CN105481676A - Ultralow molecular weight polyacrylic acid synthesis method - Google Patents
Ultralow molecular weight polyacrylic acid synthesis method Download PDFInfo
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- CN105481676A CN105481676A CN201510846447.5A CN201510846447A CN105481676A CN 105481676 A CN105481676 A CN 105481676A CN 201510846447 A CN201510846447 A CN 201510846447A CN 105481676 A CN105481676 A CN 105481676A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
Abstract
The invention relates to an ultralow molecular weight polyacrylic acid synthesis method. The method comprises adding a catalyst and deionized water into a reactor with a reflux condensing tube, a stirrer and a thermometer, carrying out stirring, heating a water bath to a temperature of 70-95 DEG C, dropwisely adding acrylic acid and an initiator into the mixture in 2-4hr, in the reaction, controlling a system pH in a range of 5-7 through dropwise addition of an alkali liquor, and after the reaction, carrying out thermal insulation for 1-4hr to obtain the ultralow molecular weight polyacrylic acid. The prepared polyacrylic acid has number-average molecular weight less than 1000, a molecular weight distribution coefficient less than 1.5 and excellent scale inhibition and dispersion performances and can be widely used in industries of water treatment, papermaking, coal water slurry and petrochemical engineering.
Description
Technical field
The invention belongs to macromolecular material production technical field, particularly one utilizes metal catalytic oxidation reduction system to synthesize the polyacrylic method of Ultra-low molecular weight.
Background technology
One of fine chemicals that polyacrylic acid (sodium) is is extensively researched and developed as recent domestic, is applied to all conglomeraties such as food, weaving, papermaking, water treatment, petrochemical complex.The relative molecular mass of polyacrylic acid (sodium) determines its application category, and the main dispersion agent being used as water treatment, pigment etc. of molecular weight 1000 ~ 5000, molecular weight is 10
4~ 10
6main be used as thickening material, stablizer etc., molecular weight is higher than 10
6then for flocculation agent, thickening material etc.Performance and its molecular weight and the arrangement etc. thereof of polyacrylic acid (sodium) have close relationship, and as water conditioner, the molecular weight of polyacrylic acid (sodium) is less, distribution is narrower to have research both domestic and external to confirm, its scale-inhibiting properties is stronger.And polyacrylic acid (sodium) molecular weight that obtains of the domestic radical polymerization processes for preparing generally adopted is substantially all more than 2000 at present, molecular weight is high, distributes wide, and product performance do not reach best.Therefore develop molecular weight lower than 1000 the polyacrylic preparation technology of Ultra-low molecular weight, very meaningful to the performance heightening currently available products.The polyacrylic acid of Ultra-low molecular weight in water as the polyelectrolyte of anionic, can adsorb by suspended particles, suspended particles surface is made to form electrostatic double layer, under the effect of static charge, particle mutually repels and makes particle suspended dispersed in water, also cover the active site of suspended particles surface continued growth simultaneously thus prevent particle growth, can also crystals be embedded and suppress crystal nucleation.
The people that how to wait quietly of Beijing Forestry University take Potassium Persulphate as initiator, Virahol is that to have synthesized a series of viscosity-average molecular weight be the sodium polyacrylate of 500 ~ 10000 to chain-transfer agent, the Gao Fengqin of Northwestern Polytechnical University adopt Dynamic Water solution polymerization process prepared a series of molecular weight 600 ~ 7000 sodium polyacrylate, this kind of traditional radical polymerization mode adopts persulphate to make initiator, and add the polyacrylic acid (sodium) that alcohols synthesizes as chain-transfer agent and there is initiator, chain-transfer agent consumption is large and the problem such as cannot to remove completely, it causes slowly, fast growth, the polyreaction that nature of of fast termination is difficult to control, make the difficulty preparing Ultra-low molecular weight and acrylate with narrow molecular weight distribution (sodium) very large.
The people such as the Niu Lei of Central South University take ammonium persulphate as initiator, sodium bisulfite has prepared the sodium polyacrylate that viscosity-average molecular weight is 2000 ~ 3000 for chain-transfer agent, the Li Shuqin of Xiangfan University take hydrogen peroxide as initiator, sodium bisulfite is chain-transfer agent, under ultrasonic assistant, has prepared the sodium polyacrylate that relative molecular weight is 2000 ~ 3000, and this traditional redox system also exists, and reductive agent add-on is more, low temperature is put and easily occurred muddiness or separate out the problems such as inorganic salt.
Summary of the invention
The object of the invention is to utilize interpolation metal to carry out the polyacrylic method of catalytic oxidation-reduction system synthesis Ultra-low molecular weight.
In order to achieve the above object, the present invention is achieved by the following technical solutions: take vinylformic acid as raw material, and under the acting in conjunction of initiator and catalyzer, polymerization generates the polyacrylic acid of Ultra-low molecular weight.
The polyacrylic synthetic method of a kind of Ultra-low molecular weight of the present invention, the method comprises the steps: reflux condensing tube is being housed, agitator, catalyzer and deionized water is added in the reactor of thermometer, catalyzer accounts for total amount 0.002wt% ~ 0.01wt%, open and stir, and make warming-in-water be heated to 70 ~ 95 DEG C, start to drip vinylformic acid and initiator, vinylformic acid accounts for the 30wt% ~ 40wt% of total amount, initiator accounts for the 0.15wt% ~ 0.8wt% of total amount, time for adding 2 ~ 4hr, reaction is simultaneously by dripping mode hierarchy of control pH=5 ~ 7 of alkali lye, obtain number-average molecular weight after insulation 1 ~ 4hr after terminating reaction and be less than 1000, the Ultra-low molecular weight polyacrylic acid that molecular weight distribution index is less than 1.5.
Described catalyzer is one or more in nano level elemental silver, Silver Nitrate, Silver monoacetate, Cobaltous diacetate, and content accounts for total amount 0.002wt% ~ 0.01wt%.
Described initiator is one or more in hydrogen peroxide, ammonium persulphate, Sodium Persulfate and Potassium Persulphate, and initiator accounts for the 0.15wt% ~ 0.8wt% of total amount.
Described alkali lye is the one in the sodium hydroxide of 1 ~ 10mol/L, potassium hydroxide, sodium carbonate solution.
Synthetic method initiator amount of the present invention is low, can not introduce be difficult to reclaim alcohols and inorganic salts, the finished product foreign matter content is extremely low, and monomer conversion is high, molecular weight and molecular weight distribution low, the dispersion agent of excellent property can be obtained.
Embodiment
Below in conjunction with method of the present invention be applied to Ultra-low molecular weight polyacrylic synthesis time effect describe in detail.
Embodiment 1
30mg nanometer silver and deionized water is added in the reactor that reflux condensing tube, agitator, thermometer are housed, open and stir, and make warming-in-water be heated to 70 DEG C, start to drip 200g vinylformic acid and 40g hydrogen peroxide, time for adding 4hr, reaction is simultaneously by dripping the mode hierarchy of control pH=5 of the sodium hydroxide solution of 10mol/L, and after terminating reaction, insulation 4hr can obtain final product, its number-average molecular weight 920, molecular weight distribution index 1.47.
Embodiment 2
20mg Silver Nitrate, 20mg Cobaltous diacetate and deionized water is added in the reactor that reflux condensing tube, agitator, thermometer are housed, open and stir, and make warming-in-water be heated to 90 DEG C, start to drip 200g vinylformic acid and 30g Sodium Persulfate, time for adding 3hr, reaction is simultaneously by dripping the mode hierarchy of control pH=6 of the sodium hydroxide solution of 5mol/L, and after terminating reaction, insulation 2hr can obtain final product, its number-average molecular weight 870, molecular weight distribution index 1.4.
Embodiment 3
10mg Silver monoacetate, 10mg Cobaltous diacetate and deionized water is added in the reactor that reflux condensing tube, agitator, thermometer are housed, open and stir, and make warming-in-water be heated to 80 DEG C, start to drip 200g vinylformic acid and 10g ammonium persulphate, 10g hydrogen peroxide, time for adding 2.5hr, reaction is simultaneously by dripping the mode hierarchy of control pH=7 of the sodium carbonate solution of 1mol/L, and after terminating reaction, insulation 3hr can obtain final product, its number-average molecular weight 850, molecular weight distribution index 1.35.
Embodiment 4
10mg Silver monoacetate and deionized water is added in the reactor that reflux condensing tube, agitator, thermometer are housed, open and stir, and make warming-in-water be heated to 95 DEG C, start to drip 200g vinylformic acid and 10g Potassium Persulphate, time for adding 3hr, reaction is simultaneously by dripping the mode hierarchy of control pH=5 of the potassium hydroxide solution of 10mol/L, and after terminating reaction, insulation 2hr can obtain final product, its number-average molecular weight 761, molecular weight distribution index 1.41.
Claims (4)
1. the polyacrylic synthetic method of Ultra-low molecular weight, is characterized in that comprising the following steps:
Reflux condensing tube is being housed, agitator, catalyzer and deionized water is added in the reactor of thermometer, catalyzer accounts for total amount 0.002wt% ~ 0.01wt%, open and stir, and make warming-in-water be heated to 70 ~ 95 DEG C, start to drip vinylformic acid and initiator, vinylformic acid accounts for the 30wt% ~ 40wt% of total amount, initiator accounts for the 0.15wt% ~ 0.8wt% of total amount, time for adding 2 ~ 4hr, reaction is simultaneously by dripping mode hierarchy of control pH=5 ~ 7 of alkali lye, obtain number-average molecular weight after insulation 1 ~ 4hr after terminating reaction and be less than 1000, the Ultra-low molecular weight polyacrylic acid that molecular weight distribution index is less than 1.5.
2. the polyacrylic synthetic method of a kind of Ultra-low molecular weight according to claim 1, it is characterized in that described catalyzer is one or more in nano level elemental silver, Silver Nitrate, Silver monoacetate, Cobaltous diacetate, content accounts for total amount 0.002wt% ~ 0.01wt%.
3. the polyacrylic synthetic method of a kind of Ultra-low molecular weight according to claim 1, it is characterized in that described initiator is one or more in hydrogen peroxide, ammonium persulphate, Sodium Persulfate and Potassium Persulphate, initiator accounts for the 0.15wt% ~ 0.8wt% of total amount.
4. the polyacrylic synthetic method of a kind of Ultra-low molecular weight according to claim 1, is characterized in that described alkali lye is the one in the sodium hydroxide of 1 ~ 10mol/L, potassium hydroxide, sodium carbonate solution.
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| CN201510846447.5A CN105481676A (en) | 2015-11-27 | 2015-11-27 | Ultralow molecular weight polyacrylic acid synthesis method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824548A (en) * | 2017-02-27 | 2017-06-13 | 中国地质科学院矿产综合利用研究所 | Flotation dispersing agent suitable for high-talc-content copper-nickel sulfide ore and preparation method thereof |
| CN112079453A (en) * | 2020-09-09 | 2020-12-15 | 南京全宇节能技术有限公司 | Polymer salt inhibitor for salt-containing wastewater back-spraying quenching tower process |
| CN114716595A (en) * | 2022-03-23 | 2022-07-08 | 佳化化学科技发展（上海）有限公司 | Ultra-low molecular weight polyacrylic acid and preparation method and application thereof |
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| WO2000034345A1 (en) * | 1998-12-10 | 2000-06-15 | Ineos Acrylics Uk Limited | Production of vinylic polymers |
| CN101484479A (en) * | 2006-08-09 | 2009-07-15 | 赢创罗姆有限责任公司 | Process for preparing halogen-free ATRP products |
| CN102492067A (en) * | 2011-12-01 | 2012-06-13 | 河南省科学院高新技术研究中心 | Preparation method of low-molecular-weight ammonium polyacrylate |
| CN102535246A (en) * | 2012-01-20 | 2012-07-04 | 中国科学院长春应用化学研究所 | Preparation method of polymeric dispersant for papermaking |
| CN104151458A (en) * | 2014-07-11 | 2014-11-19 | 南昌航空大学 | Preparation method of sodium polyacrylate having ultra-low molecular weight |
| CN104662051A (en) * | 2012-09-26 | 2015-05-27 | 可泰克斯公司 | Method for polymerising (meth)acrylic acid in solution, polymer solutions obtained and uses thereof |
-
2015
- 2015-11-27 CN CN201510846447.5A patent/CN105481676A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000034345A1 (en) * | 1998-12-10 | 2000-06-15 | Ineos Acrylics Uk Limited | Production of vinylic polymers |
| CN101484479A (en) * | 2006-08-09 | 2009-07-15 | 赢创罗姆有限责任公司 | Process for preparing halogen-free ATRP products |
| CN102492067A (en) * | 2011-12-01 | 2012-06-13 | 河南省科学院高新技术研究中心 | Preparation method of low-molecular-weight ammonium polyacrylate |
| CN102535246A (en) * | 2012-01-20 | 2012-07-04 | 中国科学院长春应用化学研究所 | Preparation method of polymeric dispersant for papermaking |
| CN104662051A (en) * | 2012-09-26 | 2015-05-27 | 可泰克斯公司 | Method for polymerising (meth)acrylic acid in solution, polymer solutions obtained and uses thereof |
| CN104151458A (en) * | 2014-07-11 | 2014-11-19 | 南昌航空大学 | Preparation method of sodium polyacrylate having ultra-low molecular weight |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824548A (en) * | 2017-02-27 | 2017-06-13 | 中国地质科学院矿产综合利用研究所 | Flotation dispersing agent suitable for high-talc-content copper-nickel sulfide ore and preparation method thereof |
| CN106824548B (en) * | 2017-02-27 | 2020-07-10 | 中国地质科学院矿产综合利用研究所 | Flotation dispersing agent suitable for high-talc-content copper-nickel sulfide ore and preparation method thereof |
| CN112079453A (en) * | 2020-09-09 | 2020-12-15 | 南京全宇节能技术有限公司 | Polymer salt inhibitor for salt-containing wastewater back-spraying quenching tower process |
| CN114716595A (en) * | 2022-03-23 | 2022-07-08 | 佳化化学科技发展（上海）有限公司 | Ultra-low molecular weight polyacrylic acid and preparation method and application thereof |
| CN114716595B (en) * | 2022-03-23 | 2023-11-03 | 佳化化学科技发展（上海）有限公司 | Ultra-low molecular weight polyacrylic acid and preparation method and application thereof |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Tianjin Chemical Research & Design Institute Applicant before: CNOOC Energy Development Co., Ltd. |
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Application publication date: 20160413 |