CN101733156B - Naphthalene sulfonate rare earth catalyst as well as preparation method and application thereof - Google Patents
Naphthalene sulfonate rare earth catalyst as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN101733156B CN101733156B CN200910217981A CN200910217981A CN101733156B CN 101733156 B CN101733156 B CN 101733156B CN 200910217981 A CN200910217981 A CN 200910217981A CN 200910217981 A CN200910217981 A CN 200910217981A CN 101733156 B CN101733156 B CN 101733156B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- catalyst
- naphthalene sulfonate
- neodymium
- sulfonic acids
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Polymerization Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a naphthalene sulfonate rare earth catalyst as well as a preparation and application thereof. The rare earth catalyst comprises a naphthalene sulfonate rare earth compound and alkyl aluminum, wherein the naphthalene sulfonate rare earth compound is a master catalyst, and the alky aluminum is an auxiliary catalyst; the mol ratio of the auxiliary catalyst of the alkyl aluminum and the master catalyst of rare earth is 20 to 60: 1; and the master catalyst and the auxiliary catalyst are aged for 60 minutes to 48 hours at -20 to 80 DEG C to obtain the naphthalene sulfonate rare earth homogeneous catalyst for isoprene polymerization; after the aging treatment, the catalyst has higher catalyst activity, the isoprene polymerization can be carried out under the conditions of both the existence and the inexistence of a solvent, and the polyisoprene rubber with the monomer conversion ratio more than 80 percent, cis 1,4 content more than 92 percent and the weight-average molecular weight equal to 2000-150000 is obtained by the polymerization. The rare earth catalyst has simple composition, low-price raw materials, wide source as well as simple and convenient preparation process, provides a new catalyst technology for the synthetic rubber industry, and broadens the application field of naphthalenesulfonic acid compounds.
Description
Technical field
The present invention relates to naphthalene sulfonate rare earth catalyst, method for making and application.
Background technology
Generally; Naphthalene sulfonic acids and compound thereof are mostly synthetic as medicine, the intermediate of biochemical material and the auxiliary material of chemical industry and building trade; Be synthetic protease inhibitors like 6-amidino groups-2-naphthyl-4-guanidine benzoate metilsulfate, trypsin-like serine proteases such as the C1r of trypsase, fibrin-ferment, plasmase, kallikrein (callicrein) and complement system classical pathway, C1S are had very strong selective inhibitory.And dinonylnaphthalene sulfonic acid (DNNSA) itself is a kind of surfactant, can be used for the catalyst of coating, also can be used as the primary raw material of producing amino-stoving varnish cooling catalyst, because of its hydrophobicity is applicable to the anodic electrophoresis paint system.2-amino-5-aminomethyl-1 naphthalene sulfonic acids (aminomethyl weave silk acid) is a kind of novel active azo dyes intermediate for another example.
And sodium naphthalene sulfonate is because soluble in water, acidproof, alkali, and salt and hard water, diffusion is good. and also can be used for textile printing and dyeing, the wettable agricultural chemicals is made dispersant, papermaking, pigment, carbon black, water soluble paint are used dispersant, electroplating additive, water treatment agent.Having substituent methyl naphthalene sulfonic acid sodium then is dye dispersant, the primary raw material of cement water reducing agent, and its consumption in commercial dye is up to 60-70%.
In addition, naphthalene series substance is that the compound of main synthesis material is mainly used in building trade, and concrete need add various additives before use, and the main application of this compounds is as the concrete auxiliary agent.Concrete admixture commonly used can be divided into water reducer, air entraining agent, set retarder, early strength agent, antifreezing agent, accelerator, swelling agent and other purposes additives by its function, and water reducer is maximum a kind of of consumption in the present concrete admixture.
There is bibliographical information to cross synthetic and sign about the naphthalene sulfonate rare earth compound; Crystal structure and steric configuration to all cpds have been carried out comparatively detailed sign; Synthetic and the application of this compounds at present mainly concentrates on medicine, printing and dyeing, building and some biochemical materials but only is confined to sign and the explanation to compound structure and building-up process; Do not relate to the research of naphthalene sulfonate rare earth application of compound particularly about being applied to the information (CrystEngComm of diene polymerization aspect; 2007,9,902-906; Inorganic Chemistry, Vol.46, No.9,20073475-3484).And it does not also see document and patent report as catalyst applications in the synthetic field of macromolecular material.
Summary of the invention
For expanding naphthalene sulfonic acids application of compound field and, the invention provides naphthalene sulfonic acids neodymium rare earth catalyst, method for making and application for China Synthetic Rubber Industry increases new catalysis technique.
Described naphthalene sulfonic acids neodymium rare earth catalyst is made up of naphthalene sulfonic acids neodymium rare earth compound and alkyl aluminum, and the mol ratio of described alkyl aluminum and naphthalene sulfonic acids neodymium rare earth compound middle rare earth neodymium is 20～60: 1;
The chemical formula of described naphthalene sulfonate rare earth compound is:
In the formula, rare earth Ln is a neodymium, R
1, R
2Be alkyl or the hydrogen atom of carbon number=1-9, wherein, R
1, R
2Identical or different, n=0 or 1;
Described alkyl aluminum is trialkylaluminium or alkyl-al hydride;
Described trialkylaluminium is triisobutyl aluminium or triethyl aluminum; Alkyl-al hydride is diisobutyl aluminium hydride or ADEH.
The method for making of naphthalene sulfonic acids neodymium rare earth catalyst provided by the present invention is characterized in that step and condition are following:
Under nitrogen protection, in the catalyst preparation device of dried, adding naphthalene sulfonic acids neodymium rare earth compound and alkyl aluminum successively, the mol ratio of described alkyl aluminum and naphthalene sulfonic acids neodymium rare earth compound middle rare earth neodymium is 20～60: 1; Add hexane again, be mixed with naphthalene sulfonic acids neodymium rare earth catalyst agent solution, making the molar concentration of naphthalene sulfonic acids neodymium rare earth compound middle rare earth neodymium in naphthalene sulfonic acids neodymium rare earth catalyst agent solution is 5 * 10
-5Mol/ml; After 60 minutes～48 hours, obtain being used for the naphthalene sulfonic acids neodymium rare earth catalyst of catalysis isoprene polymerization in-20～80 ℃ of following ageings.
The application of naphthalene sulfonic acids neodymium rare earth catalyst is characterized in that it is used for the catalysis isoprene polymerization.
Naphthalene sulfonic acids neodymium rare earth catalyst is used for the method for catalysis isoprene polymerization, and described method has following two kinds, and step and condition are following:
(1) under nitrogen protection, in the polymerizer of anhydrous and oxygen-free, add isoprene monomer, then add naphthalene sulfonic acids neodymium rare earth catalyst, the mol number of the rare earth neodymium in the naphthalene sulfonic acids neodymium rare earth catalyst and the quality g proportioning of isoprene monomer are 5.0 * 10
-7～1.0 * 10
-5: 1, all can be aggregated under solvent or the condition of no solvent, under 20～60 ℃ of temperature, reacted 20～48 hours; Use contain mass fraction be 1% 2, the ethanolic solution of 6-di-tert-butyl methyl phenol stops, after washing was pushed, vacuum drying obtained polyisoprene rubber again; Perhaps,
(2) under nitrogen protection, in the polymerizer of anhydrous and oxygen-free, add isoprene monomer, then add naphthalene sulfonic acids neodymium rare earth catalyst, add hexane again, the used solvent of described polymerization is a hexane, the proportioning of the volume of hexane and isoprene quality is 8: 1; Remaining same method (1).
Beneficial effect: naphthalene sulfonic acids neodymium rare earth catalyst provided by the invention is used for the catalysis isoprene polymerization, obtains monomer conversion＞80%, is the polyisoprene rubber of 20000-150000 along 1,4 content＞92%, weight average molecular weight.This rare earth catalyst is formed simple, inexpensive, the wide material sources of raw material, and the preparation process is easy.After ageing was handled, this catalyst had advantages of high catalytic activity, and isoprene polymerization all can carry out having under the condition of no solvent.With the naphthalene sulfonate rare earth compound as catalyst applications in the Polymer Synthesizing field, not only for China Synthetic Rubber Industry provides new catalysis technique, and expanded application for the naphthalene sulfonic acids compound.
The specific embodiment
Embodiment 1: naphthalene sulfonic acids neodymium
Preparation of Catalyst be applied to isoprene polymerization
(1) under nitrogen protection,, it is 20: 1 by the mol ratio of triisobutyl aluminium and Nd in the catalyst preparation device of dried; The naphthalene sulfonic acids neodymium compound that adds 0.25mmol successively; The 5mmol triisobutyl aluminium adds the 3.71ml hexane again, is mixed with naphthalene sulfonic acids neodymium rare earth catalyst agent solution; Wherein, the molar concentration of naphthalene sulfonic acids neodymium rare earth compound middle rare earth neodymium in naphthalene sulfonate rare earth catalyst solution is 5 * 10
-5Mol/ml after 48 hours, obtains being used for the naphthalene sulfonic acids neodymium catalyst of isoprene polymerization in-20 ℃ of following ageings.
(2) to be applied to the step and the condition of isoprene polymerization following for the naphthalene sulfonic acids neodymium catalyst: under nitrogen protection; In the polymerizer of anhydrous and oxygen-free, add the 10g isoprene monomer; Then add the above-mentioned catalyst of 0.1ml, the mol number of catalyst middle rare earth and the quality g proportioning of isoprene monomer are 5.0 * 10
-7: 1, polymerization is 24 hours under 60 ℃ of temperature; Use contain mass fraction be 1% 2, the ethanolic solution of 6-di-tert-butyl methyl phenol stops.After the washing extruding, vacuum drying is 196 hours under 40 ℃ of temperature, obtains the 8.2g polyisoprene rubber.Monomer conversion is 82%, be 150000 along 1,4 content=94.3%, weight average molecular weight.
Comparative example 1: major catalyst by the naphthalene sulfonic acids neodymium
3Change to benzene sulfonic acid neodymium Nd (C
6H
5SO
3) 3, the preparation of benzene sulfonic acid neodymium catalyst and be applied to the isoprene polymerization step and condition with embodiment 1; Confirm the basic non-activity of benzene sulfonic acid neodymium catalyst through polymerization, have to the polyisoprene rubber of trace.
Embodiment 2: methyl naphthalene sulfonic acid neodymium
Preparation of Catalyst be applied to isoprene polymerization
(1) changes to ADEH to triisobutyl aluminium; The addition of ADEH is 10mmol; The mol ratio of ADEH and Nd is 40: 1; The hexane addition becomes 3.92ml in the catalyst preparation process, and methyl naphthalene sulfonic acid neodymium catalyst preparation method's remaining step and condition are with the step (1) of embodiment 1.
(2) change catalyst into the methyl naphthalene sulfonic acid neodymium catalyst, remaining step is with the step (2) of embodiment 1.Obtain the 8.4g polyisoprene rubber.Monomer conversion is 84%, be 53000 along 1,4 content=93.8%, weight average molecular weight.
Comparative example 2: change to toluene sulfonic acide neodymium Nd (C to major catalyst by the methyl naphthalene sulfonic acid neodymium
7H
8SO
3)
3, the preparation of toluene sulfonic acide neodymium catalyst and be applied to the isoprene polymerization step and condition with embodiment 2; Confirm that through polymerization toluene sulfonic acide neodymium catalyst activity is still very low, have to the polyisoprene rubber of trace.
Embodiment 3: amyl naphthalene sulfonic acid neodymium Nd
Preparation of Catalyst be applied to isoprene polymerization
(1) changes to amyl naphthalene sulfonic acid neodymium to major catalyst by the naphthalene sulfonic acids neodymium; Amyl naphthalene sulfonic acid neodymium catalyst preparation method's remaining step and condition are with the step (1) of embodiment 1.
(2) became under 40 ℃ of temperature polymerization to polymerization time and temperature 48 hours; Amyl naphthalene sulfonic acid neodymium catalyst is applied to the step (2) of isoprene polymerization step with embodiment 1; Reaction finishes to obtain the 8.50g polyisoprene rubber; Monomer conversion is 85.0%, is 128000 along 1,4 content=92.8%, weight average molecular weight.
Embodiment 4: nonyl naphthalene sulfonic acids neodymium Nd
Preparation of Catalyst be applied to isoprene polymerization
(1) changes to nonyl naphthalene sulfonic acids neodymium to major catalyst by the naphthalene sulfonic acids neodymium; Remaining step of the concrete method for preparing catalyst of nonyl naphthalene sulfonic acids neodymium and condition are with the step (1) of embodiment 1.
(2) nonyl naphthalene sulfonic acids neodymium catalyst is applied to the step (2) of isoprene polymerization step with embodiment 1, and reaction finishes to obtain the 8.42g polyisoprene rubber, and monomer conversion is 84.2%, is 104000 along 1,4 content=93.4%, weight average molecular weight.
Embodiment 5: naphthalenedisulfonic acid neodymium
catalyst and preparation and be applied to isoprene polymerization
(1) under nitrogen protection; To in the catalyst preparation device of dried; Mol ratio by diisobutyl aluminium hydride and Nd is 60: 1, adds the naphthalenedisulfonic acid neodymium compound of 0.25mmol successively, the 15mmol diisobutyl aluminium hydride; Add the 2.33ml hexane again, be mixed with naphthalenedisulfonic acid neodymium rare earth catalyst agent solution; Wherein, the molar concentration of naphthalenedisulfonic acid neodymium rare earth compound middle rare earth neodymium in naphthalenedisulfonic acid rare earth catalyst agent solution is 5 * 10
-5Mol/ml after 60 minutes, obtains being used for the naphthalenedisulfonic acid neodymium catalyst of isoprene polymerization in 80 ℃ of following ageings.
(2) to be applied to the step and the condition of isoprene polymerization following for the naphthalenedisulfonic acid neodymium catalyst: under nitrogen protection; In the polymerizer of anhydrous and oxygen-free, add the 5g isoprene monomer; Add the 40ml hexane again; Then add the above-mentioned catalyst of 1ml, the molal quantity mol of catalyst middle rare earth neodymium and the quality g proportioning of isoprene monomer are 1.0 * 10
-5, polymerization is 20 hours under 20 ℃ of temperature; After reaction finishes, use contain mass fraction be 1% 2, the ethanolic solution of 6-di-tert-butyl methyl phenol stops.After the washing extruding, vacuum drying is 196 hours under 40 ℃ of temperature, obtains the 4.25g polyisoprene rubber.Monomer conversion is 85%, be 20000 along 1,4 content=93.1%, weight average molecular weight.
Embodiment 6:
Dinonylnaphthalene disulfonic acid neodymium
Preparation of Catalyst be applied to isoprene polymerization
(1) change to the dinonylnaphthalene disulfonic acid neodymium to major catalyst by the naphthalenedisulfonic acid neodymium, the concrete preparation method's of dinonylnaphthalene disulfonic acid neodymium catalyst remaining step and condition are with the step (1) of embodiment 5.
(2) the isoprene monomer addition becomes 10g, and the molal quantity mol of catalyst middle rare earth neodymium and the quality g proportioning of isoprene monomer become 5.0 * 10
-6, the dinonylnaphthalene disulfonic acid neodymium catalyst is applied to the step (2) of isoprene polymerization step with embodiment 5, and reaction finishes to obtain the 4.21g polyisoprene rubber.Monomer conversion is 84.2%, be 34000 along 1,4 content=93.0%, weight average molecular weight.
Embodiment 7:
Dinonylnaphthalene disulfonic acid neodymium
Preparation of Catalyst be applied to isoprene polymerization
(1) changes to triethyl aluminum to diisobutyl aluminium hydride; The addition of triethyl aluminum is 10mmol; The mol ratio of ADEH and Nd is 40: 1; The hexane addition becomes 2.23ml in the catalyst preparation process, and catalyst ageing condition becomes: 36 hours dinonylnaphthalene disulfonic acid neodymium catalysts of ageing preparation method's remaining step and condition are with the step (1) of embodiment 5 under 40 ℃ of temperature.
(2) change catalyst into the dinonylnaphthalene disulfonic acid neodymium catalyst, remaining step is with the step (2) of embodiment 5.Obtain the 4.34g polyisoprene rubber.Monomer conversion is 86.8%, be 112000 along 1,4 content=92.2%, weight average molecular weight.
Claims (5)
1. naphthalene sulfonate rare earth catalyst is characterized in that, described naphthalene sulfonate rare earth catalyst is made up of naphthalene sulfonic acids neodymium rare earth compound and alkyl aluminum, and the mol ratio of described alkyl aluminum and naphthalene sulfonic acids neodymium rare earth compound middle rare earth is 20～60: 1;
The chemical formula of described naphthalene sulfonate rare earth compound is:
In the formula, rare earth Ln is a neodymium, R
1, R
2Be alkyl or the hydrogen atom of carbon number=0-9, wherein, R
1, R
2Identical or different, n=0;
Described alkyl aluminum is trialkylaluminium or alkyl-al hydride.
2. naphthalene sulfonate rare earth catalyst as claimed in claim 1 is characterized in that described trialkylaluminium is triisobutyl aluminium or triethyl aluminum; Alkyl-al hydride is diisobutyl aluminium hydride or ADEH.
3. the method for making of the described naphthalene sulfonate rare earth catalyst of claim 1 is characterized in that step and condition are following:
Under nitrogen protection; To in the catalyst preparation device of dried, adding naphthalene sulfonic acids neodymium rare earth compound and alkyl aluminum successively; The mol ratio of described alkyl aluminum and naphthalene sulfonic acids neodymium rare earth compound middle rare earth neodymium is 20～60: 1; Add hexane again, be mixed with naphthalene sulfonic acids neodymium rare earth catalyst agent solution, making the molar concentration of naphthalene sulfonic acids neodymium rare earth compound middle rare earth neodymium in naphthalene sulfonic acids neodymium rare earth catalyst agent solution is 5 * 10
-5Mol/ml; After 60 minutes～48 hours, obtain being used for the naphthalene sulfonate rare earth catalyst of catalysis isoprene polymerization in-20～80 ℃ of following ageings.
4. the application of the described naphthalene sulfonate rare earth catalyst of claim 1 is characterized in that, it is used for the catalysis isoprene polymerization.
5. the application of the described naphthalene sulfonate rare earth catalyst of claim 4 is characterized in that, the step and the condition of method that is used for the catalysis isoprene polymerization is following:
Under nitrogen protection, in the polymerizer of anhydrous and oxygen-free, add isoprene monomer, then add naphthalene sulfonate rare earth catalyst, the mol number of the rare earth neodymium of naphthalene sulfonate rare earth catalyst and the quality g proportioning of isoprene monomer are 5.0 * 10
-7～2.0 * 10
-5: 1, all can be aggregated under solvent or the condition of no solvent, under 20～60 ℃ of temperature, reacted 20～48 hours; Use contain mass fraction be 1% 2, the ethanolic solution of 6-di-tert-butyl methyl phenol stops, after washing was pushed, vacuum drying obtained polyisoprene rubber again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910217981A CN101733156B (en) | 2009-12-11 | 2009-12-11 | Naphthalene sulfonate rare earth catalyst as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910217981A CN101733156B (en) | 2009-12-11 | 2009-12-11 | Naphthalene sulfonate rare earth catalyst as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101733156A CN101733156A (en) | 2010-06-16 |
| CN101733156B true CN101733156B (en) | 2012-09-05 |
Family
ID=42457486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910217981A Expired - Fee Related CN101733156B (en) | 2009-12-11 | 2009-12-11 | Naphthalene sulfonate rare earth catalyst as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101733156B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6084059A (en) * | 1998-04-03 | 2000-07-04 | Nippon Shokubai Co., Ltd. | Production process for organometallic fine particle and catalyst for polymerization |
| US6767927B1 (en) * | 1999-04-26 | 2004-07-27 | Rhodia Rare Earths Inc. | Synthesis of stable solutions of rare earth tris (organophosphate) in hydrocarbon solvents |
| CN1834121A (en) * | 2006-03-24 | 2006-09-20 | 中国科学院长春应用化学研究所 | Rare-earth catalyst for diolefin polymerization and its prepn. |
-
2009
- 2009-12-11 CN CN200910217981A patent/CN101733156B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6084059A (en) * | 1998-04-03 | 2000-07-04 | Nippon Shokubai Co., Ltd. | Production process for organometallic fine particle and catalyst for polymerization |
| US6767927B1 (en) * | 1999-04-26 | 2004-07-27 | Rhodia Rare Earths Inc. | Synthesis of stable solutions of rare earth tris (organophosphate) in hydrocarbon solvents |
| CN1834121A (en) * | 2006-03-24 | 2006-09-20 | 中国科学院长春应用化学研究所 | Rare-earth catalyst for diolefin polymerization and its prepn. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101733156A (en) | 2010-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103467670B (en) | Preparation method of anti-mud polycarboxylic water reducer | |
| CN103833940B (en) | A kind of containing phosphine polycarboxylate water-reducer and preparation method thereof | |
| CN109608632B (en) | Concrete anti-mud sacrificial agent and preparation method thereof | |
| CN105504261A (en) | Random copolyether macromonomer, water reducing agent prepared from same, and preparing method and application of random copolyether macromonomer | |
| CN101733156B (en) | Naphthalene sulfonate rare earth catalyst as well as preparation method and application thereof | |
| CN102807653A (en) | Co-polycarboxylic acid high efficiency water reducer capable of compounding with naphthalene formaldehyde water reducer and method for preparing same | |
| CN106746864A (en) | One kind compounding sulfonation maltodextrin water reducer and preparation method thereof | |
| CN101125819A (en) | Method for synthesizing primary octadecylamine polyoxyethylene ether | |
| CN109675507B (en) | Preparation method of micron-sized melamine resin balls | |
| CN111320415A (en) | Environment-friendly composite antifreezing pumping aid and preparation method thereof | |
| CN111533844B (en) | Modified concrete water-retaining agent and preparation method thereof | |
| CN108409170A (en) | Rapid hardening antifreezing cement and preparation method thereof | |
| CN114605274A (en) | Production process for synthesizing o-aminoanisole by hydrogenation method | |
| CN113430022A (en) | Method for preparing sodium polystyrene sulfonate by sulfonating waste polystyrene and application of sodium polystyrene sulfonate in coal water slurry | |
| CN101607212B (en) | Binary alkyl benzene sulfonic acid rare earth catalyst, preparation method and application thereof | |
| CN113980166B (en) | Polyacrylic acid thickener with glycyrrhizic acid derivative as cross-linking agent and preparation method thereof | |
| CN111607031A (en) | Preparation method of carbon six-monomer synthetic water reducing agent | |
| CN103951308B (en) | Sulfonic group modified Soxylat A 25-7 superplasticizer and preparation method thereof | |
| CN106916240B (en) | Method for preparing rare earth isoprene rubber catalyst | |
| CN108976363A (en) | A kind of high water reducing rate high-performance water reducing agent | |
| CN102850482B (en) | Acrylic emulsion preparation method with improved monomer conversion rate, and prepared acrylic emulsion | |
| CN107986673B (en) | High-efficiency environment-friendly water reducing agent and preparation method thereof | |
| CN112142912B (en) | Preparation method of ultra-high molecular weight anionic polyacrylamide | |
| CN102976658A (en) | Special additive for water-permeable concrete and preparation method of special additive | |
| CN118063127A (en) | Polycarboxylate superplasticizer and preparation method and application thereof |
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 |
Granted publication date: 20120905 Termination date: 20151211 |
|
| EXPY | Termination of patent right or utility model |