CN105566553A - Maleic anhydride-acrylic acid copolymer for washing agent and preparation method thereof - Google Patents
Maleic anhydride-acrylic acid copolymer for washing agent and preparation method thereof Download PDFInfo
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- CN105566553A CN105566553A CN201410538435.1A CN201410538435A CN105566553A CN 105566553 A CN105566553 A CN 105566553A CN 201410538435 A CN201410538435 A CN 201410538435A CN 105566553 A CN105566553 A CN 105566553A
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Abstract
The invention provides a maleic anhydride-acrylic acid copolymer for a washing agent and a preparation method thereof. The preparation method comprises the following steps: mixing water, maleic anhydride, acrylic acid monomer and an initiator, carrying out heating to 70 to 100 DEG C and then carrying out a reaction; carrying out a constant-temperature reaction for at least 1 h; and carrying out cooling to less than 60 DEG C, neutralizing the cooled mixture with aqueous alkali and collecting a polymerization product. According to the invention, a unique synthesis process is employed; acrylic acid is neutralized to a pH value of 7.0 before the reaction, so the grafting rate of maleic anhydride can be greatly increased; the preparation method has the advantages of a high conversion rate, small investment for equipment, high product purity, no discharge of waste water and exhaust gas and environment friendliness; and compared with a commercially available product, the synthesized copolymer product has substantially improved wash assisting properties like chelating force and dispersion forces and can completely or partially replace sodium tripolyphosphate for usage in the washing agent.
Description
Technical field
The present invention relates to a kind of detergent use copolymer of maleic anhydride and acrylic acid and preparation method thereof.
Background technology
Phosphoric acid salt (as tri-polyphosphate) and aluminium salt (as sodium aluminium silicate, 4A zeolite, kaolin, wilkinite Tai-Ace S 150) is typically used as washing assistant in synthetic detergent, use phosphoric acid salt as washing assistant, algae class, waterplant distorted proliferation can be made and very fast death after its washes enters lake, river, cause dirt and the anoxic of water quality, to environment.
With polycarboxylic acid high molecular polymer as washing assistant, find that polycarboxylate polymer has outstanding chelating and dissemination, be widely used in washing composition and water treatment field.Polycarboxylate polymer is as having following characteristics as washing auxiliary detergent: alkaline buffer effect, even if there are a small amount of acidic substance to exist, due to the effect of auxiliary agent, the pH of washings also noticeable change does not occur, and still has very strong soil-removing action; Have and dirt is disperseed in water and prevents dirt to fabric adventitious deposit effect again; Polycarboxylic acid high molecular polymer has a large amount of carboxylate group on side chain, therefore has very strong particle sequestering power and the ability of softening of water.In view of the washing aid performance that polycarboxylic acid high molecular polymer is outstanding, tripoly phosphate sodium STPP can be replaced wholly or in part, be used as detergent builders.
Wherein in the majority as the research of washing auxiliary detergent using polyacrylate, because the multipolymer sodium salt obtained after finding vinylformic acid and other organic unsaturated carboxylic acid copolymerization is better than acrylate homopolymer sodium salt performance, can improve Ca
2+, Mg
2+dispersive ability.Current most study be copolymer of maleic anhydride and acrylic acid sodium salt, be also the only multipolymer be applied in practice.Traditional copolymer of maleic anhydride and acrylic acid synthesis technique (as patent CNCN1099764A), adopt benzoyl peroxide as initiator, in poisonous organic solvent (as toluene, dimethylbenzene etc.), carry out solution polymerization, then become copolymer of maleic anhydride and acrylic acid through neutralizing hydrolysis.The shortcoming of this method is the expensive of initiator, and consumption is large; The toxic solvent wherein adopted is harmful to, and need be recycled after distillation, so complex process facility investment is large, the time used, long energy consumption was high, caused into product cost higher.In addition, adopt not in advance in and vinylformic acid, directly by the solution polymerization of vinylformic acid dropping, this production technique (as patent CN101921359A), maleic anhydride graft is low to the efficiency on multipolymer, the copolymer of maleic anhydride and acrylic acid product dispersion force synthesized is poor, thus affects washing aid performance.
Summary of the invention
The present invention solves the aforementioned problems in the prior proposition.
The invention provides a kind of preparation method of the copolymer of maleic anhydride and acrylic acid for washing composition, have employed unique synthesis technique, before the reaction vinylformic acid is neutralized into neutrality, significantly can improves the percentage of grafting of maleic anhydride, there is transformation efficiency high, facility investment is few, product purity is high, without sewage exhaust gas emission, and the advantages such as environmental protection, the copolymer product synthesized is compared with product on the market, and the washing aid performance such as chelating ability, dispersion force will significantly increase.
Present invention also offers a kind of detergent use copolymer of maleic anhydride and acrylic acid prepared according to above-mentioned preparation method.
For achieving the above object, the present invention is by the following technical solutions:
First aspect of the present invention is to provide a kind of preparation method of detergent use copolymer of maleic anhydride and acrylic acid, and the method comprises the steps:
Step 1, step of reaction: water (preferred deionized water), maleic anhydride, Acrylic Acid Monomer, initiator are mixed in a reservoir, is warming up to 70 DEG C-100 DEG C reactions;
Step 2, holding stage: isothermal reaction at least 1 hour, be preferably at least 1.5 hours, be more preferably at least 2 hours, be more preferably 1-5 hour, be more preferably 1.5-4 hour, be more preferably 2-3.5 hour, as 2 hours, 2.5 hours, 3 hours;
Step 3, neutralization stage: be finally cooled to less than 60 DEG C, be more preferably 5-60 DEG C, be more preferably 15-60 DEG C, be more preferably 20-55 DEG C, be more preferably 25-55 DEG C, be more preferably 30-50 DEG C, be more preferably 40-55 DEG C, be more preferably about 50 DEG C, with alkaline solution neutralization, collect polymeric reaction product.
Preferably, the acrylate solution that in described step 1, Acrylic Acid Monomer is neutral with formation in alkaline solution in advance.
Preferably, in preparation method, the parts by weight of each component are:
Preferably, in preparation method, the parts by weight of each component are:
Wherein, preferably, in described alkaline solution in and Acrylic Acid Monomer be 50-200 parts by weight, be 50-200 parts by weight for the neutralization in described step 3.
Preferably, described initiator is oxidation-reduction trigger system, comprises Oxidizing and Reducing Agents.
Preferably, the oxygenant of described initiator to be selected from ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide any one or multiple.
Preferably, the reductive agent of described initiator to be selected from hydrosulphite (such as Potassium hydrogen sulfite, sodium bisulfite, ammonium bisulfite), pyrosulfite, thiosulphate, ferrous salt, xitix any one or multiple.
Preferably, described alkaline solution be in sodium hydroxide, potassium hydroxide or ammoniacal liquor any one or multiple.
Preferably, the feed way of described step 1 is: first mixed by the reductive agent of deionized water, maleic anhydride and initiator and be warming up to 70-100 DEG C, and then drips the oxygenant of vinylformic acid and the initiator neutralized simultaneously.
In aforesaid method of the present invention, neutralize described in step 3, be preferably neutralized to pH value and be at least 6, be more preferably and be at least 6.5, be more preferably and be at least 7, be more preferably 6-8, be more preferably 6.5-7.5, be more preferably 7.
Second aspect of the present invention is to provide a kind of detergent use copolymer of maleic anhydride and acrylic acid, and the weight-average molecular weight of described copolymer of maleic anhydride and acrylic acid is 50000-100000.
Preferably, the chelating ability of described copolymer of maleic anhydride and acrylic acid is 300-400mg/gCaCO
3, dispersion force is 280-320mg/gCaCO
3, alkali cushion effect is 12-18g.
Preferably, described copolymer of maleic anhydride and acrylic acid is prepared by preparation method according to claim 1.
The present invention adopts technique scheme, compared with prior art, has following technique effect:
1, adopt unique synthesis technique of the present invention, namely before polyreaction starts to drip monomer and initiator, in advance vinylformic acid being neutralized into pH value is about 7, and then carries out solution polymerization.Adopt this synthesis technique, can greatly increase maleic anhydride graft efficiency, the copolymer of maleic anhydride and acrylic acid product color of synthesis is shallow, the washing aid performances such as chelating ability dispersion force are excellent, completely or partially can replace tripoly phosphate sodium STPP in washing composition, reduce the harm of washing composition environmental pollution, there is obvious environmental benefit, economic benefit and social benefit.
2, the copolymer of maleic anhydride and acrylic acid synthesis technique of the present invention's design is all carry out in aqueous, after end of synthesis, unnecessary noxious solvent need not be distilled out, do not have solvent based in product to remain yet, production technique is simple, energy consumption is low, plant factor is high, greatly reduce the cost of traditional mode of production copolymer of maleic anhydride and acrylic acid, be applicable to large-scale commercial production.
3, the present invention designs copolymer of maleic anhydride and acrylic acid cost-performance ratio, processibility and range of application all can meet detergent formulation requirement.
Embodiment
Carry out detailed and concrete introduction below by specific embodiment to the present invention, to make better to understand the present invention, but following embodiment does not limit the scope of the invention.
embodiment 1
First add 2kg deionized water, 6kg maleic anhydride and 6kg initiator Potassium hydrogen sulfite in the reactor, warming while stirring to 70 DEG C, drip vinylformic acid sodium salt (reaction of 126kg Acrylic Acid Monomer 185kg sodium hydroxide solution is neutralized to neutrality and obtains), 4kg initiator potassium persulfate, the reaction times is 2 hours simultaneously; Dropwise rear isothermal reaction 3 hours; Neutrality is neutralized to after completion of the reaction with 125kg sodium hydroxide solution.
embodiment 2
First add 2.5kg deionized water, 8kg maleic anhydride and 6kg initiator xitix in the reactor, warming while stirring to 80 DEG C, drip vinylformic acid sylvite (reaction of 126kg Acrylic Acid Monomer 180kg potassium hydroxide solution is neutralized to neutrality and obtains), 5kg initiator Sodium Persulfate, the reaction times is 2 hours simultaneously; Dropwise rear isothermal reaction 3 hours; Neutrality is neutralized to after completion of the reaction with 125kg potassium hydroxide solution.
embodiment 3
First add 3kg deionized water, 6kg maleic anhydride and 6kg initiator Potassium hydrogen sulfite in the reactor, warming while stirring to 80 DEG C, drip vinylformic acid sodium salt (reaction of 126kg Acrylic Acid Monomer 180kg sodium hydroxide solution is neutralized to neutrality and obtains), 4kg initiator potassium persulfate, the reaction times is 2.5 hours simultaneously; Dropwise rear isothermal reaction 2 hours; Neutrality is neutralized to after completion of the reaction with 130kg sodium hydroxide solution.
embodiment 4
First add 3kg deionized water, 7kg maleic anhydride and 5kg initiator ferrous sulfate in the reactor, warming while stirring to 90 DEG C, drip vinylformic acid sodium salt (reaction of 126kg Acrylic Acid Monomer 185kg sodium hydroxide solution is neutralized to neutrality and obtains), 4kg initiator hydrogen peroxide, the reaction times is 3 hours simultaneously; Dropwise rear isothermal reaction 3 hours; Neutrality is neutralized to after completion of the reaction with 125kg sodium hydroxide solution.
embodiment 5
First add 3kg deionized water, 5kg maleic anhydride and 6kg initiator Potassium hydrogen sulfite in the reactor, warming while stirring to 80 DEG C, drip vinylformic acid sodium salt (reaction of 126kg Acrylic Acid Monomer 185kg sodium hydroxide solution is neutralized to neutrality and obtains), 4kg initiator ammonium persulfate, the reaction times is 2 hours simultaneously; Dropwise rear isothermal reaction 3 hours; Neutrality is neutralized to after completion of the reaction with 125kg sodium hydroxide solution.
performance test
Carry out performance comparison with domestic Betengent product, ask for an interview table 1 (the physical and chemical performance contrast of each Betengent product) and table 2 (the washing aid performance contrast of each Betengent product).
In table, comparative example 1 is the similar Betengent product in Guangzhou, comparative example 2 is the similar Betengent product in Shandong, these two kinds of Betengent products are all synthesize by traditional mode of production, employing benzoyl peroxide is initiator, in poisonous organic solvent is as toluene, dimethylbenzene etc., carries out solution polymerization, then obtains copolymer of maleic anhydride and acrylic acid through neutralizing hydrolysis.
The physical and chemical performance contrast of each Betengent product of table 1
The washing aid performance contrast of each Betengent product of table 2
As can be seen from table 1, table 2, copolymer of maleic anhydride and acrylic acid washing composition of the present invention, compared to the similar Betengent product in domestic Guangzhou and Shandong, outer smooth lighter color, molecular weight are high, pH value is closer to neutrality, and chelating ability, dispersion force, alkaline buffer power are all higher, there is superior washing aid performance.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (10)
1. a preparation method for detergent use copolymer of maleic anhydride and acrylic acid, is characterized in that, the method comprises the steps:
Step 1, Jiang Shui, maleic anhydride, Acrylic Acid Monomer, initiator mix, and are warming up to 70 DEG C to 100 DEG C reactions;
Step 2, isothermal reaction at least 1 hour;
Step 3, be cooled to less than 60 DEG C, with alkaline solution neutralization, collect polymeric reaction product.
2. preparation method according to claim 1, is characterized in that, the acrylate solution that in described step 1, Acrylic Acid Monomer is neutral with formation in alkaline solution in advance.
3. preparation method according to claim 2, is characterized in that, in preparation method, the parts by weight of each component are:
4. the preparation method according to claim 1 or 3, is characterized in that, described initiator is oxidation-reduction trigger system, comprises Oxidizing and Reducing Agents.
5. preparation method according to claim 4, is characterized in that, the oxygenant of described initiator to be selected from ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide any one or multiple.
6. preparation method according to claim 4, is characterized in that, the reductive agent of described initiator to be selected from hydrosulphite, pyrosulfite, thiosulphate, ferrous salt, xitix any one or multiple.
7. the preparation method according to claim 1 or 3, is characterized in that, described alkaline solution be in sodium hydroxide, potassium hydroxide or ammoniacal liquor any one or multiple.
8. a detergent use copolymer of maleic anhydride and acrylic acid, is characterized in that, the weight-average molecular weight of described copolymer of maleic anhydride and acrylic acid is 50000-100000.
9. detergent use copolymer of maleic anhydride and acrylic acid according to claim 8, is characterized in that, the chelating ability of described copolymer of maleic anhydride and acrylic acid is 300-400mg/gCaCO
3, dispersion force is 280-320mg/gCaCO
3, alkali cushion effect is 12-18g.
10. detergent use copolymer of maleic anhydride and acrylic acid according to claim 8, is characterized in that, described copolymer of maleic anhydride and acrylic acid is prepared by preparation method according to claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085607A (en) * | 2016-06-28 | 2016-11-09 | 郭迎庆 | A kind of preparation method of high-performance enzyme detergent |
| CN108484818A (en) * | 2018-05-09 | 2018-09-04 | 合肥国轩高科动力能源有限公司 | A kind of copolymer of maleic anhydride and acrylic acid prepares and removes calcium and magnesium ion application |
| CN116497616A (en) * | 2023-04-19 | 2023-07-28 | 宁波澳翔精细化工有限公司 | Preparation method of foamless soaping agent |
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| CN106085607A (en) * | 2016-06-28 | 2016-11-09 | 郭迎庆 | A kind of preparation method of high-performance enzyme detergent |
| CN108484818A (en) * | 2018-05-09 | 2018-09-04 | 合肥国轩高科动力能源有限公司 | A kind of copolymer of maleic anhydride and acrylic acid prepares and removes calcium and magnesium ion application |
| CN116497616A (en) * | 2023-04-19 | 2023-07-28 | 宁波澳翔精细化工有限公司 | Preparation method of foamless soaping agent |
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Application publication date: 20160511 |