CN105111342A - High-concentration acrylamide water solution polymerization method - Google Patents
High-concentration acrylamide water solution polymerization method Download PDFInfo
- Publication number
- CN105111342A CN105111342A CN201510601113.1A CN201510601113A CN105111342A CN 105111342 A CN105111342 A CN 105111342A CN 201510601113 A CN201510601113 A CN 201510601113A CN 105111342 A CN105111342 A CN 105111342A
- Authority
- CN
- China
- Prior art keywords
- acrylamide
- solution
- water
- mass percent
- polymerization
- 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
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a high-concentration acrylamide water solution polymerization method, and belongs to the field of polymer synthesis. According to the method, a water solution radical polymerization method is adopted, a C1-C5 organic solvent is used as a thermal removal solvent; a water-soluble azo compound serves as an initiating agent; sodium formate and sodium hypophosphite serves as a chain transfer agent; a polyacrylamide solution with a solid content of 70.1-79.3% and the molecular weight of 6,100-65,400 can be synthesized by performing a polymerization reaction on the thermal removal solvent, the chain transfer agent and the initiating agent at 45-56 DEG C and adjusting the amounts of the thermal removal solvent, the chain transfer agent and the initiating agent. The polyacrylamide synthesized by the method has the advantages of being high in solid content, high in dilution speed and the like, and is suitable for a high-molecular emulsifier, a dispersant, a binding agent, a tackifier, a paper reinforcing agent, a textile dye printing additive and the like.
Description
Technical field
The present invention relates to the synthetic method of macromolecular compound polyacrylamide, particularly relate to a kind of high density polymerization of aqueous solution of acrylamide method, belong to Polymer Synthesizing field.
Background technology
Polyacrylamide is a kind of important water-soluble polymer, and its application widely.The method of synthesis polyacrylamide has water solution polymerization process, reversed emulsion polymerization and dispersion copolymerization method etc., water solution polymerization process simply, does not use a large amount of organic solvent to be of paramount importance method in industrial production due to synthesis technique always, but because acrylamide monomer activity is high, exothermic heat of reaction is obvious, under high monomer concentration, react easy implode, be difficult to control.The people such as Teng great Yong report the polyacrylamide solid content that synthesized by conversed phase micro emulsion copolymerization method close to 40% at 31 volumes the 6th phase " modern chemical industry " 58-61 page in 2011, this technology main inventive person with water solution polymerization process at granted patent ZL201310400295.7, ZL201110271370.5, ZL201110252665.8, ZL03126303.8, in ZL200610048457.5, be 9.5 ~ 11.5% to concentration respectively, 13.5 ~ 16.5%, 18.0 ~ 22.5%, 30%, the acrylamide solution of 40% has carried out polyreaction, acrylamide monomer concentration in patent CN102690381A is up to 55%, for the highest response monomer concentration of current bibliographical information.Monomer concentration realizes acrylamide soln polyreaction up to 66.7% ~ 67.6% and has no pertinent literature report at present.
Summary of the invention
The object of the present invention is to provide a kind of employing water solution polymerization process, under high monomer concentration, realize acrylamide soln polyreaction, synthesize the polyacrylamide that solid content is high, dilution dissolution rate is fast.
In order to realize goal of the invention, technical solution of the present invention is as follows:
Adopt water solution polymerization process, select C
1~ C
5class organic solvent is heat transferring solvent, and water-soluble azo compounds is initiator, and sodium formiate, inferior sodium phosphate are chain-transfer agent, and by regulating the consumption synthesis of high solid content polyacrylamide solution of heat transferring solvent, chain-transfer agent and initiator, concrete steps are as follows:
(1) monomer preparation: in 30 DEG C of waters bath with thermostatic control, 100g solid acrylamide and 48 ~ 50g deionized water are mixed with the acrylamide solution that mass percent concentration is 66.7% ~ 67.6%, and 0.007 ~ 0.040g water-soluble azo class initiator is dissolved in 3.0g water and is mixed with initiator solution;
(2) add 11 ~ 15gC in the reactor
1~ C
5class organic solvent, 2.4 ~ 10g sodium formiate or 3.1 ~ 16g inferior sodium phosphate or both mixtures are as chain-transfer agent, and above-mentioned acrylamide solution, the above-mentioned initiator solution prepared of 0.36g prepared of 15.0g, stirs, be progressively warming up to 45-56 DEG C.
(3), under maintenance whipped state, drip remaining acrylamide soln and remaining initiator solution by syringe or constant pressure funnel, dropwised in 2.5 hours;
(4) continue reaction stopped reaction after 2 hours, cooling, leave standstill after isolate organic solvent, obtain high solids content polyacrylamide solution.
Described water-soluble azo class initiator is azo two isobutyl tetrahydroglyoxaline hydrochloric acid (VA-044) or azo diisobutyl amidine hydrochloride (V-50), preferred azo two isobutyl imidazoline hydrochloride.
Described C
1~ C
5class organic solvent is dithiocarbonic anhydride, Skellysolve A, preferred dithiocarbonic anhydride.
Temperature of reaction preferably 45 DEG C in step (2).
Preferably 0.64:1 is composite in molar ratio for chain-transfer agent sodium formiate, both inferior sodium phosphate mixture.
Measuring its solid content by GB12005.2-89 is 70.1 ~ 79.3%, and measuring its molecular weight by GB17514-1998 is 0.61 ~ 6.54 ten thousand, and measuring monomer whose residual rate by GB12005.3-89 is 0.4 ~ 3.3%.
Beneficial effect of the present invention is: the present invention is by selecting the water-soluble azo class initiator that activation energy is low, reduce temperature of reaction, slow down speed of reaction, mate the suitable heat transferring solvent of boiling point simultaneously, in time reaction heat removed, monomer concentration up to 66.7% ~ 67.6% time pass through aqueous solution polymerization, one-step synthesis high solids content polyacrylamide, molecular weight is controllable adjustment between 0.61 ~ 6.54 ten thousand, and polyacrylamide solution solid content, more than 70%, reduces the transportation cost of product.Compared with reversed emulsion polymerization, aqueous dispersion polymerization method, the method is simple to operate, can synthesize the polyacrylamide of specific molecular weight range, is applicable to suitability for industrialized production.The polyacrylamide solution dilution dissolution rate of method synthesis is fast thus, is applicable to paper strengthening agent, polymeric retention aid emulsifying agent, textile auxiliary, tackiness agent etc.
Embodiment
In order to the present invention will be described better, enumerate embodiment as follows:
Embodiment 1
(1) in 30 DEG C of waters bath with thermostatic control, 100g solid acrylamide and 50g deionized water are mixed with the acrylamide solution that mass percent concentration is 66.7%, 0.0147g azo two isobutyl imidazoline hydrochloride is dissolved in 3.0g water and is mixed with initiator solution;
(2) in 250mL tetra-mouthfuls of reaction flasks, add 11.0g dithiocarbonic anhydride, 3.1g inferior sodium phosphate, above-mentioned acrylamide solution, the above-mentioned azo two isobutyl imidazoline hydrochloride solution prepared of 0.36g prepared of 15.0g, stir, be progressively warming up to 45 DEG C;
(3), under keeping whipped state, drip remaining acrylamide soln ， Tong Walk syringe by constant pressure funnel and coordinate the remaining azo two isobutyl imidazoline hydrochloride initiator solution of dropping, dropwised in 2.5 hours simultaneously;
(4) continue reaction 2 hours, cooling, leave standstill after isolate organic solvent, obtain high solids content polyacrylamide solution.
Measuring solid content by GB12005.2-89 is 72.8%, and measuring its molecular weight by GB17514-1998 is 1.85 ten thousand, and measuring monomer whose residual rate by GB12005.3-89 is 0.9%.
Embodiment 2
With embodiment 1, in step (2), dithiocarbonic anhydride changes Skellysolve A into.Product solid content is 70.4%, and molecular weight is 2.18 ten thousand, and monomer residue rate is 1.2%.
Embodiment 3
With embodiment 1, in step (2), 3.1g inferior sodium phosphate changes 1.6g inferior sodium phosphate and 1.5g sodium formiate mixture into.Product solid content is 70.2%, and molecular weight is 1.62 ten thousand, and monomer residue rate is 0.6%.
Embodiment 4
With embodiment 1, in step (2), 3.1g inferior sodium phosphate changes 2.2g inferior sodium phosphate and 0.9g sodium formiate mixture into.Product solid content is 74.2%, and molecular weight is 1.58 ten thousand, and monomer residue rate is 0.4%.
Embodiment 5
With embodiment 1, in step (2), temperature of reaction changes 50 DEG C into.Product solid content is 70.1%, and molecular weight is 2.21 ten thousand, and monomer residue rate is 2.2%.
Embodiment 6
With embodiment 1, in step (1), azo two isobutyl imidazoline hydrochloride changes 0.0078g into.Its solid content is 75.7%, and molecular weight is 1.95 ten thousand, and monomer residue rate is 0.9%.
Embodiment 7
With embodiment 1, in step (1), azo two isobutyl imidazoline hydrochloride changes 0.0087g into, and in step (2), inferior sodium phosphate changes 7.97g into.Its solid content is 72.3%, and molecular weight is 1.35 ten thousand, and monomer residue rate is 0.8%
Embodiment 8
With embodiment 1, in step (1), azo two isobutyl imidazoline hydrochloride changes 0.0080g into, and in step (2), inferior sodium phosphate changes 16g into.Its solid content is 72.0%, and molecular weight is 0.69 ten thousand, and monomer residue rate is 0.9%
Embodiment 9
With embodiment 1, in step (1), azo two isobutyl imidazoline hydrochloride should be 0.0164g, and in step (2), inferior sodium phosphate changes 16g into.Its solid content is 79.3%, and molecular weight is 0.61 ten thousand, and monomer residue rate is 0.8%.
Embodiment 10
With embodiment 1, in step (1), azo two isobutyl imidazoline hydrochloride should be 0.0165g, and in step (2), inferior sodium phosphate changes 9.76g inferior sodium phosphate and 6.24g sodium formiate into.Its solid content is 77.2%, and molecular weight is 0.79 ten thousand, and monomer residue rate is 0.4%.
Embodiment 11
With embodiment 1, deionized water is changed into 48g and is mixed with the acrylamide solution that mass percent concentration is 67.6% by step (1).Product solid content is 73.5%, and molecular weight is 3.82 ten thousand, and monomer residue rate is 1.8%.
Embodiment 12
(1) in 30 DEG C of waters bath with thermostatic control, 100g solid acrylamide and 50g deionized water are mixed with the acrylamide solution that mass percent concentration is 66.7%, 0.0105g azo diisobutyl amidine hydrochloride is dissolved in 3.0g water and is mixed with initiator solution;
(2) in 250mL tetra-mouthfuls of reaction flasks, add 11.0g Skellysolve A, 2.4g sodium formiate, above-mentioned acrylamide solution, the above-mentioned initiator solution prepared of 0.36g prepared of 15.0g, stir, be progressively warming up to 56 DEG C;
(3), under keeping whipped state, drip remaining acrylamide soln ， Tong Walk syringe by constant pressure funnel and coordinate the remaining initiator solution of dropping, dropwised in 2.5 hours simultaneously;
(4) continue reaction 2 hours, cooling, leave standstill after isolate organic solvent, obtain high solids content polyacrylamide solution.
Measuring solid content by GB12005.2-89 is 70.7%, is 6.54 ten thousand by GB17514-1998 determining molecular weight, and measuring monomer residue rate by GB12005.3-89 is 3.3%.
Embodiment 13
With embodiment 12, in step (1), azo diisobutyl amidine hydrochloride consumption changes 0.04g into.Its solid content is 77.0%, and molecular weight is 5.62 ten thousand, and monomer residue rate is 1.6%.
Embodiment 14
With embodiment 12, in step (2), 2.4g sodium formiate changes 3.1g inferior sodium phosphate into.Product solid content is 73.7%, and molecular weight is 3.68 ten thousand, and monomer residue rate is 2.2%.
Claims (5)
1. mass percent concentration is 66.7% ~ 67.6% polymerization of aqueous solution of acrylamide method, realizes as follows, it is characterized in that:
(1) monomer preparation: in 30 DEG C of waters bath with thermostatic control, 100g solid acrylamide and 48 ~ 50g deionized water are mixed with the acrylamide solution that mass percent concentration is 66.7% ~ 67.6%, and 0.007 ~ 0.040g water-soluble azo class initiator is dissolved in 3.0g water and is mixed with initiator solution;
(2) add 11 ~ 15gC in the reactor
1~ C
5class organic solvent, 2.4 ~ 10g sodium formiate or 3.1 ~ 16g inferior sodium phosphate or both mixtures are as chain-transfer agent, and above-mentioned acrylamide solution, the above-mentioned initiator solution prepared of 0.36g prepared of 15.0g, stirs, be progressively warming up to 45-56 DEG C;
(3), under maintenance whipped state, drip remaining acrylamide soln and remaining initiator solution by syringe or constant pressure funnel, dropwised in 2.5 hours;
(4) continue reaction stopped reaction after 2 hours, cooling, leave standstill after isolate organic solvent, obtain polyacrylamide solution;
Described water-soluble azo class initiator selects azo two isobutyl tetrahydroglyoxaline hydrochloric acid or azo diisobutyl amidine hydrochloride;
Described C
1~ C
5class organic solvent selects dithiocarbonic anhydride or Skellysolve A.
2. mass percent concentration as claimed in claim 1 is 66.7% ~ 67.6% polymerization of aqueous solution of acrylamide method, it is characterized in that: water-soluble azo class initiator preferred azo two isobutyl imidazoline hydrochloride.
3. mass percent concentration as claimed in claim 1 is 66.7% ~ 67.6% polymerization of aqueous solution of acrylamide method, it is characterized in that: C
1~ C
5the preferred dithiocarbonic anhydride of class organic solvent.
4. mass percent concentration as claimed in claim 1 is 66.7% ~ 67.6% polymerization of aqueous solution of acrylamide method, it is characterized in that: temperature of reaction preferably 45 DEG C in step (2).
5. if the mass percent concentration of claim 1-4 as described in one of them is 66.7% ~ 67.6% polymerization of aqueous solution of acrylamide method, it is characterized in that: preferably 0.64:1 is composite in molar ratio for described chain-transfer agent sodium formiate, both inferior sodium phosphate mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510601113.1A CN105111342B (en) | 2015-09-18 | 2015-09-18 | A kind of high concentration polymerization of aqueous solution of acrylamide method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510601113.1A CN105111342B (en) | 2015-09-18 | 2015-09-18 | A kind of high concentration polymerization of aqueous solution of acrylamide method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105111342A true CN105111342A (en) | 2015-12-02 |
| CN105111342B CN105111342B (en) | 2017-04-05 |
Family
ID=54659480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510601113.1A Active CN105111342B (en) | 2015-09-18 | 2015-09-18 | A kind of high concentration polymerization of aqueous solution of acrylamide method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105111342B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250456A (en) * | 2018-01-17 | 2018-07-06 | 山东诺尔生物科技有限公司 | A kind of high effective Ultra-low molecular weight polyacrylamide solution and preparation method thereof |
| CN109679008A (en) * | 2019-01-14 | 2019-04-26 | 东营市诺尔化工有限责任公司 | A kind of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887923A (en) * | 2006-07-26 | 2007-01-03 | 河南省科学院质量检验与分析测试研究中心 | Prepn of low molecular weight polyacrylamide |
| CN102690381A (en) * | 2012-06-21 | 2012-09-26 | 河南省科学院高新技术研究中心 | Preparation method of ultralow-molecular-weight (5000-20000) polyacrylamide |
| CN103435727A (en) * | 2013-09-06 | 2013-12-11 | 河南省科学院高新技术研究中心 | Preparation method of low molecular weight (LMW) polyacrylamide with molecular weight of 0.4-1 million |
-
2015
- 2015-09-18 CN CN201510601113.1A patent/CN105111342B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887923A (en) * | 2006-07-26 | 2007-01-03 | 河南省科学院质量检验与分析测试研究中心 | Prepn of low molecular weight polyacrylamide |
| CN102690381A (en) * | 2012-06-21 | 2012-09-26 | 河南省科学院高新技术研究中心 | Preparation method of ultralow-molecular-weight (5000-20000) polyacrylamide |
| CN103435727A (en) * | 2013-09-06 | 2013-12-11 | 河南省科学院高新技术研究中心 | Preparation method of low molecular weight (LMW) polyacrylamide with molecular weight of 0.4-1 million |
Non-Patent Citations (2)
| Title |
|---|
| 许寒生 等: "丙烯酰胺的固态辐射聚合", 《辐射研究与辐射工艺学报》 * |
| 赵献增 等: "高单体浓度下超低相对分子质量PAM的水溶液聚合", 《化学与黏合》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250456A (en) * | 2018-01-17 | 2018-07-06 | 山东诺尔生物科技有限公司 | A kind of high effective Ultra-low molecular weight polyacrylamide solution and preparation method thereof |
| CN108250456B (en) * | 2018-01-17 | 2021-03-26 | 山东诺尔生物科技有限公司 | High-effective ultra-low molecular weight polyacrylamide solution and preparation method thereof |
| CN109679008A (en) * | 2019-01-14 | 2019-04-26 | 东营市诺尔化工有限责任公司 | A kind of displacement of reservoir oil ultra high molecular weight anion-type polyacrylamide and its preparation method and application |
| CN109679008B (en) * | 2019-01-14 | 2021-04-30 | 东营市诺尔化工有限责任公司 | Ultrahigh molecular weight anionic polyacrylamide for oil displacement and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105111342B (en) | 2017-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103937484B (en) | Shale gas well slickwater fracturing fluid system high-efficiency emulsion quick water-soluble drag reducer | |
| US8153735B2 (en) | Continuous polymerization process | |
| CN103509154B (en) | Preparation method of zwitterionic polyacrylamide | |
| CN101544726A (en) | Method for synchronizing anode polyacrylamide latex | |
| CN102863582B (en) | Preparation method of ultra-high molecular weight cationic polyacrylamide | |
| CN100384891C (en) | Prepn of low molecular weight polyacrylamide | |
| CN109485784A (en) | A kind of method of microreactor synthesis polyacrylic acid ester soap-free emulsion | |
| CN105111342A (en) | High-concentration acrylamide water solution polymerization method | |
| CN103415538B (en) | Process for producing polymers by means of emulsion or suspension polymerization in a jet loop reactor | |
| CN102690381A (en) | Preparation method of ultralow-molecular-weight (5000-20000) polyacrylamide | |
| CN101220263A (en) | Water-based fracturing fluid gelatinizer and producing method thereof | |
| CN102492067B (en) | Preparation method of low-molecular-weight ammonium polyacrylate | |
| CN103435727B (en) | Preparation method of low molecular weight (LMW) polyacrylamide with molecular weight of 0.4-1 million | |
| CN106317324B (en) | Prepare drag reducer stabilizer and shale gas pressure break drag reducer and their preparation method | |
| CN109233757B (en) | Drilling fluid sealing agent methyl silicon resin quasi polymer and preparation method thereof | |
| CN104232055A (en) | Drag reducer for fracturing fluid and preparation method thereof | |
| CN102432721B (en) | Method for synthesizing polyacrylamide having low-molecular weight of 200000 to 450000 | |
| CN102532364B (en) | Acrylamide ultrahigh molecular weight polymerization reaction initiator | |
| CN107474177A (en) | A kind of copolymerization composition manufacture method of calcium ions modified anion polyacrylamide | |
| US9090749B2 (en) | Method for producing aqueous polymer dispersions | |
| CN101519471A (en) | Emulsion polymerization preparation method of chlorinated polyether resin | |
| CN103923582A (en) | Production method of modified emulsified binder | |
| CN105237679A (en) | Preparation method of oil well cement emulsion polymer fluid loss agent | |
| CN106279524A (en) | The preparation method of a kind of shale gas pressure break drag reducer and pressure break drag reducer | |
| CN102391404B (en) | Method for preparing low molecular weight polyacrylamide with molecular weight of 100,000 to 250,000 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |