 1/4 of the water phase in the step (2) into a high-speed homogenizing emulsifying pot, simultaneously heating the high-speed homogenizing emulsifying pot to 70-80 ℃ and starting stirring, wherein the stirring speed is 500-800 rpm, then dripping all the oil phase obtained in the step (1) through a flow liquid injector, reducing the stirring speed to 300-500 rpm after the oil phase is fed, adding the rest water phase through the flow liquid injector, starting a homogenizing emulsifying machine after the water phase is fully fed, starting the homogenizing head at 8000-10000 rpm, homogenizing and emulsifying for 5-10 minutes to form primary emulsion with uniform dispersion and particle level, then closing the homogenizing emulsifying machine, starting stirring, keeping the stirring speed for 5-10 minutes, obtaining emulsion, transferring the emulsion into a storage pot, and stirring for standby at the stirring speed of 200-300 rpm;
(4) And (3) a blade coating die: spreading the emulsion obtained in the step (3) into a crawler belt mould with a release coating for standby;
(5) And (3) carrying out microwave curing in a water bath: transferring the crawler belt mold with the emulsion in the step (4) to a water bath microwave curing oven, carrying out linear curing on the material through water bath and microwaves at the same time, controlling the linear speed to control the flowing time to be 2-5 minutes, controlling the microwave power to be 1500-3000GHz, and controlling the temperature of the water bath to be 75-95 ℃;
(6) Washing: washing the solidified raw materials, firstly washing by mixing deionized water with a surfactant solution, and then washing by using deionized water to remove residual monomers;
(7) And (3) drying: and transferring the washed raw materials into a negative pressure high temperature drying pot for drying and dewatering, wherein the pressure and the temperature are set according to the conventional method, and the drying time is 2-4 hours, so that the acrylic ester foam material is obtained.
2. The method according to claim 1, characterized in that the synthesis step of the oil-soluble initiator is as follows:
(1) Adding azodiisobutyronitrile hydrazine into a three-neck flask A provided with a stirrer, an air duct and a thermometer, adding excessive hexanol, stirring to dissolve the azodiisobutyronitrile hydrazine, cooling with ice water bath, introducing chlorine to obtain a mixture, fully stirring the mixture at a stirring speed of 30-50 r/min, and carrying out oxidation reaction for 4-5h 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 after introducing, carrying out a Pinner reaction, and carrying out suction filtration to obtain an intermediate B;
(3) Adding deionized water into a three-neck flask B, starting stirring at a stirring speed of 30-50 r/min, placing the three-neck flask B into ice water while stirring, cooling, adding an intermediate B into the three-neck flask B, heating to 20 ℃, stirring for 3-5 hours, hydrolyzing to obtain a reaction mixture, cooling the reaction mixture until solids are separated out to obtain a corresponding crude product, recrystallizing the crude product with ethanol and water to obtain a pure product, and obtaining the azobisisobutyrate dihexyl ester, namely the required oil-soluble initiator.
3. The method according to claim 1, wherein the backbone-based monomer is 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, octadecyl acrylate, and octadecyl acrylate.
4. The method according to claim 1, wherein the crosslinking monomer is one or more of 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1, 12-dodecane dimethacrylate, 1, 14-tetradecanediol dimethacrylate, ethylene glycol dimethacrylate and neopentyl triacrylate.
5. The method according to claim 1, wherein the water-soluble initiator is any one of sodium persulfate, potassium persulfate, and ammonium persulfate.
6. The method according to claim 1, characterized in that the emulsifier is a water-in-oil emulsifier having an HLB value of 3-6.
7. The method of claim 6, wherein the emulsifier is a diglycerol isostearate.
8. The method according to claim 1, characterized in that the electrolyte solution is a calcium chloride solution or a sodium chloride solution, the concentration of the electrolyte solution being 1-4%.
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| CN114207019A (en) * | 2019-08-08 | 2022-03-18 | 赢创运营有限公司 | PMMA-based cast polymers with improved mechanical properties |
| CN113637278A (en) * | 2021-09-17 | 2021-11-12 | 佛山市嘉信盈科技有限公司 | Short fiber toughened water-absorbent acrylate high polymer material and preparation method thereof |
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