CN106380541A - Preparation method of amide copolymer hydrate kinetic inhibitor - Google Patents
Preparation method of amide copolymer hydrate kinetic inhibitor Download PDFInfo
- Publication number
- CN106380541A CN106380541A CN201610802031.8A CN201610802031A CN106380541A CN 106380541 A CN106380541 A CN 106380541A CN 201610802031 A CN201610802031 A CN 201610802031A CN 106380541 A CN106380541 A CN 106380541A
- Authority
- CN
- China
- Prior art keywords
- preparation
- analog copolymer
- azo
- amide analog
- copolymer hydrate
- 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
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
- C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- 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
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of an amide copolymer hydrate kinetic inhibitor, and belongs to the technical field of preparation of chemical engineering reagents. The preparation method is concretely characterized in that the AM/AN/VCL ternary copolymer hydrate kinetic inhibitor with the molecular weight reaching 300,000-500,000 is synthesized from acrylamide (AM), acrylonitrile (AN) and vinyl caprolactam (VCL) in anoxic environment with azodiisobutyronitrile as an initiator and nonionic surfactant-containing deionized water as a disperse medium. The method has the characteristics of simple production process and low production cost, and the prepared inhibitor has the advantages of low injection dosage and long inhibition time.
Description
Technical field
The present invention relates to a kind of preparation method of gas hydrates kinetic inhibitor, particularly to a kind of amide-type altogether
The preparation method of polymers hydrate dynamic inhibitor.
Background technology
Gas hydrates are a kind of crystal with cage structure, and profile, similar to ice, has water in natural gas line
In the case of, when being in low temperature and environment under high pressure, hydrone is formed with natural gas molecule crystallization nucleation.Gas hydrates pole
Easily cause the blocking of pipeline and affect the normal conveying of natural gas, when serious, may result in security incident.In order to suppress hydrate
Formed, frequently with the method for injection thermodynamic inhibitor.This method toxicity is big, injection rate big, huge using equipment, causes to give birth to
Produce high cost and serious environmental pollution, easily impact is produced on makings simultaneously.
In recent years, the fast development of dynamic hydrate inhibitor, there is provided a kind of replacement thermodynamic inhibitor new
Technical thought.The action principle of kinetic inhibitor be different from thermodynamic inhibitor, be by reduce hydrate nucleation rate,
Delay or even stop generation, the preferred growth direction of interference hydrate crystal and the impact hydrate crystal orientation of critical nucleus steady
The generation to suppress hydrate for the mode such as qualitative.But its production cost is higher, hinder always the shortcomings of production technology is complex
It is in the large-scale application of natural gas line industry.
How to reduce kinetic inhibitor production cost, reduce production craft step, be current problem demanding prompt solution.Acyl
Amine high polymer has the advantages that low production cost, simple production process, and acylamide polymer is imitated to the suppression of hydrate simultaneously
Fruit is more notable.Therefore, developmental research effective amide-type hydrate inhibitor with low cost, new, has great economy
Meaning and industrial utility value.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of simple production process, the amide-type copolymerization of low production cost
The preparation method of thing hydrate dynamic inhibitor, simplifies inhibitor production craft step.
For solving above-mentioned technical problem, the present invention provides technical scheme as follows：
The preparation method of amide analog copolymer hydrate dynamic inhibitor comprises the following steps：
(1) weigh appropriate deionized water, pour in flask, heating in water bath, it is passed through nitrogen, deoxygenation；
(2) weigh nonionic surfactant, add in the deionized water in step (1) successively by acrylamide AM, third
Alkene nitrile AN and caprolactam VCL is added in above-mentioned solution in a nitrogen atmosphere；
(3) adjust bath temperature, add azo initiator；
(4) continue reaction 3～5h, adjust water-bath to room temperature, question response liquid is completely cooled down to room temperature；
(5) wash, be dried, obtain the inhibitor that molecular weight is 300,000～500,000.
Wherein, in described step (1), bath temperature is 60～70 DEG C, preferably 65 DEG C.
Wherein, in described step (2), described nonionic surfactant is secondary alcohol polyoxyethylene ether, n-octyl alcohol polyoxy second
Alkene ether, polyoxyethylene lauryl ether, fatty acid methyl ester APEO, OPEO, NPE
In one or more.Described nonionic surfactant quality is the 0.2%～0.7% of deionized water quality.Its objective is this
Class surfactant can play potentiation to kinetic inhibitor, extends the induction time of gas hydrate synthesis.
Wherein, in described step (2), described AM:AN:VCL mass ratio is 32～38:12～15:40～48.Described AM,
AN and VCL gross mass and deionized water quality are than for 1:15～25.
Wherein, in described step (3), bath temperature is 75～90 DEG C, preferably 80 DEG C.
Wherein, in described step (3), described azo initiator is azo-bis-isobutyl cyanide, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two are different
Butanoic acid dimethyl ester, azo-bis-isobutyrate hydrochloride, azo two isobutyl imidazoline hydrochloride, azo dicyano valeric acid, azo isobutyl
In itrile group Methanamide, the quality such as two or more compounds.Described azo initiator quality be AM, AN and VCL gross mass 2%～
5%.Its objective is that azo initiator is easily decomposed to form free radical, the generation of trigger monomer polyreaction.
Wherein, the whole stirring of described inhibitor preparation process.
The present invention compared with prior art, has the advantages that：
The invention provides a kind of preparation method of amide analog copolymer hydrate dynamic inhibitor, the method is to prepare
Amide-type high polymer as inhibitor, there is simple production process, low production cost, simplify inhibitor and produce work
Skill step, and the inhibitor prepared has the advantages that implantation dosage is low, the suppression time is long.
Specific embodiment
For making the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with being embodied as
Example is described in detail.
The present invention is higher for natural gas dynamic hydrate inhibitor production cost in prior art, and production technology is more
Complicated problem, provides a kind of preparation method of amide analog copolymer hydrate inhibitor, the method have simple production process,
The advantages of low production cost.
Embodiment 1：
Weigh the deionized water of 200g, pour in four round flask, connect nitrogen atmosphere device, and will be temporary transient for remaining mouth
Closing.Flask is placed in 65 DEG C of water-baths of constant temperature, opens nitrogen valve 20min, the oxygen in removing system.Weighing quality is 1g
OPEO nonionic surfactant, add above-mentioned deionized water in, stir 10min.Weigh pure list
Body AM, AN, VCL are respectively 3.5g, 1.5g, 4.8g, are added sequentially in a nitrogen atmosphere in flask.Adjust bath temperature to 80
DEG C, under stirring, the mixing of the 2,2'-Azobis(2,4-dimethylvaleronitrile) of the azodiisobutyronitrile of point 5 addition 0.15g and 0.15g in 5h
Thing.Continue reaction 3h, adjust water-bath to room temperature, wait until that reactant liquor is completely cooled down to room temperature.By reactant liquor using excessive just own
Alkane washs, and is filtrated to get precipitation, and precipitation adopts, and dries it for 50 DEG C afterwards, the molecule of the agent that is inhibited in vacuum drying oven
Amount average is 320,000.
Detection and mensure：In 4 DEG C of initial temperature, under the conditions of initial pressure 8.0MPa, above-mentioned inhibitor is configured to concentration
The aqueous solution of 1.5wt%, is detected by laboratory hydrate inhibitor for natural gas performance testing device, measures inhibitor suppression
The induction time that controlling the water circulation compound generates, experimental result is shown in Table 1.
Embodiment 2：
Weigh the deionized water of 250g, pour in four round flask, connect nitrogen atmosphere device, and will be temporary transient for remaining mouth
Closing.Flask is placed in 65 DEG C of water-baths of constant temperature, opens nitrogen valve 20min, the oxygen in removing system.Weighing quality is
The NPE of 0.6g and 0.6g n-octyl alcohol polyoxyethylene ether nonionic surfactant, add in deionized water,
Open stirring 10min.Weigh pure monomer AM, AN, VCL and be respectively 4.8g, 2.3g, 6g, sequentially add in a nitrogen atmosphere
To in flask.Bath temperature is adjusted to 80 DEG C, under stirring in 5h the azodiisobutyronitrile of points of 5 times addition 0.2g,
The mixture of the azo isobutyronitrile base Methanamide of the azo-bis-iso-dimethyl of 0.2g and 0.2g.Continue reaction 5h, adjust water
Bathe to room temperature, wait until that reactant liquor is completely cooled down to room temperature.By reactant liquor down to beaker, using the washing of excessive normal hexane, filter
It is precipitated, precipitation adopts washing with acetone, 50 DEG C of drying in vacuum drying oven by it afterwards, the molecular weight of the agent that is inhibited is equal
It is worth for 370,000.
Detection and mensure：In the present embodiment, the kinetic inhibitor molecular weight average of preparation is 370,000, other and embodiment 1
Identical, experimental result is shown in Table 1.
Embodiment 3：
Weigh the deionized water of 300g, pour in four round flask, connect nitrogen atmosphere device, and will be temporary transient for remaining mouth
Closing.Flask is placed in 65 DEG C of water-baths of constant temperature, opens nitrogen valve 20min, the oxygen in removing system.Weighing quality is
0.5g OPEO, the NPE of 0.5g and 0.5g n-octyl alcohol polyoxyethylene ether non-ionic surface are lived
Property agent, add deionized water in, open stirring 10min.Weigh pure monomer AM, AN, VCL and be respectively 7g, 2.6g, 8.6g,
It is added sequentially in a nitrogen atmosphere in flask.Bath temperature is adjusted to 80 DEG C, point 5 additions in 5h under stirring
The azodiisobutyronitrile of 0.17g, the azo of the 2,2'-Azobis(2,4-dimethylvaleronitrile) of 0.17g, 0.17g azo-bis-iso-dimethyl and 0.17g
The mixture of isobutyl itrile group Methanamide.Continue reaction 5h, adjust water-bath to room temperature, wait until that reactant liquor is completely cooled down to room temperature.
By reactant liquor down to beaker, using the washing of excessive normal hexane, be filtrated to get precipitation, precipitation adopts washing with acetone, afterwards by its
50 DEG C of drying in vacuum drying oven, the molecular weight average of the agent that is inhibited is 420,000.
Detection and mensure：In the present embodiment, the kinetic inhibitor molecular weight average of preparation is 420,000, other and embodiment 1
Identical, experimental result is shown in Table 1.
Embodiment 4：
Weigh the deionized water of 370g, pour in four round flask, connect nitrogen atmosphere device, and will be temporary transient for remaining mouth
Closing.Flask is placed in 65 DEG C of water-baths of constant temperature, opens nitrogen valve 20min, the oxygen in removing system.Weighing quality is
0.83g polyoxyethylene lauryl ether, the fatty acid methyl ester APEO of 0.83g and 0.83g n-octyl alcohol polyoxyethylene ether non-from
Sub- surfactant, adds in deionized water, opens stirring 10min.Weigh pure monomer AM, AN, VCL be respectively 7.6g,
3.0g, 9.6g, are added sequentially in flask in a nitrogen atmosphere.Bath temperature is adjusted to 80 DEG C, under stirring in 5h
Divide the azo isobutyronitrile base Methanamide of azodiisobutyronitrile, the 2,2'-Azobis(2,4-dimethylvaleronitrile) of 0.31g and 0.31g of 5 addition 0.31g
Mixture.Continue reaction 5h, adjust water-bath to room temperature, wait until that reactant liquor is completely cooled down to room temperature.By reactant liquor down to beaker,
Using the washing of excessive normal hexane, it is filtrated to get precipitation, precipitation adopts washing with acetone, 50 DEG C of bakings in vacuum drying oven by it afterwards
Dry, the molecular weight average of the agent that is inhibited is 500,000.
Detection and mensure：In the present embodiment, the kinetic inhibitor molecular weight average of preparation is 500,000, other and embodiment 1
Identical, experimental result is shown in Table 1.
Comparative example 1：
In the present embodiment, inhibitor is ethylene glycol, and concentration is 20%, and other tests are same as Example 1, and experimental result is shown in
Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | |
| Induction time/min | 1680 | 1830 | 1992 | 2502 | 228 |
The product of above-mentioned four, after testing, is 8.0MPa in initial pressure, and temperature is 4 DEG C, and inhibitor concentration is
1.5wt%, the longest induction time reaches 2502min, and inhibition is much higher than the thermodynamic inhibitor of alcohols, and the method has
Preparation process is simple, the advantages of low production cost.
The experiment lifted is only the preferably example of the present invention, the protection domain being not intended to limit the present invention.Should refer to
Go out, for those skilled in the art, on the premise of without departing from principle of the present invention, can also make
Some improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. the preparation method of amide analog copolymer hydrate dynamic inhibitor is it is characterised in that comprise the following steps：
(1) weigh appropriate deionized water, pour in flask, heating in water bath, it is passed through nitrogen, deoxygenation；
(2) weigh nonionic surfactant, add in the deionized water in step (1), afterwards successively by acrylamide AM, third
Alkene nitrile AN and caprolactam VCL is added in above-mentioned solution in a nitrogen atmosphere；
(3) adjust bath temperature, add azo initiator；
(4) continue reaction 3～5h, adjust water-bath to room temperature, question response liquid is completely cooled down to room temperature；
(5) wash, be dried, obtain the inhibitor that molecular weight is 300,000～500,000.
2. amide analog copolymer hydrate dynamic inhibitor according to claim 1 preparation method it is characterised in that
In described step (1), bath temperature is 60～70 DEG C, preferably 65 DEG C.
3. amide analog copolymer hydrate dynamic inhibitor according to claim 1 preparation method it is characterised in that
In described step (2), described nonionic surfactant is secondary alcohol polyoxyethylene ether, n-octyl alcohol polyoxyethylene ether, lauryl alcohol gather
In oxygen vinyl Ether, fatty acid methyl ester APEO, OPEO, NPE one or more.
4. amide analog copolymer hydrate dynamic inhibitor according to claim 3 preparation method it is characterised in that
Described nonionic surfactant quality is the 0.2%～0.7% of deionized water quality.
5. amide analog copolymer hydrate dynamic inhibitor according to claim 1 preparation method it is characterised in that
In described step (2), described AM:AN:VCL mass ratio is 32～38:12～15:40～48.
6. amide analog copolymer hydrate dynamic inhibitor according to claim 5 preparation method it is characterised in that
Described AM, AN and VCL gross mass and deionized water quality are than for 1:15～25.
7. amide analog copolymer hydrate dynamic inhibitor according to claim 1 preparation method it is characterised in that
In described step (3), bath temperature is 75～90 DEG C, preferably 80 DEG C.
8. amide analog copolymer hydrate dynamic inhibitor according to claim 1 preparation method it is characterised in that
In described step (3), described azo initiator is azo-bis-isobutyl cyanide, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo-bis-iso-dimethyl, idol
Two in nitrogen two 2,2-Dimethylaziridine hydrochlorate, azo two isobutyl imidazoline hydrochloride, azo dicyano valeric acid, azo isobutyronitrile base Methanamide
Kind or the quality such as multiple compound.
9. amide analog copolymer hydrate dynamic inhibitor according to claim 8 preparation method it is characterised in that
Described azo initiator quality is the 2%～5% of AM, AN and VCL gross mass.
10. the preparation method according to the arbitrary described amide analog copolymer hydrate dynamic inhibitor of claim 1-9, it is special
Levy and be, the whole stirring of described inhibitor preparation process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610802031.8A CN106380541B (en) | 2016-09-05 | 2016-09-05 | The preparation method of amide analog copolymer hydrate dynamic inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610802031.8A CN106380541B (en) | 2016-09-05 | 2016-09-05 | The preparation method of amide analog copolymer hydrate dynamic inhibitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106380541A true CN106380541A (en) | 2017-02-08 |
| CN106380541B CN106380541B (en) | 2018-07-13 |
Family
ID=57937979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610802031.8A Expired - Fee Related CN106380541B (en) | 2016-09-05 | 2016-09-05 | The preparation method of amide analog copolymer hydrate dynamic inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106380541B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070063A (en) * | 2017-12-29 | 2018-05-25 | 中国科学院广州能源研究所 | A kind of vinylamide based block copolymer hydrate dynamic inhibitor and preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0668958B1 (en) * | 1992-11-20 | 1998-03-18 | Colorado School Of Mines | Method for controlling clathrate hydrates in fluid systems |
| US20060058449A1 (en) * | 2002-11-06 | 2006-03-16 | Basf Aktiengesellschaft | Vinyllactam copolymers used as gas hydrate inhibitors |
| CN104263340A (en) * | 2014-09-04 | 2015-01-07 | 西南石油大学化学化工学院 | Kinetic natural gas hydrate inhibitor and preparation method thereof |
| CN105859963A (en) * | 2016-04-15 | 2016-08-17 | 西南石油大学 | Polycyclic polymerized natural gas hydrate dynamic inhibitor and preparation method |
-
2016
- 2016-09-05 CN CN201610802031.8A patent/CN106380541B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0668958B1 (en) * | 1992-11-20 | 1998-03-18 | Colorado School Of Mines | Method for controlling clathrate hydrates in fluid systems |
| US20060058449A1 (en) * | 2002-11-06 | 2006-03-16 | Basf Aktiengesellschaft | Vinyllactam copolymers used as gas hydrate inhibitors |
| CN104263340A (en) * | 2014-09-04 | 2015-01-07 | 西南石油大学化学化工学院 | Kinetic natural gas hydrate inhibitor and preparation method thereof |
| CN105859963A (en) * | 2016-04-15 | 2016-08-17 | 西南石油大学 | Polycyclic polymerized natural gas hydrate dynamic inhibitor and preparation method |
Non-Patent Citations (4)
| Title |
|---|
| 唐黎明 等: "《高分子化学》", 31 May 2009, 清华大学出版社 * |
| 张强: "新型水合物抑制剂PVCL及其共聚物的制备与应用研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑（月刊）》 * |
| 胡军: "水合物动力学抑制剂的合成和性能研究及应用", 《中国博士学位论文全文数据库 工程科技I辑（月刊）》 * |
| 马国光: "《天然气集输工程》", 28 February 2014, 石油工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070063A (en) * | 2017-12-29 | 2018-05-25 | 中国科学院广州能源研究所 | A kind of vinylamide based block copolymer hydrate dynamic inhibitor and preparation method and application |
| WO2019128102A1 (en) * | 2017-12-29 | 2019-07-04 | 中国科学院广州能源研究所 | Vinyl amide block copolymer hydrate kinetic inhibitor, preparation method therefor and application thereof |
| CN108070063B (en) * | 2017-12-29 | 2020-03-24 | 中国科学院广州能源研究所 | Vinyl amide block copolymer hydrate kinetic inhibitor and preparation method and application thereof |
| US10913813B2 (en) | 2017-12-29 | 2021-02-09 | Guangzhou Institute Of Energy Conversion, Chinese Academy Of Sciences | Vinylamide block copolymer kinetic hydrate inhibitor and preparation method and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106380541B (en) | 2018-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3227672A (en) | Water soluble cationic copolymers of beta-hydroxyalkyl ethlenically unsaturated ester with vinyl tertiary amine | |
| CN103396515B (en) | A kind of high temperature resistance treated starch fluid loss agent and preparation method thereof | |
| CN106543381A (en) | A kind of hydroxyl polyacrylate aqueous dispersion and preparation method thereof | |
| WO2018209716A1 (en) | Sulfonate-betaine-type hydrophobic associated polymer and preparation method therefor | |
| CN105111362B (en) | A kind of powdery paints heavy duty detergent minute surface levelling agent and preparation method and application | |
| GB842215A (en) | Adhesively bonded non-woven fibrous product and method of making same | |
| CN101921359A (en) | Polyacrylic acid or copolymer thereof and preparation method of polyacrylate or copolymer salt thereof | |
| CN104530298B (en) | A kind of acrylic ester emulsion, preparation method and application thereof | |
| KR20140116133A (en) | Method of preparing acrylic polymers and products produced thereby | |
| EA201100876A1 (en) | METHOD FOR OBTAINING CHAOTIC RADICAL COPOLYMERS AND ACTIVE SUBSTANCE COMPOSITIONS OBTAINED FROM | |
| TW201333046A (en) | Method for the preparation of styrenic fluoropolymers | |
| CN107964063B (en) | PFOA-free polymer and preparation method and application thereof | |
| CN111138597B (en) | Organosilicon modified cationic acrylic acid secondary dispersion and preparation method thereof | |
| CN106380541A (en) | Preparation method of amide copolymer hydrate kinetic inhibitor | |
| CN105693944B (en) | A kind of preparation method of heat resist modification styrene-acrylic emulsion | |
| CN103980418A (en) | Cationic waterborne organic fluorine acrylate polymer as well as preparation method and application of cationic waterborne organic fluorine acrylate polymer | |
| CN103880995B (en) | A kind of method of well-controlled radical polymerization and polyvinyl | |
| CN106396142B (en) | A kind of scale preventative and preparation method thereof | |
| CN105408374A (en) | Hydrophobic alkali soluble emulsion thickener | |
| CN105001365A (en) | Anionic polyacrylamide corrosion inhibitor and preparing method thereof | |
| CN105837745B (en) | Micro- auxiliary agent and preparation method thereof | |
| Hou et al. | Determination of monomer apparent reactivity ratios for acrylonitrile-acrylamide copolymerization system | |
| CN103408698A (en) | In-situ redox initiation for preparing polyacrylamide water-drum water dispersion | |
| CN103665237B (en) | A kind of method improving polyvinyl chloride (PVC) RESINS combined coefficient | |
| CN113372483A (en) | Water-based fluorine-containing acrylic resin, preparation method thereof and application thereof in coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Lu Dianxun Inventor after: Cheng Changqi Inventor before: Lu Shusong Inventor before: Lu Dianxun Inventor before: Cheng Changqi Inventor before: Cheng Xuefeng Inventor before: Cheng Xueyu |
|
| GR01 | Patent grant | ||
| 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: 20180713 Termination date: 20190905 |