CN1367200A - Denaturated sodium polyacrylate phosphorus-free adjuvant preparation process - Google Patents
Denaturated sodium polyacrylate phosphorus-free adjuvant preparation process Download PDFInfo
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- CN1367200A CN1367200A CN 02113413 CN02113413A CN1367200A CN 1367200 A CN1367200 A CN 1367200A CN 02113413 CN02113413 CN 02113413 CN 02113413 A CN02113413 A CN 02113413A CN 1367200 A CN1367200 A CN 1367200A
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Abstract
The present invention discloses a new process for preparing modified sodium polyacrylate non-phosphate adjuvant, and is characterized by that the acrylic acie whose molecular weight is 4000-10000 and maleic acid (anhydride) copolymer or acrylic acid homopolymer and sodium silicate aqueous solution are undergone the process of polymerization reaction and formed into the complex body formed from sodium salt of silic acid, sodium silicate and acrylic-maleic acid (anhydride) copolymer with active silanol group or the complex body formed from sodium salt of silic acid, sodium silicate and acrylic acid homopolymer, then the said complex body is spray-dried and made into the solid powdered product with strong adsorption force.
Description
Belongs to the technical field of:
the invention relates to a high-efficiency phosphate-free washing assistant, in particular to a novel preparation process using modified sodium polyacrylate as a phosphate-free assistant.
Background art:
sodium tripolyphosphate is a well-known excellent washing assistant, but the problem of over-fertilization caused by phosphorus-rich causes environmental pollution, and the country prohibits the production and use of phosphorus-containing washing products. Although sodium citrate does not contain phosphorus, it is not compatible with sodium dodecylbenzene sulfonate as well as Sodium Tripolyphosphate (STPP) and is expensive. Sodium tritiat triacetate (NTA) has three carboxylate radicals and has good chelating capacity with calcium, magnesium and other heavy metal ions, but after the NTA enters a washing powder formula, the safety of the NTA to human bodies and environmental ecology is not familiar to society. The 4A zeolite as the main assistant of detergent has poor magnesium ion exchange capacity and needs small amount of co-assistant, mainly polycarboxylate, such as sodium polyacrylate, polyacrylic acid-maleic acid salt, etc. The precipitated silica can replace STPP, is an amorphous substance, has no pollution to human body and environment, high adsorption capacity, good dispersibility and suspension property, certain exchange capacity of calcium and magnesium ions, and can be used as a washing assistant to prepare phosphorus-free washing powder with performance equivalent to that of phosphorus-containing washing powder. Sodium polyacrylate has been widely used in the synthetic detergent industry as a detergent builder, but because of its high cost, it is only used in small amounts in formulations as an auxiliary detergent. Because it is a high molecular polyelectrolyte, it can be adsorbed on the surface of washed matter and dirt surface, and has high charge density, so that it can raise the electrostatic repulsion between dirt and washed matter surface, and is favourable for removing dirt.
The invention content is as follows:
the invention aims to provide a novel preparation process of a modified sodium polyacrylate non-phosphorus auxiliary agent with good calcium and magnesium ion exchange capacity and anti-fouling redeposition property.
The technical scheme of the inventionis as follows:
the invention is characterized in that: acrylic acid with the molecular weight of 4000-10000 and maleic acid (anhydride) copolymer or acrylic acid homopolymer are selected to be polymerized with sodium silicate aqueous solution to form a complex body consisting of silicic acid with active silanol group, sodium silicate and sodium salt of acrylic acid maleic acid (anhydride) copolymer or a slurry complex body consisting of silicic acid with active silanol group, sodium silicate and sodium salt of acrylic acid homopolymer.
The slurry complex is spray dried to form a solid powder product.
The process of the invention comprises the following steps:
A. slowly adding acrylic acid with the molecular weight of 4000-10000 and maleic acid (anhydride) copolymer or acrylic acid homopolymer into sodium silicate aqueous solution with the Baume degree of 20, and intensively stirring, wherein the mass ratio of the acrylic acid to the maleic acid (anhydride) copolymer or the acrylic acid homopolymer is (10-20) to (130-10000) until the PH value is below 5, and generating white amorphous precipitate;
B. stirring the white silicon dioxide precipitate for 10-15 minutes, adding sodium silicate with Baume degree of 40, and uniformly stirring, wherein the mass ratio of the sodium silicate to the sodium silicate aqueous solution is (180) plus 200 to (130) plus 160;
C. adding an acidic substance and uniformly stirring, wherein the mass ratio of the acidic substance to the sodium silicate aqueous solution is 1: 130-; adding sodium carbonate and sodium sulfate, stirring, and heating to 50-75 deg.C to obtain slurry complex; the mass ratio of the sodium carbonate to the sodium silicate aqueous solution is (18-20) to (130-;
D. after the temperature of the slurry complex is raised, the slurry complex is spray-dried into a solid powdery product at the temperature of 280 ℃ and 330 ℃.
The reaction formula of the invention is as follows:
the preparation method of the acrylic acid and maleic acid (anhydride) copolymer or acrylic acid homopolymer is as follows:
A. weighing acrylic acid and maleic acid (anhydride) or acrylic acid according to the molar ratio of 1: 1, and adding a small amount of surfactant and a proper amount of water;
B. heating the mixture to 60-70 deg.C under vigorous stirring to disperse thoroughly in water;
C. adding a proper amount of sodium persulfate, continuously heating to 140-160 ℃ under stirring, and finishing the polymerization reaction within 12-15 minutes;
D. the average molecular weight of the copolymer is measured by a gel chromatography (GPC) method, and an acrylic acid and maleic acid (anhydride) copolymer or acrylic acid homopolymer with the molecular weight of 4000-10000 is selected.
The acidic substance in the invention is itaconic acid, citric acid or oxalic acid.
The molecular weight of the acrylic acid and maleic acid (anhydride) copolymer or acrylic acid homopolymer of the present invention is preferably 4000-4500.
The mechanism of the invention is as follows:
a phosphorus-free detergent with high effect comparable to that of sodium acrylate homopolymer or copolymer of acrylic acid and maleic acid (anhydride) is prepared from low-cost raw material and sodium acrylate homopolymer or copolymer of acrylic acid and maleic acid (anhydride) sodium salt through reaction of inorganic or organic acid on aqueous solution ofsodium silicate to generate precipitated silica (SiO silicate) with different physical properties2·H2O, amorphous silica). The silicic acid has active silanol group, high adsorption capacity, good dispersibility and certain exchange capacity of calcium and magnesium ions. The precipitated silica is substantially a silica gel having a surface comprising a layer of Silanol (SiOH) and physically adsorbed water, the majority of which can be obtained at a temperature of 125-Drying to remove, and leaving the silanol groups on the surface in the following three different configurations: isolated form (a), twin form (b) and vicinal form (c).
The newly formed siloxane chains are very reactive and the rehydration of the dehydrated surface is completely reversible as long as the drying temperature is below 345 ℃.
Silanol groups on the surface of the silicate are weak acids whose protons are capable of ion-exchanging with various metal cations. The exchange form can be represented by the following formula:
it is concluded that precipitated silicas used as washing aids have ion-exchange properties, the exchange capacity of which depends on the concentration of alkanol groups at the surface.
The quality indexes of the modified sodium polyacrylate of the invention are as follows:
pH value of 1% water solution is less than or equal to 11
12-15% of modified sodium polyacrylate
CaCO for calcium exchange capacity3mg/g≥450
Whiteness is greater than or equal to 95
Water binding% is more than or equal to 3
Humidity (H)2O)％≤6
The raw materials used in the invention are all easily biodegradable and do not contain phosphide; the LD50 is 6800mg/Kg after a half lethal dose toxicity test; is a green and environment-friendly product which has no pollution to the environment, particularly no pollution to water quality and is safe.
The modified sodium polyacrylate of the invention not only maintains the characteristics of high charge density and strong dirt removal performance of the original acrylic acid and maleic acid (anhydride) copolymer or acrylic acid homopolymer, but also has strong adsorption capacity of active silicic acid (amorphous precipitated silica), good dispersibility, good calcium-magnesium ion exchange capacity and anti-dirt redeposition performance, and is a good phosphate-free assistant and a good scale remover which have the advantages of low price, simple process and no pollution to the environment.
The specific implementation mode is as follows:
example 1:
slowly adding 15 parts of acrylic maleic acid (anhydride) copolymer into 150 parts of sodium silicate aqueous solution with Baume degree of 20, stirring under strong stirring until the PH is 4.5 to generate white amorphous precipitated silica, continuing stirring for 10 minutes, adding 200 parts of sodium silicate with Baume degree of 40, stirring uniformly, adding 1 part of itaconic acid, stirring uniformly, adding 20 parts of sodium carbonate and 30 parts of sodium sulfate, stirring uniformly, heating to 65 ℃ to form slurry, and spray drying at 325 ℃ to obtain a powdery product. The physical and chemical indexes are as follows:
whiteness 96, pH10.7, bound water 3.5%, humidity (H)2O) 5% calcium exchange capacity 450CaCO3mg/g, 13 percent of modified sodium polyacrylate.
Wherein: the preparation of the acrylic acid and maleic acid (anhydride) copolymer was: weighing acrylic acid with one molar mass and maleic acid (anhydride) with one molar mass, and adding a small amount of surfactant sodium lauryl sulfate and a proper amount of water; heating to 70 deg.C under strong stirring to make it fully disperse in water; adding 3 parts of proper amount of sodium persulfate, continuously heating to 150 ℃ under stirring, and reacting for 14 minutes under stirring to complete the polymerization reaction; the average molecular weight of the copolymer was 4200 as measured by Gel Permeation Chromatography (GPC).
Example 2: slowly adding 20 parts of acrylic acid homopolymer into 180 parts of sodium silicate with Baume degree of 20 under strong stirring until the pH value reaches 5 to generate white amorphous precipitated silicon dioxide, continuously stirring for 12 minutes, adding 200 parts of sodium silicate with Baume degree of 40, uniformly stirring, adding 1 part of oxalic acid, uniformly stirring, adding 25 parts of sodium carbonate and 35 parts of sodium sulfate, heating to 75 ℃, and performing spray drying at 325 ℃ to obtain a powdery product. The physical and chemical indexes are as follows:
whiteness 96, pH10.8, bound water 3.8%, humidity (H)2O) 5.5% and calcium exchange Capacity 460 CaCO3mg/g, 15 percent of modified sodium polyacrylate.
Wherein: the preparation of the acrylic homopolymer is: weighing acrylic acid with one molar mass, and adding a small amount of surfactant sodium lauryl sulfate and a proper amount of water; heating to 70 deg.C under strong stirring to make it fully disperse in water; then adding 3 parts of proper amount of sodium hydrogen peroxydisulfate, continuously heating to 160 ℃ under stirring, and reacting for 13 minutes under stirring to complete the polymerization reaction; the average molecular weight of the copolymer was 6000 as measured by Gel Permeation Chromatography (GPC).
The modified sodium polyacrylate of the invention is compared with STPP and 4A zeolite, and is respectively added into washing powder with the same formula by the dosage of 18 percent of the same mass, and the detergency index is determined as follows:
| name of auxiliary agent | The dosage in the formula | Index of detergency |
| The modified sodium polyacrylate of the invention | 18.0 | 1.15 |
| Sodium tripolyphosphate | 18.0 | 1.00 |
| 4A zeolite | 18.0 | 0.90 |
The detergency/price ratio of the modified sodium polyacrylate of the invention to related auxiliary agents in the formula of the washing powder is shown in the following table:
| auxiliary agent Name (R) | Binding power of calcium CaCO3mg/g | pH value | In the washing powder The dosage of the prescription is% | Detergency Index of refraction | Selling price Yuan/ton | Detergency/cost Ratio of |
| The invention changes Modified polypropylene Sodium salt | 450.0 | 11 | 18.0 | 1.15 | 3500.00 | 1.8 |
| Application for patent Number (C) 01107318.7 Modified polypropylene Sodium olefine acid | 442.8 | 11 | 18.0 | 1.10 | 4700.00 | 1.3 |
| 4A zeolite | 325.0 | 11 | 18.0 | 0.90 | 3200.00 | 1.5 |
| PAA/PAM | 430.0 | 11 | 18.0 | 1.35 | 20000.00 | 0.4 |
| Tripolyphosphoric acid Sodium (STPP) | 390.0 | 11 | 18.0 | 1.00 | 3700.00 | 1.5 |
As can be seen from the above table, the detergency/cost ratio of the denatured sodium polyacrylate of the present invention is the best.
The raw materials used in the invention are all easily biodegradable and do not contain phosphide; LD through semi-lethal dose toxicity test506800 mg/Kg; is a green and environment-friendly product which has no pollution to the environment, particularly no pollution to water quality and is safe.
The modified sodium polyacrylate of the invention not only maintains the characteristics of high charge density and strong dirt removal performance of the original acrylic acid and maleic acid (anhydride) copolymer or acrylic acid homopolymer, but also has strong adsorption capacity of active silicic acid (amorphous precipitated silica), good dispersibility, good calcium-magnesium ion exchange capacity and anti-dirt redeposition performance, and is a good phosphate-free assistant and a good scale remover which have the advantages of low price, simple process and no pollution to the environment.
Claims (6)
1. The new preparation process of modified sodium polyacrylate non-phosphate assistant features that: acrylic acid with the molecular weight of 4000-10000 and maleic acid (anhydride) copolymer or acrylic acid homopolymer are selected to be polymerized with sodium silicate aqueous solution to form a complex body consisting of silicic acid with active silanol group, sodium silicate and sodium salt of acrylic acid maleic acid (anhydride) copolymer ora slurry complex body consisting of silicic acid with active silanol group, sodium silicate and sodium salt of acrylic acid homopolymer.
2. The novel process for preparing the modified sodium polyacrylate non-phosphorus additive according to claim 1, which is characterized by comprising the following steps of:
A. acrylic acid with molecular weight of 4000-10000 and maleic acid (anhydride) copolymer or acrylic acid homopolymer are slowly added into sodium silicate aqueous solution with Baume degree of 20 and strongly stirred, the mass ratio is (10-15): (130-160) until the PH value is below 5, and white amorphous precipitate is generated;
B. stirring the white silicon dioxide precipitate for 10-15 minutes, adding sodium silicate with Baume degree of 40, and uniformly stirring, wherein the mass ratio of the sodium silicate to the sodium silicate aqueous solution is (180-) - (200-) - (130-) - (160-);
C. adding an acidic substance and uniformly stirring, wherein the mass ratio of the acidic substance to the sodium silicate aqueous solution is 1: 130-; adding sodium carbonate and sodium sulfate, stirring uniformly, heating to 50-75 ℃ to form a slurry-like complex, wherein the mass ratio of the sodium carbonate to the sodium silicate aqueous solution is (18-20) to (130-.
3. The novel process for preparing the modified sodium polyacrylate non-phosphorus additive according to claim 1 or 2, which is characterized in that: the preparation method of the acrylic acid and maleic acid (anhydride) copolymer or acrylic acid homopolymer comprises the following steps:
A. weighing acrylic acid and maleic acid (anhydride) or acrylic acid according to the molar ratio of 1: 1, and adding a small amount of surfactant and a proper amount of water;
B. heating the mixture to 60-70 deg.C under vigorous stirring to disperse thoroughly in water;
C. adding a proper amount of sodium persulfate, continuously heating to 140-160 ℃ under stirring, and finishing the polymerization reaction within 12-15 minutes;
D. the average molecular weight of the copolymer is measured by a gel chromatography (GPC) method, and the copolymer of acrylic acid and maleic acid (anhydride) or acrylic acid homopolymer is selected with the weight ratio of 4000-10000.
4. The novel process for preparing the modified sodium polyacrylate non-phosphorus additive according to claim 1 or 3, which is characterized in that: the acidic substance is itaconic acid, citric acid or oxalic acid.
5. The novel process for preparing the modified sodium polyacrylate non-phosphorus additive according to claim 1, which is characterized by comprising the following steps of: the slurry complex is spray dried to form a solid powdery product.
6. The novel process for preparing the modified sodium polyacrylate non-phosphorus additive according to claim 1, which is characterized by comprising the following steps of: the molecular weight of the acrylic acid-maleic acid (anhydride) copolymer or acrylic acid homopolymer is 4000-4500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113413 CN1127542C (en) | 2002-03-04 | 2002-03-04 | Denaturated sodium polyacrylate phosphorus-free adjuvant preparation process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02113413 CN1127542C (en) | 2002-03-04 | 2002-03-04 | Denaturated sodium polyacrylate phosphorus-free adjuvant preparation process |
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| Publication Number | Publication Date |
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| CN1367200A true CN1367200A (en) | 2002-09-04 |
| CN1127542C CN1127542C (en) | 2003-11-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 02113413 Expired - Fee Related CN1127542C (en) | 2002-03-04 | 2002-03-04 | Denaturated sodium polyacrylate phosphorus-free adjuvant preparation process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106890630A (en) * | 2017-03-28 | 2017-06-27 | 中国天辰工程有限公司 | A kind of preparation method of high water absorption core ﹣ shell structures discoloration silica-gel desiccant |
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2002
- 2002-03-04 CN CN 02113413 patent/CN1127542C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106890630A (en) * | 2017-03-28 | 2017-06-27 | 中国天辰工程有限公司 | A kind of preparation method of high water absorption core ﹣ shell structures discoloration silica-gel desiccant |
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| CN1127542C (en) | 2003-11-12 |
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