CN112978943B - Preparation method of controllable environment-friendly scale inhibitor with comb-shaped structure - Google Patents
Preparation method of controllable environment-friendly scale inhibitor with comb-shaped structure Download PDFInfo
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- CN112978943B CN112978943B CN201911298562.8A CN201911298562A CN112978943B CN 112978943 B CN112978943 B CN 112978943B CN 201911298562 A CN201911298562 A CN 201911298562A CN 112978943 B CN112978943 B CN 112978943B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
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Abstract
The invention relates to the field of scale inhibitors, in particular to a preparation method of a controllable comb-structure environment-friendly scale inhibitor. The scale inhibitor with a comb-shaped structure is prepared by taking environment-friendly materials with multiple functionality, namely polyvinyl alcohol, 2-bromo-2-methylpropanoic acid-2, 5-dioxopyrrolidone-1-acyl ester and alpha, beta-unsaturated carbonyl compound as raw materials through Atom Transfer Radical Polymerization (ATRP). The controllability of the scale inhibition performance is realized by regulating and controlling the types of the polyvinyl alcohol and the branched chain and the feed ratio of the components.
Description
Technical Field
The invention relates to the field of scale inhibitors, in particular to a preparation method of an environment-friendly scale inhibitor with a controllable comb-shaped structure.
Background
Scaling is a difficult problem that plagues the normal operation of systems in industrial cooling water systems, heat exchangers, reverse osmosis membrane surfaces and oil field industries where water usage is extremely high. The scale will reduce the heat transfer efficiency, block the water flow, cause the scale corrosion and other consequences, which will affect the operation of the cooling water system. According to different water quality conditions, inorganic salt scale is often calcium carbonate, calcium sulfate, calcium silicate, magnesium silicate, calcium phosphate and the like, and the scale is compact in crystallization, relatively hard, strong in adhesive force and not easy to wash away. The prior solutions mainly comprise physical methods and chemical methods, wherein the former has certain application value under certain specific conditions, but the scale inhibition performance of the former cannot be compared with that of the latter. As for the chemical method, the softening treatment method aims at eliminating scaling ions in the water solution, has higher cost and is only suitable for places with higher requirements on water quality; the acidification method and the carbonization method may cause corrosion of equipment in an industrial process, thereby complicating the equipment, so that such methods have been rarely used at present. At present, circulating cooling water systems in domestic and foreign production processes mainly adopt scale inhibitors to prevent and treat scaling on heat exchange surfaces, and the measure is convenient, economic and efficient.
With the continuous enhancement of the environmental protection consciousness of people, the environment-friendly scale inhibitor is more and more favored by people, and more environment-friendly scale inhibitors are gradually applied to actual life and production.
Disclosure of Invention
The invention aims to provide a preparation method of an environment-friendly scale inhibitor with a controllable comb-shaped structure.
In order to realize the purpose of the invention, the technical scheme is as follows:
the invention relates to a controllable environment-friendly scale inhibitor with a comb-shaped structure, which is characterized in that the scale inhibitor is prepared by taking environment-friendly materials with multiple functionality, namely polyvinyl alcohol, 2-bromine-2-methylpropanoic acid-2, 5-dioxopyrrolidine-1-ester and alpha, beta-unsaturated carbonyl compound as raw materials based on Atom Transfer Radical Polymerization (ATRP). The controllability of the scale inhibition performance is realized by regulating and controlling the types of the polyvinyl alcohol and the branched chain and the feed ratio of the components. The method is characterized by comprising the following steps: (1) heating the mixed solution of polyvinyl alcohol and 2-bromo-2-methylpropanoic acid-2, 5-dioxopyrrolidine-1-ester for a certain time to obtain brominated polyvinyl alcohol. (2) Bromopolyvinyl alcohol and alpha, beta-unsaturated carbonyl compound are used as raw materials, and o-bipyridine and cuprous halide (the molar ratio of bromopolyvinyl alcohol to o-bipyridine to cuprous halide is 1: 2: 1) are used as catalysts, and the raw materials are reacted for a period of time at a certain temperature, and n-hexane is used for precipitation to obtain the product.
The first preferred technical scheme of the invention is as follows: in the above steps, the polyvinyl alcohol has an average molecular weight of 20000g/mol to 200000g/mol and an alcoholysis degree of 85% to 89%.
The second preferred technical scheme of the invention is as follows: the heating temperature in the step (1) is 60-100 ℃.
The third preferred technical scheme of the invention is as follows: the heating time in the step (1) is 0.5-6 h.
The fourth preferred technical scheme of the invention is as follows: the α, β -unsaturated carbonyl compound has a functional group such as a carboxyl group, a hydroxyl group, and a sulfonic acid group.
The fifth preferred technical scheme of the invention is as follows: the proportion of the alpha, beta-unsaturated carbonyl compound is 10-50%.
The sixth preferred technical scheme of the invention is as follows: the reaction temperature in the step (2) is 80-130 ℃.
The seventh preferred technical scheme of the invention is as follows: the reaction time in the step (2) is 1-6 h.
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with the benefit of the present disclosure with additional guidance to adapt the invention without departing from the scope of the invention as defined by the appended claims.
Detailed Description
Example 1
Heating a mixed solution of polyvinyl alcohol with the molecular weight of 20000g/mol and alcoholysis degree of 87% and 2-bromo-2-methylpropanoic acid-2, 5-dioxopyrrolidine-1-ester to 90 ℃ for reaction for 4.5h to obtain brominated polyvinyl alcohol. Brominated polyvinyl alcohol and 30.0 percent of alpha, beta-unsaturated carbonyl compound containing hydroxyl are used as raw materials, and o-bipyridine and cuprous halide (the molar ratio of the brominated polyvinyl alcohol to the o-bipyridine to the cuprous halide is 1: 2: 1) are used as catalysts to react for 4 hours at 130 ℃, and normal hexane is used for precipitation to obtain the product. The scale inhibition rate is 89.1 percent by adopting a static scale inhibition method.
Example 2
Heating a mixed solution of polyvinyl alcohol with the molecular weight of 168000g/mol and the alcoholysis degree of 86 percent and 2-bromo-2-methylpropanoic acid-2, 5-dioxopyrrolidine-1-ester to 60 ℃ for reaction for 0.5h to obtain brominated polyvinyl alcohol. The method comprises the steps of taking brominated polyvinyl alcohol and 10.0% of carboxyl-containing alpha, beta-unsaturated carbonyl compound as raw materials, reacting o-bipyridine and cuprous halide (the molar ratio of the brominated polyvinyl alcohol to the o-bipyridine to the cuprous halide is 1: 2: 1) in the presence of a catalyst at 120 ℃ for 5 hours, and precipitating with n-hexane to obtain the product. The scale inhibition rate is 89.2% by adopting a static scale inhibition method.
Example 3
Heating a mixed solution of polyvinyl alcohol with molecular weight of 67000g/mol and alcoholysis degree of 85% and 2-bromo-2-methylpropanoic acid-2, 5-dioxopyrrolidine-1-ester to 70 ℃ for reaction for 2.5h to obtain brominated polyvinyl alcohol. Brominated polyvinyl alcohol and 20.0 percent of alpha, beta-unsaturated carbonyl compound containing hydroxyl are used as raw materials, and o-bipyridine and cuprous halide (the molar ratio of the brominated polyvinyl alcohol to the o-bipyridine to the cuprous halide is 1: 2: 1) are used as catalysts to react for 6h at 80 ℃, and normal hexane is used for precipitation to obtain the product. The scale inhibition rate is 87.2 percent by adopting a static scale inhibition method.
Example 4
Heating a mixed solution of polyvinyl alcohol with the molecular weight of 200000g/mol and the alcoholysis degree of 88 percent and 2-bromo-2-methylpropanoic acid-2, 5-dioxopyrrolidine-1-ester to 80 ℃ for reaction for 3h to obtain brominated polyvinyl alcohol. Brominated polyvinyl alcohol and 50.0 percent of alpha, beta-unsaturated carbonyl compound containing sulfonic group are used as raw materials, and o-bipyridine and cuprous halide (the molar ratio of the brominated polyvinyl alcohol to the o-bipyridine to the cuprous halide is 1: 2: 1) are used as catalysts to react for 1h at 105 ℃, and normal hexane is used for precipitation to obtain the product. The scale inhibition rate is 86.8 percent by adopting a static scale inhibition method.
Example 5
Heating a mixed solution of polyvinyl alcohol with the molecular weight of 145000g/mol and the alcoholysis degree of 89% and 2-bromo-2-methylpropanoic acid-2, 5-dioxopyrrolidine-1-ester to 100 ℃ for reaction for 6h to obtain brominated polyvinyl alcohol. Brominated polyvinyl alcohol and 40.0 percent of alpha, beta-unsaturated carbonyl compound containing sulfonic group are used as raw materials, and o-bipyridine and cuprous halide (the molar ratio of the brominated polyvinyl alcohol to the o-bipyridine to the cuprous halide is 1: 2: 1) are used as catalysts to react for 2h at 100 ℃, and normal hexane is used for precipitation to obtain the product. The scale inhibition rate is 87.9 percent by adopting a static scale inhibition method.
Claims (8)
1. The controllable environment-friendly scale inhibitor with the comb-shaped structure is characterized in that the scale inhibitor is based on atom transfer radical polymerization reaction, takes environment-friendly materials with multiple functionality degrees, namely polyvinyl alcohol, 2-bromo-2-methylpropanoic acid-2, 5-dioxopyrrolidine-1-ester and alpha, beta-unsaturated carbonyl compounds as raw materials, and realizes the controllability of scale inhibition performance through the regulation and control of the types of polyvinyl alcohol and branched chains and the component feed ratio;
The preparation method of the controllable environmentally-friendly scale inhibitor with the comb-shaped structure comprises the following steps:
(1) heating a mixed solution of polyvinyl alcohol and 2-bromo-2-methylpropanoic acid-2, 5-dioxopyrrolidine-1-ester for a certain time to obtain brominated polyvinyl alcohol;
(2) the method comprises the following steps of taking brominated polyvinyl alcohol and an alpha, beta-unsaturated carbonyl compound as raw materials, taking o-bipyridine and cuprous halide as catalysts, wherein the molar ratio of the brominated polyvinyl alcohol to the o-bipyridine to the cuprous halide is 1: 2: 1, reacting for a period of time at a certain temperature, and precipitating by using n-hexane to obtain a product.
2. The controllable comb-shaped environment-friendly scale inhibitor as claimed in claim 1, wherein the average molecular weight of the polyvinyl alcohol is 20000 g/mol-200000 g/mol, and the alcoholysis degree is 85% -89%.
3. The controllable comb-shaped environment-friendly scale inhibitor as claimed in claim 1, wherein the heating temperature in step (1) is 60-100 ℃.
4. The controllable comb-shaped environment-friendly scale inhibitor as claimed in claim 1, wherein the heating time in step (1) is 0.5 h-6 h.
5. The controllable comb-shaped environment-friendly scale inhibitor as claimed in claim 1, wherein the α, β -unsaturated carbonyl compound has carboxyl, hydroxyl and sulfonic functional groups.
6. The controllable comb-shaped environment-friendly scale inhibitor as claimed in claim 1, wherein the proportion of the α, β -unsaturated carbonyl compound is 10-50%.
7. The controllable comb-structured environment-friendly scale inhibitor as claimed in claim 1, wherein the reaction temperature in step (2) is 80-130 ℃.
8. The controllable comb-shaped environment-friendly scale inhibitor as claimed in claim 1, wherein the reaction time in step (2) is 1-6 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005163044A (en) * | 1995-06-05 | 2005-06-23 | Cirs Spa | Anti-scaling agent for polymerization reactor and producing method therefor |
| CN105985492A (en) * | 2015-02-04 | 2016-10-05 | 浙江大学 | Cationic functional vinyl chloride polymer and preparation method thereof |
| CN108569777A (en) * | 2018-04-24 | 2018-09-25 | 常州市蒽盗钟情生物科技有限公司 | A kind of scale inhibitor microcapsules and preparation method thereof |
| CN110099931A (en) * | 2016-12-21 | 2019-08-06 | 三菱化学株式会社 | Polyvinyl alcohol resin, dispersing agent and dispersant for suspension polymerization |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2867014B2 (en) * | 1994-09-09 | 1999-03-08 | 第一工業製薬株式会社 | Modified polyvinyl alcohol and method for producing the same |
| ES2532289T3 (en) * | 2008-03-31 | 2015-03-25 | The Procter & Gamble Company | Dishwasher composition containing a sulfonated copolymer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005163044A (en) * | 1995-06-05 | 2005-06-23 | Cirs Spa | Anti-scaling agent for polymerization reactor and producing method therefor |
| CN105985492A (en) * | 2015-02-04 | 2016-10-05 | 浙江大学 | Cationic functional vinyl chloride polymer and preparation method thereof |
| CN110099931A (en) * | 2016-12-21 | 2019-08-06 | 三菱化学株式会社 | Polyvinyl alcohol resin, dispersing agent and dispersant for suspension polymerization |
| CN108569777A (en) * | 2018-04-24 | 2018-09-25 | 常州市蒽盗钟情生物科技有限公司 | A kind of scale inhibitor microcapsules and preparation method thereof |
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