CN101029099A - Fast hydrolyzation of polyacrylamide - Google Patents
Fast hydrolyzation of polyacrylamide Download PDFInfo
- Publication number
- CN101029099A CN101029099A CN 200710038965 CN200710038965A CN101029099A CN 101029099 A CN101029099 A CN 101029099A CN 200710038965 CN200710038965 CN 200710038965 CN 200710038965 A CN200710038965 A CN 200710038965A CN 101029099 A CN101029099 A CN 101029099A
- Authority
- CN
- China
- Prior art keywords
- polyacrylamide
- hydrolysis
- fast
- hydrolyzation
- granulation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A fast method for hydrolyzing propathene amine is carried out by homo-polymerizing for acrylic amide solution by thermal polymerization or ultraviolet radiant polymerization to obtain propathene amine rubber slabs, cutting them into strips or blocks by crusher, granulating, adding into alkali as hydrolytic agent, hydrolyzing by microwave radiating, drying and crushing to obtain 2-55% granular propathene with different hydrolytic degree. It's cheap, efficient and reliable and has no environmental pollution.
Description
Technical field
The present invention relates to the environmental protection field, relate in particular to a kind of fast hydrolyzation of novel polyacrylamide.
Background technology
At present, the production of anion-polyacrylamide preparation both at home and abroad mainly contain copolymerization, polymerization posthydrolysis and before add three kinds of technologies of alkali homopolymerization cohydrolysis.
Copolymerization process refers to that Acrylic Acid Monomer is through alkali neutralization and acrylamide, though this method does not need hydrolysis, but material purity is required high, and be difficult to obtain high molecular weight products, acrylamide polymerization concentration 31.5% among the US3732193, sodium acrylate content accounts for 41.5% in the mix monomer, the Molecular Weight for Polyacrylamide that makes only more than 1,000 ten thousand.
Polymerization posthydrolysis technology refers to alkaline hydrolysis after the acrylamide homopolymerization, the Molecular Weight for Polyacrylamide of this method preparation is higher, molecular weight can be up to 3,000 ten thousand, but also there is obvious defects, US40482682 discloses the method that alkaline hydrolysis after a kind of acrylamide homopolymerization prepares the powdered polypropylene acid amides, after the acrylamide solution homopolymerization of 30% concentration, through mechanical pelleting, when the about 4mm of particle diameter, add 45% sodium hydroxide and carry out thermal conduction form hydrolysis reaction, dry, pulverize and make the powdered polypropylene acid amides; CN1057057A also discloses the instant anionic polyacrylamide method of a kind of preparation: the colloid that the acrylamide monomer polymerization makes is mediated by adding alkali, and pyrohydrolysis 5～20 hours makes fast-dissolving anion type polyacrylamide; In the method for hydrolysis in CN148908A super high molecular weight polyacrylamide synthesis technology, directly throw certain proportion after the blob of viscose granulation and sneak into solid base, utilize the hydrolyzer of band heating jacket and the agitator prepared in reaction hydrolyzed polyacrylamide with ultra-high molecular weight that is hydrolyzed; In addition, then disclose a kind of colloid that is used among the CN2531868Y and mediated the granulating integrated kneader of hydrolysis, this equipment is provided with hydrolytic tank, stirring arm and granulation spiral conveyer etc.; Although the outstanding advantage of this technology is to be fit to preparation high molecular even extra high molecular polymer, but no matter adding alkali mediates after hydrolysis or the granulation and the direct conglomerate integration hydrolysis of solid caustic soda, alkaline hydrolysis technology all exists open defect such as production efficiency is low after all these class polymerizations, facility investment is big, energy consumption is high, and because high molecular polymeric gel piece heat-conductive characteristic is poor, hydrolysis time is long, hydrolysis is incomplete, the shearing action and the hot environment of mediating in addition in the hydrolytic process also easily cause the polymer macromolecule degraded, cause molecular weight product to descend.
Before add alkali homopolymerization cohydrolysis technology and be meant and before polymerization, add alkali, pH value by control polymerization of aqueous solution of acrylamide system, reach the purpose of polymerization cohydrolysis, as proposing to adopt sodium hydroxide-boric acid in Japan's special permission communique clear 5224295 and 52137483, the pH value of sodium hydroxide-Starso control acrylamide solution, but add-on is few, degree of hydrolysis is low, add-on is big, though can obtain the polyacrylamide of higher degree of hydrolysis, but same difficult acquisition high-molecular weight polyacrylamide, and the posthydrolysis time is long.Disclose among the CN1168894A and added the alkali mode before a kind of and by blasting CO
2The homopolymerization cohydrolysis of control reacting system PH value prepares the method for polyacrylamide, but the same hydrolysis time of this method is long, and the polyacrylamide hydrolysis degree that makes low (24～30%).
In addition, a kind of method of new type ultrasonic hydrolysis acylamide polymer is also disclosed among the flat 3-93807 of day disclosure special permission communique, but this method still needs to cooperate higher hydrolysis temperature, and hydrolysis time is still long, and high-intensity ultrasonic wave radiation easily causes polymericular weight degraded, product quality to worsen.In CN1283641A, add the alkali copolymerization before having adopted and prepare anion-polyacrylamide by the mode of microwave hydrolysis again, although this method adopts the microwave hydrolysis mode, improved hydrolysis efficiency, but still adding the alkali copolymerization technology before belonging to, high pH polymerization system environment makes the preparation super high molecular weight polyacrylamide still difficult.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the weak point that above-mentioned prior art exists that a kind of technology is reliable, the fast hydrolyzation of environmental protection, energy-saving and cost-reducing polyacrylamide.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of fast hydrolyzation of polyacrylamide, it is characterized in that, this method is that acrylamide solution is made high-molecular weight polyacrylamide blob of viscose by thermopolymerization or the homopolymerization of uv-radiation polymerization methods, with knife mill the polyacrylamide blob of viscose is cut into small pieces or strip, send granulating equipment again to and carry out granulation, add alkali after the granulation as hydrolytic reagent, finish hydrolysis reaction fast by the microwave radiation mode, drying, pulverizing make the powdered polypropylene acid amides of 2～55% different degree of hydrolysis again.
Described polyacrylamide blob of viscose molecular weight is between 500～3,000 ten thousand, between water ratio 55～80wt%.
Described polyacrylamide gel granulation, particle diameter are 1～5mm, preferred 1.0～2.0mm.
Described hydrolytic reagent comprises anhydrous sodium carbonate, Anhydrous potassium carbonate, sodium bicarbonate, saleratus, solid sodium hydroxide or solid potassium hydroxide, and its form can be sheet, granular or solution.
The described alkali mode that adds can be that the hot glue grain is directly mixed with solid caustic soda, and preferred granular hydrolytic reagent carries out batch mixing by the blender of being with stirring rake, or carries out batch mixing by machinery rotation formula blender.
The described alkali mode that adds can be in granulation, finishes by thermotropism micelle spraying high density liquid caustic soda, and used alkali is selected the alkaline solution of 20～50wt% or greater concn, the sodium hydroxide solution of preferred 40～50wt%.
It is to adopt tunnel like or rotary type radial pattern hydrolysis reactor, microwave radiation: 0.01～15W/cm that described microwave radiation mode is finished hydrolysis reaction fast
2, radiation frequency: adopt the industrial frequency of utilization 915MHz or the 2450MHz of national regulation, hydrolysis time: 0.3～10min.
Described powdered polypropylene acid amides can obtain different degree of hydrolysis by the add-on of control hydrolysis agent, and drying, mechanical disintegration make the powdery anion-polyacrylamide.
The present invention proposes the method for the quick hydrolysis of a kind of polyacrylamide microwave, the acrylamide polymer blob of viscose of high molecular even ultra-high molecular weight can obtain through at present known disclosed polymerization process, fresh polymerization blob of viscose directly mixes with solid caustic soda when granulating equipment granulation 1～5mm or by going into the microwave reactor water and separate to micelle surface spraying high density liquid caustic soda being laggard, intramolecularly heat effect that microwave produces and non-thermal effect can high speed catalysis be finished the HYDROLYSIS OF POLYACRYLAMIDE AND ITS COPOLYMERS reaction in 0.3～10min, hydrolysis efficiency is high, and the NH of hydrolysis generation
3Not only technology is reliable for convenient recovery the, microwave hydrolysis, environmental protection, and aspect energy-saving and cost-reducing realistic meaning is arranged also.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Heat effect and catalyzed chemical reaction mechanism about microwave:
The fundamental research of microwave and matter interaction is pointed out: different media necessarily means the transformation of energy with certain form to the absorption of microwave, the microcosm of medium is by many end positively chargeds, the electronegative molecule of the other end (or dipole) is formed, in the microwave field, the polar dipole hinders mutually, rubs in the mixed and disorderly thermal motion that aligns repeatedly in the motion with dipole itself of high frequency, produce the intramolecularly heat effect, then show as the material absorbing microwave on the macroscopic view and be transformed into heat energy, this also is common described microwave heating principle.
Microwave heating is that thermal conduction is different with common type of heating, and microwave is by the absorption loss of medium and is converted into a kind of intramolecularly heat effect, rather than relies on the thermal conduction of material itself, so homogeneous heating and rapid.Polyacrylamide adds the hydrolysis heating behind the alkali, and common heating mode effect is unsatisfactory, and this is because the heat-conductive characteristic of polyacrylamide blob of viscose is poor, but microwave heating can be from the inner heating of material, and therefore heating rapidly and evenly.
In addition, experiment finds that microwave has excitation effect to chemical reaction process, and microwave electromagnetic field can directly act on chemical reaction system, thereby chemical reaction process is quickened in catalysis.Hydrolysis of polyacrylamide reaction of the present invention is carried out under the microwave field effect just, and the present invention specifically is described below:
1, polyacrylamide blob of viscose of the present invention can be through disclosed method acquisition at present, commonplace employing acrylamide solution radical polymerization, such as the redox initiation system that can form by persulphate and hydrosulphite, water-soluble azo salt thermal initiator, or the acrylamide triggered polymerization of composite initiator, also can utilize photoinitiator such as benzoin alkylether (ketone) compounds, photosensitive azo-compound, and the photoinitiator Irgacure 2959 that in the CN1396931A polymerization process, mentions, 1173 (CibaSepcialty Chemical companies) etc., make high molecular even super high molecular weight polyacrylamide blob of viscose by the polymerization of optical radiation mode, it is characterised in that typically molecular weight is 500-3000 ten thousand polyacrylamide blob of viscose among the present invention, water ratio 55-80%.
2, continuous or the semi continuous operating procedure of preferential selective polymerization-granulation among the present invention, to guarantee that fresh polymeric gel deblocking temperature is unlikely to undue cooling, can be laminar by the polyacrylamide that obtains in above-mentioned 1 than piece, it also can be the big bulk of still formula polymeric, select earlier to send the granulating equipment granulation again to be cut into small pieces shape or strip of knife mill, also can directly directly the polymerization blob of viscose be cut into the granular size that meets the requirements by roll-type or vertical knife mill, particle diameter 1-5mm, during preferable particle size 1.0-2.0mm, add a certain proportion of solid caustic soda, or the high density liquid caustic soda of thermotropism micelle surface spraying proportional.Wherein the hybrid mode of solid caustic soda and hot glue grain can adopt the blender of band stirring rake to carry out batch mixing, also can carry out batch mixing by machinery rotation formula blender.The release agent that can select to add specified quantitative when solid caustic soda mixes with micelle is to guarantee the micelle easily disperse that do not lump.
3, the alkali described in above-mentioned 2 can be sodium hydroxide (potassium), yellow soda ash (potassium), sodium bicarbonate alkali in general sense such as (potassium) among the present invention, and its form can be sheet, granular or solution shape.When the hot glue grain directly mixes with solid caustic soda, preferred granular or sheet alkali is as hydrolytic reagent, spraying adds the alkaline solution that the alkali mode is selected 20～50wt% or greater concn, the preferential sodium hydroxide solution of selecting 40～50wt%, the add-on of hydrolysising alkali is usually according to experiment experience, when selecting sodium hydroxide as hydrolytic reagent, the molar ratio amount that waits that add-on is generally pressed the theoretical hydrolysis of amide group adds, and 1.5 times of molar ratio amounts of pressing the theoretical hydrolysis of amide group when selecting yellow soda ash as hydrolytic reagent add.
4, with described in above-mentioned 2 through solid caustic soda blended hot glue grain or through the hot glue grain of alkali lye spraying; deliver to the reaction that is hydrolyzed in the microwave reactor by handling equipment; microwave reactor can be the tunnel like operate continuously, also can be the rotary type operation, and microwave radiation preferably is not less than 0.01W/cm
2But be not higher than 15W/cm
2, when being lower than 0.01W/cm
2The time, too low the carrying out that influences hydrolysis reaction of the energy of microwave radiation, hydrolysis rate is slow, reaction is incomplete, and can cause the decline of production efficiency, when described microwave radiation is higher than 15W/cm
2The time, then can cause hydrolysis reaction violent, the micelle temperature is too high, polymer molecule degraded, crosslinked, even the phenomenon that causes product quality to worsen such as local coking.Described microwave radiation more preferably is not less than 0.1W/cm
2, be not higher than 10W/cm
2Under above-mentioned described yield of radiation, the hydrolysis of polyacrylamide time preferably is not shorter than 0.3min, more preferably is not shorter than 1min, and radiated time is too short, and hydrolysis reaction is incomplete, but radiated time is no longer than 10min, more preferably in no longer than 8min.Radiated time is long, easily causes the polymericular weight degraded, even the crosslinked product decreased solubility that makes.The microwave radiation frequency adopts the industrial frequency of utilization 915MHz or the 2450MHz of national regulation.
5, the polyacrylamide hydrolysis degree scope that obtains of the method for the employing microwave hydrolysis in above-mentioned 4 is between 2-55%, degree of hydrolysis is to obtain by the add-on of controlling alkali, adopt sodium hydroxide as hydrolytic reagent, the molar ratio amount that waits that dosage is pressed the theoretical hydrolysis of amide group adds, and presses 1.5 times of molar ratio amounts of the theoretical hydrolysis of amide group according to practical experience when selecting yellow soda ash as hydrolytic reagent and adds.Hydrolysis unit operations such as micelle drying, pulverizing completely can make the powdery anion-polyacrylamide product of different degree of hydrolysis.
Embodiment 1
The fresh polymerization blob of viscose weight 800kg of water ratio 68.3%; be cut into small pieces or strip with knife mill; deliver to the tablets press granulation through handling equipment; when granulation diameter 1.5-2.5mm; in the 50% concentration hydrogen sodium hydroxide solution of tablets press one side with spray gun thermotropism micelle spraying 71.5kg; granulation finishes to guarantee that alkali lye spraying synchronously finishes, and the micelle that the surface is coated with alkali lye is delivered to van-type microwave reactor (microwave radiation frequency 2450MHz), yield of radiation 3W/cm
2, hydrolysis time 4.5min, reaction finishes discharging, carries out drying, pulverizes.The leading indicator of product sees Table 1.
Embodiment 2:
The fresh polymerization blob of viscose weight 2000kg of water ratio 70%; be cut into small pieces or strip with knife mill; deliver to the tablets press granulation through handling equipment; granulation diameter 1.5-2.5mm; the hot glue grain of making directly enters the blender of band stirring arm, adds granular sodium hydroxide 135kg, mixes; discharging is to van-type microwave reactor (microwave radiation frequency 2450MHz), yield of radiation 5.5W/cm
2, hydrolysis time 2.0min, reaction finishes discharging, carries out drying, pulverizes.The leading indicator of product sees Table 1.
Embodiment 3:
The fresh polymerization blob of viscose weight 1500kg of water ratio 69%; be cut into small pieces or strip with knife mill; deliver to the tablets press granulation through handling equipment; granulation diameter 1.5-2.5mm; the hot glue grain of making directly enters the blender of band stirring arm, adds granular yellow soda ash 286kg, mixes; discharging is to van-type microwave reactor (microwave radiation frequency 2450MHz), yield of radiation 5.5W/cm
2, hydrolysis time 2.0min, reaction finishes discharging, carries out drying, pulverizes.The leading indicator of product sees Table 1.
Comparative example 1
The fresh polymerization blob of viscose weight 500kg of the water ratio 70% among the embodiment 2; be cut into small pieces or strip with knife mill; deliver to the tablets press granulation through handling equipment, the straight 1.5-2.5mm of granulation, the hot glue grain of making directly enter the hydrolyzer that band stirs and chuck heats; hydrolyzer is heated to temperature of charge and reaches about 50-80 ℃; and start the agitator stirring, add granular sodium hydroxide 25.5kg and be hydrolyzed, hydrolysis discharging after 3 hours; carry out drying and crushing and handle, the leading indicator of product sees Table 1.
Comparative example 2
The fresh polymerization blob of viscose weight 500kg of the water ratio 68.3% among the embodiment 1, and molten the joining in the kneader of 50% concentration hydrogen sodium oxide of 44.6kg mediated 3 hours down at 75-85 ℃, 85-95 ℃ of hydrolysis 10 hours, granulation, drying, the leading indicator of product sees Table 1.
The key technical indexes of table 1 embodiment and comparative example hydro-polyacrylamide
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 3 | Comparative example 4 | Testing method |
| Degree of hydrolysis, % | 24.32 | 34.61 | 53.55 | 29.21 | 17.38 | GB17514-1998 |
| Molecular weight, ten thousand | 2360 | 3089 | 2102 | 2872 | 2096 | GB17514-1998 ① |
| Dissolution rate, min | ≤90 | ≤120 | ≤90 | ≤120 | ≤90 | GB17514-1998 |
1.: the molecular weight M among the GB17514-1998 is M=([η]/K) by formula
1/ αCalculate K=3.73 * 10
-4, α=0.66.
Claims (8)
1. the fast hydrolyzation of a polyacrylamide, it is characterized in that, this method is that acrylamide solution is made high-molecular weight polyacrylamide blob of viscose by thermopolymerization or the homopolymerization of uv-radiation polymerization methods, with knife mill the polyacrylamide blob of viscose is cut into small pieces or strip, send granulating equipment again to and carry out granulation, add alkali after the granulation as hydrolytic reagent, finish hydrolysis reaction fast by the microwave radiation mode, drying, pulverizing make the powdered polypropylene acid amides of 2～55% different degree of hydrolysis again.
2. the fast hydrolyzation of a kind of polyacrylamide according to claim 1 is characterized in that, described polyacrylamide blob of viscose molecular weight is between 500～3,000 ten thousand, between water ratio 55～80wt%.
3. the fast hydrolyzation of a kind of polyacrylamide according to claim 1 is characterized in that, described polyacrylamide gel granulation, and particle diameter is 1～5mm, preferred 1.0～2.0mm.
4. the fast hydrolyzation of a kind of polyacrylamide according to claim 1, it is characterized in that, described hydrolytic reagent comprises anhydrous sodium carbonate, Anhydrous potassium carbonate, sodium bicarbonate, saleratus, solid sodium hydroxide or solid potassium hydroxide, and its form can be sheet, granular or solution.
5. the fast hydrolyzation of a kind of polyacrylamide according to claim 1, it is characterized in that, the described alkali mode that adds can be that the hot glue grain is directly mixed with solid caustic soda, preferred granular hydrolytic reagent, blender by the band stirring rake carries out batch mixing, or carries out batch mixing by machinery rotation formula blender.
6. the fast hydrolyzation of a kind of polyacrylamide according to claim 1, it is characterized in that, the described alkali mode that adds can be in granulation, finish by thermotropism micelle spraying high density liquid caustic soda, used alkali is selected the alkaline solution of 20～50wt% or greater concn, the sodium hydroxide solution of preferred 40～50wt%.
7. the fast hydrolyzation of a kind of polyacrylamide according to claim 1 is characterized in that, it is to adopt tunnel like or rotary type radial pattern hydrolysis reactor, microwave radiation: 0.01～15W/cm that described microwave radiation mode is finished hydrolysis reaction fast
2, radiation frequency: adopt the industrial frequency of utilization 915MHz or the 2450MHz of national regulation, hydrolysis time: 0.3～10min.
8. the fast hydrolyzation of a kind of polyacrylamide according to claim 1, it is characterized in that, described powdered polypropylene acid amides can obtain different degree of hydrolysis by the add-on of control hydrolysis agent, and drying, mechanical disintegration make the powdery anion-polyacrylamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710038965XA CN100543045C (en) | 2007-04-02 | 2007-04-02 | A kind of fast hydrolyzation of polyacrylamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200710038965XA CN100543045C (en) | 2007-04-02 | 2007-04-02 | A kind of fast hydrolyzation of polyacrylamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101029099A true CN101029099A (en) | 2007-09-05 |
| CN100543045C CN100543045C (en) | 2009-09-23 |
Family
ID=38714665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200710038965XA Expired - Fee Related CN100543045C (en) | 2007-04-02 | 2007-04-02 | A kind of fast hydrolyzation of polyacrylamide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100543045C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071439A (en) * | 2012-12-11 | 2013-05-01 | 山东宝莫生物化工股份有限公司 | Jacketed-type storage bin hot water heating hydrolysis system |
| CN105424533A (en) * | 2015-11-14 | 2016-03-23 | 山东宝莫生物化工股份有限公司 | Hydrolysis degree determination method for polyacrylamide with high hydrolysis degree |
| CN112679632A (en) * | 2020-12-25 | 2021-04-20 | 东营宝莫环境工程有限公司 | Novel efficient mixed hydrolysis method for producing polyacrylamide |
| CN113021670A (en) * | 2021-03-08 | 2021-06-25 | 东营科创生物化工有限公司 | Device and method for producing polyacrylamide |
| CN113861314A (en) * | 2021-09-24 | 2021-12-31 | 宁波锋成先进能源材料研究院有限公司 | Polyacrylamide hydrolytic agent and preparation method and application thereof |
-
2007
- 2007-04-02 CN CNB200710038965XA patent/CN100543045C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103071439A (en) * | 2012-12-11 | 2013-05-01 | 山东宝莫生物化工股份有限公司 | Jacketed-type storage bin hot water heating hydrolysis system |
| CN105424533A (en) * | 2015-11-14 | 2016-03-23 | 山东宝莫生物化工股份有限公司 | Hydrolysis degree determination method for polyacrylamide with high hydrolysis degree |
| CN112679632A (en) * | 2020-12-25 | 2021-04-20 | 东营宝莫环境工程有限公司 | Novel efficient mixed hydrolysis method for producing polyacrylamide |
| CN112679632B (en) * | 2020-12-25 | 2022-12-06 | 东营宝莫环境工程有限公司 | Efficient mixed hydrolysis method for producing polyacrylamide |
| CN113021670A (en) * | 2021-03-08 | 2021-06-25 | 东营科创生物化工有限公司 | Device and method for producing polyacrylamide |
| CN113861314A (en) * | 2021-09-24 | 2021-12-31 | 宁波锋成先进能源材料研究院有限公司 | Polyacrylamide hydrolytic agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100543045C (en) | 2009-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100543045C (en) | A kind of fast hydrolyzation of polyacrylamide | |
| JP2008023433A (en) | Granulation auxiliary and granulation method for composition containing calcium carbonate | |
| JP7455155B2 (en) | Polyvinyl alcohol resin and its manufacturing method | |
| CN106496413A (en) | The copolymerization composition manufacture method of the polyacrylamide of ultra-low residue content of monomer | |
| CN101831030B (en) | Preparation method of anionic polyacrylamide | |
| CN102336645B (en) | Granular stearate, and preparation method and application thereof | |
| CN102701985A (en) | Method for preparing epoxy resin curing agent by performing alcoholysis on PET (Polyethylene Terephthalate) polyester | |
| CN104845032A (en) | Preparation method of toughened 3D (three-dimensional) printing consumables | |
| CN106496412A (en) | The copolymerization composition manufacture method of rapid-dissoved PAMA | |
| CN101735376B (en) | Preparation method of red mud sinking agent | |
| CN101143912B (en) | Method for producing high-performance high water absorption resin | |
| CN104262517A (en) | Continuous posthydrolysis method for polyacrylamide | |
| CN1275993C (en) | Method of oreparing starch grafting type high water absorption resin by wave polymerization | |
| CN116897077A (en) | Micronizing device for super absorbent polymer hydrogel | |
| CN101230212A (en) | White carbon black surface recombination modified preparation method | |
| JPH02123102A (en) | Production of partially hydrolyzed acrylamide-based polymer fine particle | |
| CN105399075A (en) | Method for recycling waste tires through ammonia-process low-temperature desulfurization | |
| CN219400115U (en) | Preparation facilities of calcium stearate | |
| CN202921309U (en) | Device for producing stearate at low temperature by dry method continuously | |
| CN107973877A (en) | A kind of copolymerization composition manufacture method of the polyacrylamide of modified anion containing magnesium ion | |
| CN107903439A (en) | A kind of method of One-step production barium zinc stabilizer | |
| CN112387229B (en) | Device and method for continuously producing aluminum sulfate octadecatriend hydrate | |
| CN215234008U (en) | A prilling granulator for monoammonium phosphate production | |
| CN116143608A (en) | Preparation method and preparation device of calcium stearate | |
| CN117049556A (en) | Recycling method and system for sodium silicate insoluble waste residues |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090923 Termination date: 20180402 |