CN101532266B - Synthesis and production method for star polymer for paper making dispersant - Google Patents
Synthesis and production method for star polymer for paper making dispersant Download PDFInfo
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- CN101532266B CN101532266B CN 200810240878 CN200810240878A CN101532266B CN 101532266 B CN101532266 B CN 101532266B CN 200810240878 CN200810240878 CN 200810240878 CN 200810240878 A CN200810240878 A CN 200810240878A CN 101532266 B CN101532266 B CN 101532266B
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Abstract
The invention provides a paper making process additive, and relates to a star polymer used for a paper making dispersant, in particular to a dispersant for paper for daily use. The dispersant is copolymerized by five monomers of acrylamide (AM), acrylonitrile (AN), sodium acrylate, 2-acrylamide-2-methyl propane sulphonate and methacrylamide (AAM). The invention also relates to a production method for the dispersant. An aqueous solution catalyst method is used to produce free radicals so as to copolymerize the monomers. The dispersant has the characteristics of high viscosity, good water solubility, high solution rate, and good flocculability and lubricity.
Description
Technical field
The present invention relates to a kind of paper technology additive, be specifically related to a kind of star-type polymer and be used for paper-making dispersant agent, in particular for the dispersant in the paper for daily use, and the production method of described dispersant.
Background technology
Along with China's economic grows continuously and fast and the improving constantly of people's living standard, the consumer is also more and more higher to the requirement of paper for daily use.3,000 ten thousand tons of paper for daily uses of the annual approximately consumption in the whole world, pre-capita consumption is approximately 3.4 kilograms.The per capita paper for daily use consumption figure of the developed countries such as America and Europe is then far above average level, and the pre-capita consumption paper for daily use amount in its Middle and North America, area, Northern Europe has surpassed 20 kilograms.
The growth in China paper for daily use market has become one of focus of global concern.Along with the growth of China's per capita disposable income and the quickening of rhythm of life, the paper for daily use demand will constantly enlarge.It is predicted that the increment of the five-year China can account for half of the whole world, and wherein the fine tissue product will become the main flow in market.
At present toilet paper the consumption figure of China the chances are annual 4000000 tons, the U.S. the chances are 8,000,000 tons, the chances are in Europe more than 800 ten thousand tons.The increased requirement of 1,600,000 tons of toilet papers is arranged in China in the recent period, all is high-grade paper using.The consumption of China's sanitary paper expectation will be with annual about 8% speed increment in the years to come.
Pulp dispersant also is one of the indispensable a kind of chemical assistant that improves the quality of products in paper for daily use production.Require dispersant to have viscosity height, good water solubility, flocculability is good and lubricity is good characteristics, a small amount of dispersant of interpolation in the online slurry can obviously improve the evenness of page, reaches the purpose of improving page pliability and feel.
China's polymeric dispersant has polyethylene glycol oxide (PEO), anionic polyacrylamide at present.And but polyethylene glycol oxide good dispersion price is high.Wanting of import is per ton more than 80,000, and the PEO of production domesticization also will between ten thousand yuan of 5-6, improve the manufacturing cost of single ton of paper so now.The relative PEO price of polyacrylamide is cheap, economic and practical, yet the polyacrylamide major part that is used for paper-making dispersant agent is obtained by acrylamide and two kinds of monomer copolymerizations of sodium acrylate, and the enterprise that technology is perfect can realize with hydrolysis process after the part copolymerization part.The product dissolution velocity of producing is slower, generally is ability dissolving in 60-90 minute, and has insoluble matter, uses the quality that affects finished paper.
Summary of the invention
The purpose of this invention is to provide a kind of star-type polymer dispersant that is applied in the papermaking, this dispersant has viscosity height, good water solubility, dissolution velocity is fast, flocculability good and lubricity is good characteristics.
Another object of the present invention is to provide a kind of method of producing above-mentioned dispersant.
Dispersant of the present invention is to be formed by acrylamide (AM), acrylonitrile (AN), sodium acrylate, 2-acrylamide-2-methyl propane sulfonic acid salt and five kinds of monomer copolymerizations of Methacrylamide (AAM).
The percentage by weight of each monomer of the present invention and water consists of:
(a) acrylamide of 25 to 35 % by weight;
(b) sodium acrylate of 20 to 25 % by weight;
(c) acrylonitrile of 1 to 3 % by weight (AN);
(d) the 2-acrylamide of 5 to 8 % by weight-2-methyl propane sulfonic acid salt;
(e) Methacrylamide of 2 to 5 % by weight (AAM);
(f) surplus is water.
More preferably be that the optimum weight percentage of each monomer and water consists of:
Acrylamide (AM): 30%
Sodium acrylate (AAN): 22%
Acrylonitrile (AN): 2%
2-acrylamide-2-methyl propane sulfonic acid salt (AMPS): 7%
Methacrylamide (AAM): 3%
Water: 36%
Acrylamide (AM), acrylonitrile (AN), sodium acrylate, 2-acrylamide-2-methyl propane sulfonic acid salt and five kinds of monomer copolymerizations of Methacrylamide (AAM) can form the polymer with the linear chain structure of side group.The introducing of 2-acrylamide-2-methyl propane sulfonic acid salt can so that this structure adaptability speed carried near 40-60 minute by original 60-90 minute.Methacrylamide and 2-acrylamide-2-methyl propane sulfonic acid salt with side group so that polymer fully contact with paper pulp fiber, the association of mutually tangling of the empennage of molecule, the large molecule of association slabbing, with after paper pulp fiber mixes, the flank that moves about in its side can be arrested fiber effectively, so that fiber becomes ordered arrangement, thereby reach effective dispersion.
A kind of method of producing above-mentioned dispersant, it comprises the steps:
(1) selected acrylamide (AM), acrylonitrile (AN), sodium acrylate, 2-acrylamide-2-methyl propane sulfonic acid salt and five kinds of monomers of Methacrylamide (AAM) carry out proportioning according to a certain percentage;
(2) monomer that said ratio is good is put into the preparation that distilled water carries out solution;
(3) pH value and the temperature of adjustment solution make the pH value of solution 6.5 ± 0.5, and described temperature is 15 ± 1 ℃;
(4) produce free radical with aqueous solution catalyst method and make above-mentioned monomer generation polymerization.
Described aqueous solution catalyst method namely refers in the building-up process of dispersant, protects 20 minutes to the monomer solution nitrogen blowing for preparing, and then adds catalyst in solution, brings out 10-15 minute with the generation free radical, thereby makes monomer generation polymerization.Its building-up process can be envisioned for following molecular pattern:
In with the process of aqueous solution polymerization, need solution nitrogen blowing 20 minutes; to remove the dissolved oxygen in anhydrating; then under the protection of nitrogen, add catalyst; stop nitrogen blowing and polymeric kettle is airtight; brought out 10-15 minute, and observed whether temperature rise was arranged, 2 ℃ temperature rise is arranged in inductive phase; be considered as causing successfully, again cause otherwise need to again add catalyst.Under the insulation airtight condition, until intensification finishes, be incubated 3 hours.
Initiation initial temperature of the present invention is controlled within the 10-20 ℃ of scope.Preferred initial temperature is 15 ± 1 ℃.The pH value is controlled between the 6.0-7.5.PH alkalescence mediator agent mainly contains NaOH, potash, ammoniacal liquor.The pH acid regulator mainly contains phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid.Preferred pH value is controlled at 6.5 ± 0.5.
Be not particularly limited for described catalyst.The oxidant of polymerization catalyst is persulfate or peroxide, for example ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, benzoyl peroxide or tert-butyl peroxide.Can use oxidant to form redox system with reductant among the present invention, described reductant can be sulphite, bisulfites, protosalt, organic amine etc.
Azo-compound also is one of preferred catalyst of the present invention, and applicable typical azo-compound has azodiisobutyronitrile (AZDN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (V65), azo diisobutyl amidine hydrochloride (V50) etc.Can use simultaneously two or more above-mentioned catalyst, the amount of catalyst is generally the 0.001-3% weight of monomer.
Dispersant of the present invention is applicable to the dispersant in the paper making additive, is that a kind of viscosity height, good water solubility, dissolution velocity are fast, flocculability and the good star-like high molecular polymer of lubricity.Thereby being dissolution velocity, its main feature can save soon dissolution time raising paper motor speed raising output; The toilet paper good hand touch that the product flocculability is good and lubricity is produced well, good dispersion so that finished paper without characteristics such as eye, the high single ton of paper consumption of viscosity are few.
The specific embodiment
The below will be described in detail dispersant of the present invention and production process thereof according to specific embodiment.
Embodiment 1
The percentage by weight of each monomer and water: AM: AAN: AN: AMPS: AAM: H
2O=30: 22: 2: 7: 3: 36.
The preparation of solution: in the 2000ml beaker, add distilled water 360g, add AM monomer 300g, AAN monomer 220g, add AN monomer 20g, add AMPS monomer 70g, add AAM monomer 30g, stirring and dissolving 30 minutes slowly adds neutralizer (NaOH) to pH6.5 under stirring condition.Continue agitating solution slaking 30 minutes.
The adjustment of solution: again regulate pH value to 6.5 ± 0.5, regulate 15 ± 1 ℃ of temperature.
The polymerization of solution: nitrogen blowing deoxygenation 20 minutes; under nitrogen protection, add successively catalyst V 650.5g/L; V50 0.05g/L, ammonium persulfate 0.03g/L, sodium formaldehyde sulphoxylate 0.03g/L; stop nitrogen blowing and polymeric kettle is airtight; brought out 15-20 minute, and observed whether temperature rise was arranged, 2 ℃ temperature rise is arranged in inductive phase; be considered as causing successfully, again cause otherwise need to again add catalyst.Under the insulation airtight condition, until intensification finishes, be incubated 3 hours.
The post processing of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders, is numbered F-1 and waits detection.
Embodiment 2
The percentage by weight of each monomer and water: AM: AAN: AN: AMPS: AAM: H
2O=25: 20: 1: 5: 2: 47.
The preparation of solution: in the 2000ml beaker, add distilled water 470g, add AM monomer 250g, add AAN monomer 200g, add AN monomer 10g, add AMPS monomer 50g, add AAM monomer 20g, stirring and dissolving 30 minutes slowly adds neutralizer (NaOH) to pH6.5 under stirring condition.Continue agitating solution slaking 30 minutes.
The adjustment of solution: again regulate pH value to 6.5 ± 0.5, regulate 15 ± 1 ℃ of temperature.
The polymerization of solution: nitrogen blowing deoxygenation 20 minutes; under nitrogen protection, add successively catalyst V 650.4g/L; V50 0.04g/L, ammonium persulfate 0.03g/L, sodium formaldehyde sulphoxylate 0.03g/L; stop nitrogen blowing and polymeric kettle is airtight; brought out 15-20 minute, and observed whether temperature rise was arranged, 2 ℃ temperature rise is arranged in inductive phase; be considered as causing successfully, again cause otherwise need to again add catalyst.Under the insulation airtight condition, until intensification finishes, be incubated 3 hours.
The post processing of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders, is numbered F-2 and waits detection.
Embodiment 3
The percentage by weight of each monomer and water: AM: AAN: AN: AMPS: AAM: H
2O=35: 20: 1: 5: 2: 37.
The preparation of solution: in the 2000ml beaker, add distilled water 370g, add AM monomer 350g, add AAN monomer 200g, add AN monomer 10g, add AMPS monomer 50g, add AAM monomer 20g, stirring and dissolving 30 minutes slowly adds neutralizer (NaOH) to pH6.5 under stirring condition.Continue agitating solution slaking 30 minutes.
The adjustment of solution: again regulate pH value to 6.5 ± 0.5, regulate 15 ± 1 ℃ of temperature.
The polymerization of solution: nitrogen blowing deoxygenation 20 minutes; under nitrogen protection, add successively catalyst V 650.6g/L; V50 0.06g/L, ammonium persulfate 0.04g/L, sodium formaldehyde sulphoxylate 0.04g/L; stop nitrogen blowing and polymeric kettle is airtight; brought out 15-20 minute, and observed whether temperature rise was arranged, 2 ℃ temperature rise is arranged in inductive phase; be considered as causing successfully, again cause otherwise need to again add catalyst.Under the insulation airtight condition, until intensification finishes, be incubated 3 hours.
The post processing of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders, is numbered F-3 and waits detection.
Embodiment 4
The percentage by weight of each monomer and water: AM: AAN: AN: AMPS: AAM: H
2O=25: 25: 3: 8: 5: 34.
The preparation of solution: in the 2000ml beaker, add distilled water 340g, add AM monomer 250g, add AAN monomer 250g, add AN monomer 30g, add AMPS monomer 80g, add AAM monomer 50g, stirring and dissolving 30 minutes slowly adds neutralizer (NaOH) to pH6.5 under stirring condition.Continue agitating solution slaking 30 minutes.
The adjustment of solution: again regulate pH value to 6.5 ± 0.5, regulate 15 ± 1 ℃ of temperature.
The polymerization of solution: nitrogen blowing deoxygenation 20 minutes; under nitrogen protection, add successively catalyst V 650.8g/L; V50 0.08g/L, ammonium persulfate 0.05g/L, sodium formaldehyde sulphoxylate 0.05g/L; stop nitrogen blowing and polymeric kettle is airtight; brought out 15-20 minute, and observed whether temperature rise was arranged, 2 ℃ temperature rise is arranged in inductive phase; be considered as causing successfully, again cause otherwise need to again add catalyst.Under the insulation airtight condition, until intensification finishes, be incubated 3 hours.
The post processing of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders, is numbered F-4 and waits detection.
Embodiment 5
The percentage by weight of each monomer and water: AM: AAN: AN: AMPS: AAM: H
2O=30: 20: 1: 5: 2: 42.
The preparation of solution: in the 2000ml beaker, add distilled water 420g, add AM monomer 300g, add AAN monomer 200g, add AN monomer 10g, add AMPS monomer 50g, add AAM monomer 20g, stirring and dissolving 30 minutes slowly adds neutralizer (NaOH) to pH6.5 under stirring condition.Continue agitating solution slaking 30 minutes.
The adjustment of solution: again regulate pH value to 6.5 ± 0.5, regulate 15 ± 1 ℃ of temperature.
The polymerization of solution: nitrogen blowing deoxygenation 20 minutes; under nitrogen protection, add successively catalyst V 650.5g/L; V50 0.04g/L, ammonium persulfate 0.02g/L, sodium formaldehyde sulphoxylate 0.02g/L; stop nitrogen blowing and polymeric kettle is airtight; brought out 15-20 minute, and observed whether temperature rise was arranged, 2 ℃ temperature rise is arranged in inductive phase; be considered as causing successfully, again cause otherwise need to again add catalyst.Under the insulation airtight condition, until intensification finishes, be incubated 3 hours.
The post processing of product: the colloid that polymerization is good is carried out granulation, and oven dry is ground into 30 orders, is numbered F-5 and waits detection.
The main polymerization catalyzed agent prescription of above-described embodiment gathers (such as table 1).
Table 1
Wherein, AO1 is ammonium persulfate, and NFS is sodium formaldehyde sulphoxylate
Above-described embodiment product is carried out key property detect (result such as table 2).
Table 2
Claims (6)
1. dispersant that is used for paper technology, it is characterized in that: the weight proportion of each monomer and water satisfies a kind of polymer that following proportioning is synthesized in polymerization process:
(a) acrylamide of 25 to 35 % by weight;
(b) sodium acrylate of 20 to 25 % by weight;
(c) the acrylonitrile AN of 1 to 3 % by weight;
(d) the 2-acrylamide of 5 to 8 % by weight-2-methyl propane sulfonic acid salt;
(e) the Methacrylamide AAM of 2 to 5 % by weight;
(f) surplus is water.
2. method of producing the described dispersant of claim 1, it comprises the steps:
(1) selected acrylamide AM, acrylonitrile AN, sodium acrylate, 2-acrylamide-2-methyl propane sulfonic acid salt and five kinds of monomers of Methacrylamide AAM carry out proportioning according to a certain percentage;
(2) monomer that said ratio is good is put into the preparation that distilled water carries out solution;
(3) pH value and the temperature of adjustment solution make the pH value 6.5 ± 0.5, and described temperature is 15 ± 1 ℃;
(4) monomer solution for preparing is added in the reaction vessel, protect 20 minutes to the monomer solution nitrogen blowing for preparing, then in solution, add catalyst, bring out 15-20 minute with the generation free radical, thereby make monomer generation polymerization.
3. method as claimed in claim 2, it is characterized in that: the weight ratio of described five kinds of monomers and water is:
Acrylamide AM:30%;
Sodium acrylate AAN:22%;
Acrylonitrile AN:2%;
2-acrylamide-2-methyl propane sulfonic acid salt AMPS:7%;
Methacrylamide AAM:3%;
Water: 36%.
4. method as claimed in claim 2, it is characterized in that: described catalyst is persulfate or peroxide; Perhaps form redox system with reductant for persulfate or peroxide; It perhaps is azo-compound; Described catalyst also can be comprised of two or more catalyst in the above-mentioned catalyst type.
5. method as claimed in claim 4, it is characterized in that: described persulfate is one or more in ammonium persulfate, potassium peroxydisulfate, the sodium peroxydisulfate; Described peroxide is one or more in hydrogen peroxide, benzoyl peroxide, formyl and the tert-butyl peroxide; Described reductant is one or more in sulphite, bisulfites, protosalt, the organic amine; Described azo-compound is one or more in azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), the azo diisobutyl amidine hydrochloride.
6. method as claimed in claim 2, it is characterized in that: the amount of catalyst is the 0.001-3% of monomer weight.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104404824A (en) * | 2014-11-07 | 2015-03-11 | 安徽天润化学工业股份有限公司 | Star-shaped polymer papermaking dispersant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105315402A (en) * | 2014-07-04 | 2016-02-10 | 山东诺尔生物科技有限公司 | Preparation method of quick-dissolving polyacrylamide papermaking dispersant |
| CN105315405A (en) * | 2015-11-17 | 2016-02-10 | 山东诺尔生物科技有限公司 | Preparation method of quick-dissolving polyacrylamide paper-making dispersing agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197080A (en) * | 1997-04-21 | 1998-10-28 | 南京义利物资销售中心 | Tech. for preparing paper-making dispersant agent |
| CN1986581A (en) * | 2006-11-29 | 2007-06-27 | 淮阴工学院 | Production process of low molecular weight polysodium acrylate as papermaking dispersant |
| CN101314626A (en) * | 2008-07-16 | 2008-12-03 | 太原理工大学 | Method for preparing cation polyacrylamide dispersion |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1197080A (en) * | 1997-04-21 | 1998-10-28 | 南京义利物资销售中心 | Tech. for preparing paper-making dispersant agent |
| CN1986581A (en) * | 2006-11-29 | 2007-06-27 | 淮阴工学院 | Production process of low molecular weight polysodium acrylate as papermaking dispersant |
| CN101314626A (en) * | 2008-07-16 | 2008-12-03 | 太原理工大学 | Method for preparing cation polyacrylamide dispersion |
Non-Patent Citations (1)
| Title |
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| JP特开2006-77379A 2006.03.23 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104404824A (en) * | 2014-11-07 | 2015-03-11 | 安徽天润化学工业股份有限公司 | Star-shaped polymer papermaking dispersant and preparation method thereof |
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