CN115010851B - Preparation method of poly glycidyl methacrylate microsphere - Google Patents
Preparation method of poly glycidyl methacrylate microsphere Download PDFInfo
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- CN115010851B CN115010851B CN202210768345.6A CN202210768345A CN115010851B CN 115010851 B CN115010851 B CN 115010851B CN 202210768345 A CN202210768345 A CN 202210768345A CN 115010851 B CN115010851 B CN 115010851B
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- 239000004005 microsphere Substances 0.000 title claims abstract description 52
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 170
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 113
- 239000000047 product Substances 0.000 claims abstract description 61
- 238000005406 washing Methods 0.000 claims abstract description 56
- 238000001914 filtration Methods 0.000 claims abstract description 53
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 47
- 239000012043 crude product Substances 0.000 claims abstract description 40
- 238000004806 packaging method and process Methods 0.000 claims abstract description 23
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims abstract description 18
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004342 Benzoyl peroxide Substances 0.000 claims abstract description 15
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 15
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 13
- 238000005086 pumping Methods 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000007689 inspection Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- 239000000839 emulsion Substances 0.000 claims description 56
- 238000004140 cleaning Methods 0.000 claims description 47
- 238000004062 sedimentation Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 36
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 32
- 239000002912 waste gas Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000004945 emulsification Methods 0.000 claims description 16
- 239000002351 wastewater Substances 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 239000012452 mother liquor Substances 0.000 claims description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 2
- 239000011324 bead Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 18
- 239000003999 initiator Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 49
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 28
- 239000010865 sewage Substances 0.000 description 11
- 229920000058 polyacrylate Polymers 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- 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
- C08J11/00—Recovery or working-up of waste materials
-
- 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/02—Recovery or working-up of waste materials of solvents, plasticisers or unreacted monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a poly glycidyl methacrylate microsphere, which comprises the steps of emulsifying the poly glycidyl methacrylate, the ethylene glycol dimethacrylate and water, and carrying out polymerization reaction on the poly glycidyl methacrylate and the ethylene glycol dimethacrylate by taking benzoyl peroxide as an initiator; filtering the crude product; washing the filtered crude product with water and ethanol; transferring the obtained product into a settling tank for settling, and pumping out and filtering an upper suspension after natural settling; and (3) soaking the filtered product in an ethanol water solution, then inspecting the product, packaging and warehousing after the inspection is qualified. The prepared polyglycidyl methacrylate microsphere has larger pore diameter and more concentrated pore diameter size, and can realize the control of the pore diameter of the polyglycidyl methacrylate microsphere.
Description
Technical Field
The invention relates to a preparation method of a poly glycidyl methacrylate microsphere.
Background
The poly glycidyl methacrylate (Polyglycidyl methacrylate, PGMA) microsphere is a functional polymer material rich in epoxy groups, and has a specific physical structure and good chemical reaction performance. The ultra-large pore PGMA microsphere has the characteristics of high rigidity and stable property, and the surface of the ultra-large pore PGMA microsphere contains epoxy groups, so that the surface of the ultra-large pore PGMA microsphere has hydrophobicity, can be subjected to hydrophilic modification and further functionalized to prepare a required medium, so that the ultra-large pore PGMA microsphere has wide prospect in rapid separation and purification.
The aperture of the PGMA microsphere prepared by the existing preparation method of the PGMA microsphere is generally not more than 22nm, the aperture is smaller, the rigidity is smaller, and the size of the aperture is more dispersed, so that the performance difference of the PGMA microsphere prepared in the same batch is larger and the PGMA microsphere is not easy to control.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of the poly (glycidyl methacrylate) microsphere, the prepared poly (glycidyl methacrylate) microsphere has larger pore diameter and more concentrated pore size, and the pore diameter of the poly (glycidyl methacrylate) microsphere can be controlled.
The invention is realized by the following technical scheme:
the preparation method of the polyglycidyl methacrylate microsphere comprises the following steps:
adding glycidyl methacrylate, ethylene glycol dimethacrylate and water into an emulsifying machine, fully mixing the glycidyl methacrylate with the water and homogenizing to form an emulsion, adding an aqueous solution of sodium dodecyl sulfate and homogenizing to form an emulsion, adding benzoyl peroxide and water and homogenizing to form an emulsion, transferring to a reaction kettle, and adding toluene and water to form an emulsion; the mass ratio of the glycidyl methacrylate to the ethylene glycol dimethacrylate is 1:0.5-1; the mass ratio of the glycidyl methacrylate to the benzoyl peroxide is 1:0.003-0.01; the mass ratio of the glycidyl methacrylate to the toluene is 1:1.2-2;
polymerization reaction: stirring the emulsion obtained after emulsification uniformly in a closed polymerization reaction kettle, stirring and heating, and after full reaction, reducing the temperature to room temperature to obtain a crude product;
filtering and collecting, namely filtering the crude product, and then washing the crude product by pure water;
ethanol cleaning: placing the crude product into a cleaner, and adding ethanol for cleaning;
washing the crude product with pure water in a washer;
sedimentation, namely filtering the product obtained after water washing, transferring the product into a sedimentation tank, stirring the product uniformly by pure water, and pumping out and filtering an upper suspension after natural sedimentation; repeated sedimentation is carried out for a plurality of times.
Further, the mass ratio of the glycidyl methacrylate to the sodium dodecyl sulfate is 100:0.0305-0.3.
Further, the total input amount of the water is 1 to 2 times of the total mass of the glycidyl methacrylate, the ethylene glycol dimethacrylate and the toluene.
Further, the filtering and collecting step further includes: and collecting and layering the filtrate discharged by filtering the crude product, and separating the filtrate into filtered wastewater and reaction waste liquid.
Further, the ethanol cleaning step further comprises: recovering ethanol mother liquor generated after cleaning; the recovery method of the ethanol mother liquor in the ethanol cleaning step comprises the following steps:
and (3) distilling: putting the ethanol mother liquor collected in a plurality of batches into an ethanol distillation kettle for recycling distillation;
condensing: condensing the ethanol solvent obtained after distillation, and recovering the condensed ethanol solvent.
Further, it also comprises the following steps:
and packaging and warehousing, namely soaking the settled product in ethanol water solution, then inspecting the product, packaging and warehousing after the inspection is qualified.
Further, the chemical reaction formula occurring in the polymerization reaction is:
further, in the polymerization step, the temperature is raised to 65 ℃ by stirring, and the reaction time of the polymerization is at least 20 hours.
Further, the ratio of ethanol to water in the ethanol solution in the packaging and warehousing step is 1:4.
Further, various waste gases are generated in the preparation process of the poly glycidyl methacrylate microspheres, and the waste gas treatment method comprises the following steps: and collecting various waste gases, performing two-stage alkali liquor spraying, biological composite filter bed filtering and active carbon fiber adsorption, and then discharging the waste gases to the atmosphere.
Compared with the prior art, the invention has the advantages that:
1. the invention provides a preparation method for preparing a polyglycidyl methacrylate microsphere with larger pore diameter and more concentrated pore size; the performance of the poly (glycidyl methacrylate) microspheres is improved, and the performance difference of the poly (glycidyl methacrylate) microspheres in the same production batch is reduced; and the aperture of the finally prepared PGMA microsphere can be controlled by controlling the feeding amount of toluene.
2. The invention provides a method for recovering ethanol mother liquor by distillation and condensation, which can achieve more than 60% of ethanol recovery rate in the ethanol mother liquor and improve the ethanol recovery rate.
Drawings
FIG. 1 is a flow chart of a method for preparing a polyglycidyl methacrylate microsphere according to the invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent, so that those skilled in the art can fully understand the technical contents of the present invention. It is to be understood that the following examples are given by way of illustration of the present invention and are not to be construed as limiting the scope of the present invention, since various modifications and alterations of no particular nature will fall within the scope of the invention as defined by the appended claims. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
Emulsification, namely, putting 24g of glycidyl methacrylate, 12g of ethylene glycol dimethacrylate and 72g of water into an emulsifying machine, fully mixing and homogenizing the glycidyl methacrylate and the water to form an emulsion, adding an aqueous solution containing 0.072g of sodium dodecyl sulfate to form an emulsion again, adding 0.072g of benzoyl peroxide and water to form the emulsion again, transferring the emulsion to a reaction kettle, and adding 28.8g of toluene and 58g of water to form the emulsion.
Polymerization reaction: and (3) uniformly stirring the emulsion finally produced after emulsification in a closed polymerization reaction kettle, heating to 65 ℃ with stirring, reacting for 20 hours, and then reducing the temperature to room temperature to obtain a crude product. And (3) generating reaction waste gas containing toluene in the polymerization reaction, collecting the reaction waste gas generated in the polymerization reaction, and conveying the reaction waste gas to a waste gas treatment device for treatment after the preparation of the PGMA microspheres is completed.
Wherein the molecular formula of the glycidyl methacrylate is as follows:
the molecular formula of the ethylene glycol dimethacrylate is as follows:
the molecular formula of benzoyl peroxide is:
the chemical reaction formula occurring in the polymerization reaction is:
the reaction principle is as follows: the polyglycidyl methacrylate microsphere is prepared by the polymerization reaction of glycidyl methacrylate and ethylene glycol dimethacrylate in an aqueous phase under the action of benzoyl peroxide serving as an initiator.
Filtering and collecting, namely filtering the crude product obtained after the polymerization reaction to remove filtrate. And (3) generating filtered waste gas containing toluene in the process of filtering treatment, collecting the filtered waste gas generated in the filtering process, and conveying the filtered waste gas to a waste gas treatment device for treatment after the preparation of the PGMA microspheres is completed. Layering the filtrate produced after the filtering treatment to obtain the washing wastewater and the reaction waste liquid. Discharging the cleaning wastewater generated in the layering treatment process into a sewage treatment station for treatment; and collecting and delivering the reaction waste liquid generated in the layering treatment process to units with treatment qualification for treatment. And (3) layering waste gas containing toluene is generated in the layering process, the separated waste gas generated in the layering process is collected, and the waste gas is conveyed to a waste gas treatment device for treatment after the preparation of the PGMA microspheres is completed. The crude product after the filtration treatment was washed 5 times with 200ml of pure water each time. During the washing process, a washing waste gas containing toluene and washing waste water are generated. Collecting the cleaning waste gas generated in the washing process, and conveying the waste gas to a waste gas treatment device for treatment after the preparation of the PGMA microspheres is completed; and discharging the cleaning wastewater generated in the cleaning process into a sewage treatment station for treatment.
Ethanol cleaning, namely placing the washed crude product into a cleaner, and cleaning the crude product with ethanol for 3 times, wherein 100g of ethanol is used for cleaning each time to remove residual organic matters such as glycidyl methacrylate, dimethyl glycol acrylate and the like. The ethanol cleaning process generates cleaning waste gas containing ethanol and ethanol mother liquor. And collecting the cleaning waste gas generated in the ethanol cleaning process, and conveying the waste gas to a waste gas treatment device for treatment after the preparation of the PGMA microspheres is completed. And recovering the ethanol mother liquor generated in the ethanol cleaning process and carrying out corresponding treatment.
The treatment mode of the ethanol mother liquor generated in the ethanol cleaning process is as follows: putting the ethanol mother liquor collected in a plurality of batches into an ethanol distillation kettle for recycling distillation; condensing the ethanol solvent obtained after distillation, recycling the condensed ethanol solvent for production, and treating the distillation residual liquid in the ethanol distillation kettle by a unit with treatment qualification. And collecting noncondensable gas generated in the condensation process, and conveying the noncondensable gas to an exhaust gas treatment device for treatment after the preparation of the PGMA microspheres is completed. By treating the ethanol mother liquor in this way, the recovery rate of ethanol can reach more than 60%.
And (3) water washing, namely washing the material subjected to ethanol washing in a washer with pure water for 5 times to remove foam generated by the material in the polymerization reaction, wherein 200ml of pure water is used for each washing. During the washing process, a washing waste gas containing ethanol and a washing waste water are generated. Collecting the cleaning waste gas generated in the water cleaning process, and conveying the waste gas to a waste gas treatment device for treatment after the preparation of the PGMA microspheres is completed; and discharging the cleaning wastewater generated in the water cleaning process into a sewage treatment station for treatment.
Settling, namely filtering and drying the product after water washing, transferring the product into a settling tank, adding pure water, stirring uniformly, naturally settling, pumping out the upper suspension, filtering, and repeating for 5 times; wherein 500ml of pure water was added for the first time, followed by 400ml of pure water each time. And discharging the sedimentation wastewater generated in the sedimentation process into a sewage treatment station for treatment. And obtaining a finished product material containing polyacrylate-based spheres after sedimentation.
And packaging and warehousing, namely adding 20% ethanol aqueous solution into the finished product materials obtained after sedimentation treatment for soaking, checking the soaked finished product materials, and packaging and warehousing the finished product materials after the checking is qualified.
The polyacrylate-based spheres are PGMA microspheres prepared by taking glycidyl methacrylate as a monomer.
The treatment method of the exhaust gas collected for multiple times comprises the following steps: and collecting various waste gases, performing two-stage alkali liquor spraying, biological composite filter bed filtering and active carbon fiber adsorption, and then discharging the waste gases to the atmosphere through an exhaust pipe with the height of 33 meters.
Example 2
Emulsification, namely, putting 24g of glycidyl methacrylate, 18g of ethylene glycol dimethacrylate and 60g of water into an emulsifying machine, fully mixing and homogenizing the glycidyl methacrylate and the water to form an emulsion, adding an aqueous solution containing 0.04g of sodium dodecyl sulfate to form an emulsion again, adding 0.15g of benzoyl peroxide and the water to form the emulsion again, transferring the emulsion to a reaction kettle, and adding 28.8g of toluene and 58g of water to form the emulsion.
Polymerization reaction: and (3) uniformly stirring the emulsion finally produced after emulsification in a closed polymerization reaction kettle, heating to 65 ℃ with stirring, reacting for 20 hours, and then reducing the temperature to room temperature to obtain a crude product.
Filtering and collecting, namely filtering the crude product obtained after the polymerization reaction to remove filtrate.
Ethanol cleaning, namely placing the washed crude product into a cleaner, and cleaning with ethanol for 3 times, wherein 100g of ethanol is used for cleaning each time
And (3) water washing, namely washing the material subjected to ethanol washing in a washer with pure water for 5 times to remove foam generated by the material in the polymerization reaction, wherein 200ml of pure water is used for each washing.
Settling, namely filtering and drying the product after water washing, transferring the product into a settling tank, adding pure water, stirring uniformly, naturally settling, pumping out the upper suspension, filtering, and repeating for 5 times; wherein 500ml of pure water was added for the first time, followed by 400ml of pure water each time. And discharging the sedimentation wastewater generated in the sedimentation process into a sewage treatment station for treatment. And obtaining a finished product material containing polyacrylate-based spheres after sedimentation.
And packaging and warehousing, namely adding 20% ethanol aqueous solution into the finished product materials obtained after sedimentation treatment for soaking, checking the soaked finished product materials, and packaging and warehousing the finished product materials after the checking is qualified.
Example 3
Emulsification, namely, putting 24g of glycidyl methacrylate, 24g of ethylene glycol dimethacrylate and 96g of water into an emulsifying machine, fully mixing and homogenizing the glycidyl methacrylate and the water to form an emulsion, adding an aqueous solution containing 0.0074g of sodium dodecyl sulfate to form an emulsion again, adding 0.24g of benzoyl peroxide and the water to form the emulsion again, transferring the emulsion to a reaction kettle, and adding 28.8g of toluene and 58g of water to form the emulsion.
Polymerization reaction: and (3) uniformly stirring the emulsion finally produced after emulsification in a closed polymerization reaction kettle, heating to 65 ℃ with stirring, reacting for 20 hours, and then reducing the temperature to room temperature to obtain a crude product.
Filtering and collecting, namely filtering the crude product obtained after the polymerization reaction to remove filtrate.
Ethanol cleaning, namely placing the washed crude product into a cleaner, and cleaning with ethanol for 3 times, wherein 100g of ethanol is used for cleaning each time
And (3) water washing, namely washing the material subjected to ethanol washing in a washer with pure water for 5 times to remove foam generated by the material in the polymerization reaction, wherein 200ml of pure water is used for each washing.
Settling, namely filtering and drying the product after water washing, transferring the product into a settling tank, adding pure water, stirring uniformly, naturally settling, pumping out the upper suspension, filtering, and repeating for 5 times; wherein 500ml of pure water was added for the first time, followed by 400ml of pure water each time. And discharging the sedimentation wastewater generated in the sedimentation process into a sewage treatment station for treatment. And obtaining a finished product material containing polyacrylate-based spheres after sedimentation.
And packaging and warehousing, namely adding 20% ethanol aqueous solution into the finished product materials obtained after sedimentation treatment for soaking, checking the soaked finished product materials, and packaging and warehousing the finished product materials after the checking is qualified.
Example 4
Emulsifying, namely adding 24g of glycidyl methacrylate, 12g of ethylene glycol dimethacrylate and 40g of water into an emulsifying machine, fully mixing and homogenizing the glycidyl methacrylate and the water to form an emulsion, adding an aqueous solution containing 0.072g of sodium dodecyl sulfate, homogenizing again to form an emulsion, adding 0.072g of benzoyl peroxide and the water, homogenizing again to form an emulsion, transferring to a reaction kettle, and adding 38g of toluene and 40g of water to form an emulsion.
Polymerization reaction: and (3) uniformly stirring the emulsion finally produced after emulsification in a closed polymerization reaction kettle, heating to 65 ℃ with stirring, reacting for 20 hours, and then reducing the temperature to room temperature to obtain a crude product.
Filtering and collecting, namely filtering the crude product obtained after the polymerization reaction to remove filtrate.
Ethanol cleaning, namely placing the washed crude product into a cleaner, and cleaning with ethanol for 3 times, wherein 100g of ethanol is used for cleaning each time
And (3) water washing, namely washing the material subjected to ethanol washing in a washer with pure water for 5 times to remove foam generated by the material in the polymerization reaction, wherein 200ml of pure water is used for each washing.
Settling, namely filtering and drying the product after water washing, transferring the product into a settling tank, adding pure water, stirring uniformly, naturally settling, pumping out the upper suspension, filtering, and repeating for 5 times; wherein 500ml of pure water was added for the first time, followed by 400ml of pure water each time. And discharging the sedimentation wastewater generated in the sedimentation process into a sewage treatment station for treatment. And obtaining a finished product material containing polyacrylate-based spheres after sedimentation.
And packaging and warehousing, namely adding 20% ethanol aqueous solution into the finished product materials obtained after sedimentation treatment for soaking, checking the soaked finished product materials, and packaging and warehousing the finished product materials after the checking is qualified.
Example 5
Emulsification, namely, putting 24g of glycidyl methacrylate, 18g of ethylene glycol dimethacrylate and 60g of water into an emulsifying machine, fully mixing and homogenizing the glycidyl methacrylate and the water to form an emulsion, adding an aqueous solution containing 0.04g of sodium dodecyl sulfate to form an emulsion again, adding 0.15g of benzoyl peroxide and the water to form the emulsion again, transferring the emulsion to a reaction kettle, and adding 38g of toluene and 40g of water to form the emulsion.
Polymerization reaction: and (3) uniformly stirring the emulsion finally produced after emulsification in a closed polymerization reaction kettle, heating to 65 ℃ with stirring, reacting for 20 hours, and then reducing the temperature to room temperature to obtain a crude product.
Filtering and collecting, namely filtering the crude product obtained after the polymerization reaction to remove filtrate.
Ethanol cleaning, namely placing the washed crude product into a cleaner, and cleaning with ethanol for 3 times, wherein 100g of ethanol is used for cleaning each time
And (3) water washing, namely washing the material subjected to ethanol washing in a washer with pure water for 5 times to remove foam generated by the material in the polymerization reaction, wherein 200ml of pure water is used for each washing.
Settling, namely filtering and drying the product after water washing, transferring the product into a settling tank, adding pure water, stirring uniformly, naturally settling, pumping out the upper suspension, filtering, and repeating for 5 times; wherein 500ml of pure water was added for the first time, followed by 400ml of pure water each time. And discharging the sedimentation wastewater generated in the sedimentation process into a sewage treatment station for treatment. And obtaining a finished product material containing polyacrylate-based spheres after sedimentation.
And packaging and warehousing, namely adding 20% ethanol aqueous solution into the finished product materials obtained after sedimentation treatment for soaking, checking the soaked finished product materials, and packaging and warehousing the finished product materials after the checking is qualified.
Example 6
Emulsification, namely, putting 24g of glycidyl methacrylate, 24g of ethylene glycol dimethacrylate and 50g of water into an emulsifying machine, fully mixing and homogenizing the glycidyl methacrylate and the water to form an emulsion, adding an aqueous solution containing 0.0074g of sodium dodecyl sulfate to form an emulsion again, adding 0.24g of benzoyl peroxide and the water to form the emulsion again, transferring the emulsion to a reaction kettle, and adding 38g of toluene and 40g of water to form the emulsion.
Polymerization reaction: and (3) uniformly stirring the emulsion finally produced after emulsification in a closed polymerization reaction kettle, heating to 65 ℃ with stirring, reacting for 20 hours, and then reducing the temperature to room temperature to obtain a crude product.
Filtering and collecting, namely filtering the crude product obtained after the polymerization reaction to remove filtrate.
Ethanol cleaning, namely placing the washed crude product into a cleaner, and cleaning with ethanol for 3 times, wherein 100g of ethanol is used for cleaning each time
And (3) water washing, namely washing the material subjected to ethanol washing in a washer with pure water for 5 times to remove foam generated by the material in the polymerization reaction, wherein 200ml of pure water is used for each washing.
Settling, namely filtering and drying the product after water washing, transferring the product into a settling tank, adding pure water, stirring uniformly, naturally settling, pumping out the upper suspension, filtering, and repeating for 5 times; wherein 500ml of pure water was added for the first time, followed by 400ml of pure water each time. And discharging the sedimentation wastewater generated in the sedimentation process into a sewage treatment station for treatment. And obtaining a finished product material containing polyacrylate-based spheres after sedimentation.
And packaging and warehousing, namely adding 20% ethanol aqueous solution into the finished product materials obtained after sedimentation treatment for soaking, checking the soaked finished product materials, and packaging and warehousing the finished product materials after the checking is qualified.
Example 7
Emulsifying, namely adding 24g of glycidyl methacrylate, 12g of ethylene glycol dimethacrylate and 50g of water into an emulsifying machine, fully mixing and homogenizing the glycidyl methacrylate and the water to form an emulsion, adding an aqueous solution containing 0.072g of sodium dodecyl sulfate, homogenizing again to form an emulsion, adding 0.072g of benzoyl peroxide and water, homogenizing again to form an emulsion, transferring to a reaction kettle, and adding 48g of toluene and 60g of water to form an emulsion.
Polymerization reaction: and (3) uniformly stirring the emulsion finally produced after emulsification in a closed polymerization reaction kettle, heating to 65 ℃ with stirring, reacting for 20 hours, and then reducing the temperature to room temperature to obtain a crude product.
Filtering and collecting, namely filtering the crude product obtained after the polymerization reaction to remove filtrate.
Ethanol cleaning, namely placing the washed crude product into a cleaner, and cleaning with ethanol for 3 times, wherein 100g of ethanol is used for cleaning each time
And (3) water washing, namely washing the material subjected to ethanol washing in a washer with pure water for 5 times to remove foam generated by the material in the polymerization reaction, wherein 200ml of pure water is used for each washing.
Settling, namely filtering and drying the product after water washing, transferring the product into a settling tank, adding pure water, stirring uniformly, naturally settling, pumping out the upper suspension, filtering, and repeating for 5 times; wherein 500ml of pure water was added for the first time, followed by 400ml of pure water each time. And discharging the sedimentation wastewater generated in the sedimentation process into a sewage treatment station for treatment. And obtaining a finished product material containing polyacrylate-based spheres after sedimentation.
And packaging and warehousing, namely adding 20% ethanol aqueous solution into the finished product materials obtained after sedimentation treatment for soaking, checking the soaked finished product materials, and packaging and warehousing the finished product materials after the checking is qualified.
Example 8
Emulsification, namely, putting 24g of glycidyl methacrylate, 24g of ethylene glycol dimethacrylate and 60g of water into an emulsifying machine, fully mixing and homogenizing the glycidyl methacrylate and the water to form an emulsion, adding an aqueous solution containing 0.0074g of sodium dodecyl sulfate to form an emulsion again, adding 0.24g of benzoyl peroxide and the water to form the emulsion again, transferring the emulsion to a reaction kettle, and adding 48g of toluene and 60g of water to form the emulsion.
Polymerization reaction: and (3) uniformly stirring the emulsion finally produced after emulsification in a closed polymerization reaction kettle, heating to 65 ℃ with stirring, reacting for 20 hours, and then reducing the temperature to room temperature to obtain a crude product.
Filtering and collecting, namely filtering the crude product obtained after the polymerization reaction to remove filtrate.
Ethanol cleaning, namely placing the washed crude product into a cleaner, and cleaning with ethanol for 3 times, wherein 100g of ethanol is used for cleaning each time
And (3) water washing, namely washing the material subjected to ethanol washing in a washer with pure water for 5 times to remove foam generated by the material in the polymerization reaction, wherein 200ml of pure water is used for each washing.
Settling, namely filtering and drying the product after water washing, transferring the product into a settling tank, adding pure water, stirring uniformly, naturally settling, pumping out the upper suspension, filtering, and repeating for 5 times; wherein 500ml of pure water was added for the first time, followed by 400ml of pure water each time. And discharging the sedimentation wastewater generated in the sedimentation process into a sewage treatment station for treatment. And obtaining a finished product material containing polyacrylate-based spheres after sedimentation.
And packaging and warehousing, namely adding 20% ethanol aqueous solution into the finished product materials obtained after sedimentation treatment for soaking, checking the soaked finished product materials, and packaging and warehousing the finished product materials after the checking is qualified.
The average specific surface area, average pore volume and average pore diameter of PGMA microspheres prepared in examples 1 to 8 are shown in the following table:
from the data in the table, it can be seen that the pore diameter of the PGMA microsphere prepared by the preparation method of the present invention is mainly affected by the toluene feeding amount, and the pore diameter of the PGMA microsphere prepared by the preparation method is smaller under the condition that the toluene feeding amount is the same or similar, and the pore diameter of the PGMA microsphere gradually increases with the increase of the toluene feeding amount. Therefore, the preparation method provided by the invention can control the aperture size of the PGMA microspheres by controlling the feeding amount of toluene, and when the mass percentages of the fed toluene are similar, the PGMA microspheres have small size difference and similar performance; preferably, the further control of the PGMA microsphere pore size is achieved by controlling the amount of other materials fed. The aperture of the PGMA microsphere prepared by the preparation method is between 22.2 and 28.9nm, and compared with the aperture of the PGMA microsphere prepared by the existing preparation method, the aperture of the PGMA microsphere is further increased, and the performance is further improved.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the polyglycidyl methacrylate microsphere is characterized by comprising the following steps of:
adding glycidyl methacrylate, ethylene glycol dimethacrylate and water into an emulsifying machine, fully mixing the glycidyl methacrylate with the water and homogenizing to form an emulsion, adding an aqueous solution of sodium dodecyl sulfate and homogenizing to form an emulsion, adding benzoyl peroxide and water and homogenizing to form an emulsion, transferring to a reaction kettle, and adding toluene and water to form an emulsion; the mass ratio of the glycidyl methacrylate to the ethylene glycol dimethacrylate is 1:0.5-1; the mass ratio of the glycidyl methacrylate to the benzoyl peroxide is 1:0.003-0.01; the mass ratio of the glycidyl methacrylate to the toluene is 1:1.2-2;
polymerization reaction: stirring the emulsion obtained after emulsification uniformly in a closed polymerization reaction kettle, stirring and heating, and after full reaction, reducing the temperature to room temperature to obtain a crude product;
filtering and collecting, namely filtering the crude product, and then washing the crude product by pure water;
ethanol cleaning: placing the crude product into a cleaner, and adding ethanol for cleaning;
washing the crude product with pure water in a washer;
sedimentation, namely filtering the product obtained after water washing, transferring the product into a sedimentation tank, stirring the product uniformly by pure water, and pumping out and filtering an upper suspension after natural sedimentation; repeated sedimentation is carried out for a plurality of times.
2. The preparation method of the polyglycidyl methacrylate microsphere according to claim 1, wherein the mass ratio of the glycidyl methacrylate to the sodium dodecyl sulfate is 100:0.0305-0.3.
3. The method for producing polyglycidyl methacrylate beads according to claim 1, wherein the total amount of water added is 1 to 2 times the total mass of glycidyl methacrylate, ethylene glycol dimethacrylate and toluene.
4. The method for preparing the polyglycidyl methacrylate microspheres according to claim 1, wherein the step of collecting by filtration further comprises: and collecting and layering the filtrate discharged by filtering the crude product, and separating the filtrate into filtered wastewater and reaction waste liquid.
5. The method for preparing the polyglycidyl methacrylate microspheres according to claim 1, wherein the ethanol washing step further comprises: recovering ethanol mother liquor generated after cleaning; the recovery method of the ethanol mother liquor in the ethanol cleaning step comprises the following steps:
and (3) distilling: putting the ethanol mother liquor collected in a plurality of batches into an ethanol distillation kettle for recycling distillation;
condensing: condensing the ethanol solvent obtained after distillation, and recovering the condensed ethanol solvent.
6. The method for preparing the polyglycidyl methacrylate microsphere according to claim 1, characterized in that it further comprises the steps of:
and packaging and warehousing, namely soaking the settled product in ethanol water solution, then inspecting the product, packaging and warehousing after the inspection is qualified.
7. The method for preparing the polyglycidyl methacrylate microsphere as claimed in claim 1, wherein the chemical reaction formula occurring in the polymerization reaction is:
8. the method for producing the polyglycidyl methacrylate particles according to claim 1, wherein the temperature is raised to 65℃with stirring in the step of polymerization, and the reaction time of the polymerization is at least 20 hours.
9. The method for preparing the polyglycidyl methacrylate particles according to claim 6, wherein the ratio of ethanol to water in the ethanol solution in the packaging and warehousing step is 1:4.
10. The method for producing the polyglycidyl methacrylate microsphere according to any one of claims 1 to 9, characterized in that various exhaust gases are generated in the process of producing the polyglycidyl methacrylate microsphere, and the method for treating the exhaust gases is as follows: and collecting various waste gases, performing two-stage alkali liquor spraying, biological composite filter bed filtering and active carbon fiber adsorption, and then discharging the waste gases to the atmosphere.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417552A (en) * | 2011-09-22 | 2012-04-18 | 中国科学院过程工程研究所 | Polymer nanomicrosphere product with uniform and controllable size and preparation method thereof |
| CN102617804A (en) * | 2011-01-28 | 2012-08-01 | 中国科学院化学研究所 | Diplopore nanoscale poly(glycidyl methacrylate)-ethylene glycol dimethacrylate (PGMA-EDMA) cross-linked microballoons and preparation method thereof |
| CN104275166A (en) * | 2013-07-05 | 2015-01-14 | 无锡加莱克色谱科技有限公司 | Anion exchange chromatographic filler for purification of low molecular weight heparin, preparation method, chromatographic column filled thereby and purification method |
| CN108467461A (en) * | 2018-02-28 | 2018-08-31 | 苏州为度生物技术有限公司 | The preparation method of surface carboxyl groups nucleocapsid superparamagnetism microballoon |
| CN114470308A (en) * | 2022-03-01 | 2022-05-13 | 苏州森康微球医疗科技有限公司 | Preparation process of macroporous sodium polyacrylate embolism microsphere |
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| EP2088160B1 (en) * | 2006-12-01 | 2012-10-31 | Institute of Process Engineering Chinese Academy of Sciences | A super macroporous polymeric microsphere and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617804A (en) * | 2011-01-28 | 2012-08-01 | 中国科学院化学研究所 | Diplopore nanoscale poly(glycidyl methacrylate)-ethylene glycol dimethacrylate (PGMA-EDMA) cross-linked microballoons and preparation method thereof |
| CN102417552A (en) * | 2011-09-22 | 2012-04-18 | 中国科学院过程工程研究所 | Polymer nanomicrosphere product with uniform and controllable size and preparation method thereof |
| CN104275166A (en) * | 2013-07-05 | 2015-01-14 | 无锡加莱克色谱科技有限公司 | Anion exchange chromatographic filler for purification of low molecular weight heparin, preparation method, chromatographic column filled thereby and purification method |
| CN108467461A (en) * | 2018-02-28 | 2018-08-31 | 苏州为度生物技术有限公司 | The preparation method of surface carboxyl groups nucleocapsid superparamagnetism microballoon |
| CN114470308A (en) * | 2022-03-01 | 2022-05-13 | 苏州森康微球医疗科技有限公司 | Preparation process of macroporous sodium polyacrylate embolism microsphere |
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