CN1152053A - Hyperconcentrated demulsification polymerization to produce printing thickening agent - Google Patents
Hyperconcentrated demulsification polymerization to produce printing thickening agent Download PDFInfo
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- CN1152053A CN1152053A CN 96115979 CN96115979A CN1152053A CN 1152053 A CN1152053 A CN 1152053A CN 96115979 CN96115979 CN 96115979 CN 96115979 A CN96115979 A CN 96115979A CN 1152053 A CN1152053 A CN 1152053A
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Abstract
The present invention produces printing densifer by selecting water-soluble monomer, water, organic solvent, emulsifier, crosslinking agent, primer and other material and through mixing via stirring in container, leading in nitrogen to remove oxygen, and polymeriation during integral or sectional heating. The polymerization system has a water phase not less than 74%. The said method is simple, low in cost and less in pollution, and can obtain product with good densifying effect.
Description
The present invention relates to a kind of is the method that polymerizable raw material is produced the printing thickening agent that is used for textile product stamp field with acrylic acid, acrylamide, water, organic solvent etc.Printing thickening agent belongs to a kind of fine chemical product, is the micro-crosslinked polymer of a class water-soluble monomer, adds can reach very high denseness on a small quantity in water, especially in order to increase the denseness of printing paste.
Because the needs energy-conservation and minimizing is polluted, synthetic printing thickening agent just is being tending towards replacing fully the emulsion thickening made from kerosene, water and emulsifying agent.The method that present synthetic thickening agent is adopted has: emulsion polymerisation, inverse emulsion polymerization, polymerisation in solution, precipitation polymerization.Wherein therefore inverse emulsion polymerization is widely used in the preparation of thickener because have advantages such as reaction speed is fast, the high easily-controlled operation of molecular weight.But because inverse emulsion polymerization has used a large amount of organic solvents such as varsol (being generally the 40-70% of system gross weight), improved cost, caused too much pollution and waste.
On the other hand, the thickening capabilities of thickener is directly connected to the amount retained of thickening polymer in the cost of product and the seal slurry, and the latter to stamp after the feel of fabric exert an influence.Therefore domestic and international research person is how improving thickening capabilities as main goal in research.For example E.P0150933 adds methacrylic acid octadecanol ester when polymerization; U.S.P5086142 adds the thickening effect that polyalkylene glycol acrylate ethers etc. increases product when producing O/w emulsion.
End is got up, and it is many that existing synthetic textile product printing thickening agent ubiquity the varsol consumption, product cost height, shortcoming such as thickening effect is undesirable.
The objective of the invention is to overcome existing polymerization and produce the shortcoming that exists in the printing thickening agent technology, make every effort to reduce the consumption of organic solvent in the polymerization system and improve the thickening capabilities of product, reduce and pollute, adopt super dense inverse emulsion polymerization to produce printing thickening agent.
In order to realize the foregoing invention purpose, the present invention adds raw materials such as monomer, water, organic solvent, emulsifying agent, crosslinking agent and initator by proportioning in aggregation container, feeds nitrogen and get rid of oxygen, polymerization at a certain temperature under stirring condition.The water percent by volume is not less than 74% in whole polymerization system, forms super dense reversed-phase emulsion.Monomer is selected water-soluble monomers such as acrylic acid (salt), methacrylic acid (salt), acrylamide for use; Its organic solvent is often selected varsol for use, generally chooses kerosene, gasoline and white oil; Its emulsifying agent can be selected the water-in-oil type surfactant for use; Its initator is oil-soluble or water-solublely all can; Its crosslinking agent is chosen polyfunctional monomers such as divinylbenzene, methylene-bisacrylamide, Ethylene glycol dimethacrylate.
The present invention compares with existing thickener preparation technique, it is simple to have prescription and technology, raw material is easy to get, the product stamp thickening effect height that its polymerization is produced, the printing paste that uses this product to be mixed with is compared with domestic and international product, its viscosity improves more than 40%, and the pollution level in the production process descends.
The present invention has adopted super dense inverse emulsion polymerization, and promptly the decentralized photo volume is not less than 74% emulsion polymerisation.Owing to reduced oily use amount, increased the monomer solution phase, make that the thickening effect of polymerizate improved greatly when monomer concentration maintained in the acceptable scope in the system.
The key that realizes super dense inverse emulsion polymerization is the selection of emulsifying agent, can adopt the independent or composite uses of water-in-oil type surfactant such as SPAN-60, SPAN-80.Sometimes can add high molecular surfactant (block of a kind of hydrophilic monomer and hydrophobic monomer or graft polymers) in right amount in order to improve polymerization stability.
The used organic solvent of the present invention is generally varsol, the most frequently used is kerosene cheap and easy to get, gasoline, white oil etc.Its consumption should be less than 26% of cumulative volume, and is generally between 26%～17%, too harsh to requirement for experiment condition when consumption is very few.
The used monomer of the present invention can be acrylic acid (salt), methacryloxyethyl acid (salt), acrylamide, Methacrylamide, allyl sulphonic acid (salt) etc.Copolymerization ratio between them can be regulated arbitrarily, but the monomer of Electrolyte type helps improving the thickening power of product.Add cross-linking monomers such as a spot of methylene-bisacrylamide, divinylbenzene, diallyl phthalate, make it crosslinked.Consumption can be 0～1% of monomer weight.But the consumption of (methyl) acrylic acid and its salt was at 100: 0～50: 50; The ratio of (methyl) acrylic acid or its salt and acrylamide is 100: 0～20: 80; The consumption of cross-linking monomer is better at 0.05%～0.5% o'clock polymerization result.
The ratio of aqueous phase water and monomer can be selected arbitrarily, but considers polymerization efficiency and polymerization stability, accounts for 40～80% of water gross weight with the consumption of water and is advisable.
Initator not only can adopt oil-soluble initiator but also can adopt water soluble starter, and the most frequently used is ammonium persulfate, consumption 0.1～0.5%.
Polymerization temperature can be selected 20～80 ℃ of constant temperature polymerizations or alternating temperature stage feeding polymerization according to used initator and actual needs.But the product thickening effect with low temperature polymerization is better.
The present invention has been owing to used super dense inverse emulsion polymerization, makes that the consumption of organic solvent is limited in (weight ratio) 20% below in the polymerization system, and thickening capabilities press the unit polymer conversion of product, than at present domestic and international product raising about 30～50%.
Embodiment 1:
In the 250ml conical flask, feed intake in following ratio:
Acrylic acid: 27g acrylamide: 3g
Ammoniacal liquor: 5g water: 70g
Methylene-bisacrylamide: 0.06g
Ammonium persulfate: 0.09g SPAN-60:1.5g
Kerosene: 20g
Add magnetic agitation, logical nitrogen deoxygenation, polymerization 15hr under the room temperature is heated to 70 ℃ of polyase 13 0min.Can obtain white viscous emulsion, its polymer content is about 24%.Get two these products of gram, add running water 80 gram, add ammoniacal liquor modulation neutrality after, with NDJ-II type rotation viscometer 4* rotor viscosimetric, viscosity was 80 when rotating speed was 6 rev/mins, 000mPa.s.
Embodiment 2:
Adopt polymerization formula and the technology identical, just change the ratio of acrylic acid and acrylamide: acrylic acid 10g, acrylamide 20g with example 1
The polymerizate outward appearance is identical with example 1, gets 2 these products of gram, is 50 by example 1 method viscosimetric, 000mPa.s.
Embodiment 3:
Adopt prescription and the technology identical with example 1, just polymerization temperature changes 60 ℃ of polyase 13s hour into, and the products therefrom outward appearance is identical with example 1, and get 2 and restrain these products, be 50 by example 1 method viscosimetric, 000mPa.s
Embodiment 4:
Adopt embodiment 1 proportioning, the raw material consumption is enlarged 500～1000 times, select for use 150 liters above stainless steel or enamel still to expand examination, other conditions are all undertaken by step and the condition of embodiment 1, and through suitably handling, resulting thickener properties of product are as follows:
Product appearance: translucent yellow liquid;
Shelf stability: the long-term placement never degenerated, and be not stratified;
Solid content: about 40%
Using method: after directly adding the water stirring, can become to stick with paste rapidly;
Thickening capabilities: 2% water is stuck with paste viscosity 60, and 000mPa.s presses following formulated printing paste:
Adhesive 20
Mill base 5
Thickener 2
Water 73
Total amount 100
Measuring viscosity is 30,000mPa.s
This thickener is made into printing paste and uses the result good through the textile product printing and dyeing, especially in imperviousization, and feel aspect excellent performance.
Claims (4)
1. one kind is raw material with water-soluble monomer, organic solvent etc., add the water polymerization and produce the super dense inverse emulsion polymerization of the printing thickening agent that is used for the printing in textiles field, it is characterized in that in container by raw materials such as proportioning adding monomer, water, organic solvent, emulsifying agent, crosslinking agent and initators, logical nitrogen deoxygenation under the stirring condition, carry out polymerization under the uniform temperature, its product is a kind of efficient printing thickening agent.
2. the method for thickener is produced in super dense inverse emulsion polymerization according to claim 1, it is characterized in that the percent by volume that water accounts for whole system is not less than 74%.Form super dense reversed-phase emulsion state.
3. the method for printing thickening agent is produced in described super dense inverse emulsion polymerization according to claim 1, it is characterized in that monomer selects water-soluble monomers such as acrylic acid (salt), methacrylic acid (salt), acrylamide for use; Organic solvent often adopts varsol, generally selects gasoline, kerosene and white oil for use.
4. the method for printing thickening agent is produced in described super dense inverse emulsion polymerization according to claim 1, it is characterized in that emulsifying agent selects the surfactant of water-in-oil type for use; Initator is oil-soluble or water-solublely all can; Crosslinking agent is chosen polyfunctional monomers such as divinylbenzene, methylene-bisacrylamide, Ethylene glycol dimethacrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115979A CN1056659C (en) | 1996-09-14 | 1996-09-14 | Hyperconcentrated demulsification polymerization to produce printing thickening agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115979A CN1056659C (en) | 1996-09-14 | 1996-09-14 | Hyperconcentrated demulsification polymerization to produce printing thickening agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1152053A true CN1152053A (en) | 1997-06-18 |
| CN1056659C CN1056659C (en) | 2000-09-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96115979A Expired - Fee Related CN1056659C (en) | 1996-09-14 | 1996-09-14 | Hyperconcentrated demulsification polymerization to produce printing thickening agent |
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| CN (1) | CN1056659C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445305C (en) * | 2005-12-22 | 2008-12-24 | 南化集团研究院 | Inverse emulsion synthesis process of printing paint thickener |
| CN101775099A (en) * | 2010-03-10 | 2010-07-14 | 杭州传化精细化工有限公司 | Paint thickener for printing and preparation method thereof |
| CN104356277A (en) * | 2014-10-22 | 2015-02-18 | 上海中博生物科技有限公司 | Thickener capable of improving hand feeling of pigment print and preparation method of thickener |
| CN115260379A (en) * | 2022-08-30 | 2022-11-01 | 无锡德冠生物科技有限公司 | Bio-based pigment printing thickener and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR910015597A (en) * | 1990-02-14 | 1991-09-30 | 원본미기재 | Polymer Thickener |
-
1996
- 1996-09-14 CN CN96115979A patent/CN1056659C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445305C (en) * | 2005-12-22 | 2008-12-24 | 南化集团研究院 | Inverse emulsion synthesis process of printing paint thickener |
| CN101775099A (en) * | 2010-03-10 | 2010-07-14 | 杭州传化精细化工有限公司 | Paint thickener for printing and preparation method thereof |
| CN101775099B (en) * | 2010-03-10 | 2012-10-03 | 杭州传化精细化工有限公司 | Paint thickener for printing and preparation method thereof |
| CN104356277A (en) * | 2014-10-22 | 2015-02-18 | 上海中博生物科技有限公司 | Thickener capable of improving hand feeling of pigment print and preparation method of thickener |
| CN104356277B (en) * | 2014-10-22 | 2016-08-17 | 上海中博生物科技有限公司 | A kind of thickening agent that can improve pigment printing feel and preparation method thereof |
| CN115260379A (en) * | 2022-08-30 | 2022-11-01 | 无锡德冠生物科技有限公司 | Bio-based pigment printing thickener and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1056659C (en) | 2000-09-20 |
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