CN102140267B - Special cross-linking agent for polyacrylic acid thickening agent and preparation method thereof - Google Patents
Special cross-linking agent for polyacrylic acid thickening agent and preparation method thereof Download PDFInfo
- Publication number
- CN102140267B CN102140267B CN 201110009723 CN201110009723A CN102140267B CN 102140267 B CN102140267 B CN 102140267B CN 201110009723 CN201110009723 CN 201110009723 CN 201110009723 A CN201110009723 A CN 201110009723A CN 102140267 B CN102140267 B CN 102140267B
- Authority
- CN
- China
- Prior art keywords
- linking agent
- acid
- polyacrylic acid
- agent
- special cross
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
The invention discloses a special cross-linking agent for a polyacrylic acid thickening agent, which is characterized in that the special cross-linking agent is obtained by reacting a polyhydroxy group compound accounting for 50 to 80% of the total weight of a reactant and a polycarboxylic group compound accounting for 20 to 50% of the total weight of the reactant with the presence of a catalytic agent at a reaction temperature of 80 to 150 DEG C; and the catalytic agent is a high-temperature processing product of tellurium oxide and zirconium oxide, wherein the molar ratio of tellurium oxide to zirconium oxide is 1:1. The special cross-linking agent solves the difficult problems that the existing polyacrylic acid thickening agent has low thickening multiple and bad salt tolerance performance and is not suitable for acidic and active dye printing and the like.
Description
Technical field
The invention belongs to the coatings additive(s) synthesis technical field, be specifically related to a kind of special cross-linking agent for polyacrylic acid thickening agent and preparation method thereof.
Background technology
The consumption of coatings additive(s) in coating seldom but can significantly improve coating property, become the indispensable integral part of coating.The auxiliary agent that water-borne coatings is commonly used has film coalescence aid, thickening material, dispersion agent, wetting agent, defoamer, softening agent, antimildew disinfectant etc.Thickening material is a kind of auxiliary rheological agents, not only can make the coating thickening, prevents from the sagging phenomenon occurring in the construction, and can give mechanical property and the package stability of coating excellence.For the lower water-borne coatings of viscosity, it is a very important analog assistant.
Available thickening material kind is a lot of in the market, mainly contains inorganic thickening agent, cellulose family, polyacrylic acid and association type polyurethane thickener four classes.The polyacrylic thickening material can be divided into two kinds basically: a kind of is water miscible polyacrylate; Another kind is homopolymer or the copolymer emulsion thickening material of vinylformic acid, methacrylic acid, and this thickening material itself is acid, must just can reach thickening effectiveness with alkali or ammonia neutralization to pH8～9, is also referred to as propylene soda acid swelling thickening material.At present, the polyacrylic thickening material in fields such as water-borne coatings, pigment printings in occupation of the huge market space.According to incompletely statistics, only the Yangtze River Delta and area, Pearl River Delta just reach more than 3,000 ten thousand tons the annual requirement of polyacrylic thickening material.
Its thickening mechanism of agent for polyacrylic acid thickening is that thickening material is soluble in water, and by the same sex electrostatic repulsion of carboxylic acid ion, molecular chain is stretched to bar-shaped by spirrillum, thereby has improved the viscosity of water.It also forms reticulated structure by building bridge between emulsion particle and pigment in addition, has increased the viscosity of system.The agent for polyacrylic acid thickening agent for polyacrylic acid thickening has stronger thickening property and levelling property preferably, and biologically stable is good, but responsive, water-fast to the pH value, alkali resistance is not good.But because the deficiency that the structure of agent for polyacrylic acid thickening own forms, its thickening multiplying power is not high, and its salt resistant character is not good simultaneously, has greatly limited the expansion of its Application Areas.Especially in the pigment printing field, also only be only applicable at present Disperse Printing, then helpless to slurries such as reactive dyestuffs a large amount of on the market, matching stains.
Therefore, for a long time, it is good to develop a kind of thickening effectiveness, and the thickening material kind that saline-alkaline tolerance is strong just becomes the heat subject of agent for polyacrylic acid thickening industry.The raw material that Chinese patent application CN200510075291.1, CN200610131697, CN200680026485 change respectively existing thickening material forms, perhaps obtained corresponding product by the method for introducing particular monomers etc., so that the saline-alkaline tolerance of agent for polyacrylic acid thickening is able to lifting to a certain degree, but the thickening material high cost that obtains is difficult to industrialization.The present invention therefore.
Summary of the invention
The problems such as the object of the invention is to provide a kind of special cross-linking agent for polyacrylic acid thickening agent, and it is not high to have solved in the prior art agent for polyacrylic acid thickening thickening multiplying power, and its salt resistant character is not good simultaneously.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
A kind of special cross-linking agent for polyacrylic acid thickening agent is characterized in that described linking agent gets for the polyol that makes the gross weight 50-80% that accounts for reactant under the condition that exists at catalyzer, the multi-carboxy compound that accounts for the gross weight 20-50% of reactant react when temperature of reaction is 80-150 ℃; Wherein polyol is selected from one or more kinds of any mixing of following oxy-compound: butanols, octanol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, ethylene glycol, propylene glycol, butyleneglycol, polyether Glycols, polyester diol, glycerol, tetramethylolmethane, glucose, sucrose, fructose, polysorbas20, polysorbate40, polysorbate60, tween 80, polysorbate85, tween 90, tween 95, this dish 20, this dish 40, this dish 60, span 80, this dish 85, this dish 90, this dish 95, AEO4, AEO 7, AEO 10, sorbyl alcohol, polyvinyl alcohol; Multi-carboxy compound is selected from one or more kinds of any mixing of following carboxylic compound: acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, phenylformic acid, sad, enanthic acid, lauric acid, oleic acid, stearic acid, oxalic acid, propanedioic acid, Succinic Acid, flesh diacid, nonane diacid, phthalic acid, terephthalic acid, maleic acid anhydride, butene dioic acid, polyacrylic acid, polymethyl acrylic acid; Described catalyzer is tellurium oxide and zirconic pyroprocessing product, and wherein tellurium oxide and zirconic mol ratio are 1: 1.
The present invention also provides a kind of preparation method of special cross-linking agent for polyacrylic acid thickening agent, it is characterized in that the step that described method is included in the polyol that makes the gross weight 50-80% that accounts for reactant under the condition that catalyzer exists, the multi-carboxy compound that accounts for the gross weight 20-50% of reactant react the described special-purpose linking agent of acquisition when temperature of reaction is 80-150 ℃; Wherein polyol is selected from one or more kinds of any mixing of following oxy-compound: butanols, octanol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol, ethylene glycol, propylene glycol, butyleneglycol, polyether Glycols, polyester diol, glycerol, tetramethylolmethane, glucose, sucrose, fructose, polysorbas20, polysorbate40, polysorbate60, tween 80, polysorbate85, tween 90, tween 95, this dish 20, this dish 40, this dish 60, span 80, this dish 85, this dish 90, this dish 95, AEO 4, AEO 7, AEO 10, sorbyl alcohol, polyvinyl alcohol; Multi-carboxy compound is selected from one or more kinds of any mixing of following carboxylic compound: acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, phenylformic acid, sad, enanthic acid, lauric acid, oleic acid, stearic acid, oxalic acid, propanedioic acid, Succinic Acid, flesh diacid, nonane diacid, phthalic acid, terephthalic acid, maleic acid anhydride, butene dioic acid, polyacrylic acid, polymethyl acrylic acid; Described catalyzer is tellurium oxide and zirconic pyroprocessing product, and wherein tellurium oxide and zirconic mol ratio are 1: 1.
In the technical solution of the present invention: the linking agent of agent for polyacrylic acid thickening special use is mainly reacted under 80-150 ℃ of condition by the catalyzer that comprises polyol 50-80%, modification multi-carboxy compound 20-50% and trace in its weight percent content and gets.Wherein polyol comprises the one or any two kinds mixture of following oxy-compound: monohydroxy-alcohol such as butanols, octanol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol etc., dibasic alcohol such as ethylene glycol, propylene glycol, the polyether Glycols of butyleneglycol and different molecular weight, polyester diol etc., trivalent alcohol such as glycerol, tetravalent alcohol such as tetramethylolmethane, natural product such as glucose, sucrose, fructose etc., and related derivatives such as soil temperature (20,40,60,80,85,90,95 etc.), this dish (20,40,60,80,85,90,95 etc.), AEO (4,7,10 etc.), sorbyl alcohol and low-molecular-weight polyvinyl alcohol etc.; Multi-carboxy compound comprises the one or any two kinds mixture of following carboxylic compound: monoprotic acid such as acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, phenylformic acid, sad, enanthic acid, lauric acid, oleic acid, stearic acid etc., diprotic acid such as oxalic acid, propanedioic acid, Succinic Acid, flesh diacid, nonane diacid, phthalic acid, terephthalic acid, along (instead) maleic acid anhydride, gather (methyl) vinylformic acid etc. along (instead) butene dioic acid and lower molecular weight.Described catalyzer is tellurium oxide and zirconic pyroprocessing product, and wherein tellurium oxide and zirconic mol ratio are 1: 1.
When the present invention specifically prepares, polyol 50-80% is dropped in the reactor, slowly be warmed up to 80-100 ℃, until the still material melts fully; The catalyzer tellurium Zirconium oxide that adds trace stirs until mix.Slowly add multi-carboxy compound 20-50%, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition.Cooling discharging namely gets the linking agent of agent for polyacrylic acid thickening special use.
With respect to scheme of the prior art, advantage of the present invention is:
Raw material of the present invention all is industrial raw material, inexpensively easily purchases.Raw material does not need to carry out purification before the reaction, only need to react in the presence of controlling catalyst in this laboratory under certain temperature, certain stirring velocity, just can obtain needed linking agent, and preparation technology is simple.The prepared linking agent of the present invention can promote the thickening properties of agent for polyacrylic acid thickening greatly, improves the saline-alkaline tolerance of slurry, especially is suitable for the pigment printing industry.
In sum, the invention discloses a kind of linking agent that is applied to agent for polyacrylic acid thickening and preparation method thereof.It is characterized in that described linking agent is mainly reacted and got by the catalyzer tellurium Zirconium oxide that comprises polyol 50-80%, modification multi-carboxy compound 20-50% and trace in its weight percent content under 80-150 ℃ of condition.It is low to the invention solves existing agent for polyacrylic acid thickening thickening multiple, and anti-salt property is not good, can't be applicable to the difficult problem of the dye printings such as acidity, activity.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Embodiment 1
Get propylene glycol 400kg and low molecular weight polyethylene alcohol 200kg and drop in the reactor, slowly be warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix.Slowly add oleic acid 200kg and vinylformic acid 200kg, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition.Cooling discharging namely gets the linking agent of agent for polyacrylic acid thickening special use.After measured, the gained linking agent is elementary composition to be C55.18, H9.58, O35.24.
Embodiment 2
Get glycerol 500kg and tetramethylolmethane 200kg and drop in the reactor, slowly be warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix.Slowly add Succinic Acid 100kg and along (instead) maleic acid anhydride 200kg, after question response mixed, holding temperature was being reacted 2 hours at 80-100 ℃, again slaking 2 hours under 80-150 ℃ of condition.Cooling discharging namely gets the linking agent of agent for polyacrylic acid thickening special use.After measured, the gained linking agent is elementary composition to be C42.67, H7.47, O49.86.
Embodiment 3
Get this dish-20600kg and AEO-7 150kg and drop in the reactor, slowly be warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix.Slowly add MALEIC ANHYDRIDE 200kg and methacrylic acid 50kg, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition.Cooling discharging namely gets the linking agent of agent for polyacrylic acid thickening special use.After measured, the gained linking agent is elementary composition to be C56.51, H7.77, O35.72.
Embodiment 4
Get 200kg soil temperature 20 and 600kg span 80 and drop in the reactor, slowly be warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix.Slowly add maleic acid 200kg, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition.Cooling discharging namely gets the linking agent of agent for polyacrylic acid thickening special use.After measured, the gained linking agent is elementary composition to be C60.10, H8.72, O31.18.
Embodiment 5
Get stearyl alcohol 250kg, sorbyl alcohol 100kg and AEO-7350kg and drop in the reactor, slowly be warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix.Slowly add terephthalic acid 200kg and low-molecular-weight polypropylene acid 100kg, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition.Cooling discharging namely gets the linking agent of agent for polyacrylic acid thickening special use.After measured, the gained linking agent is elementary composition to be C62.62, H8.01, O29.37.
Embodiment 6
Get sorbyl alcohol 450kg and drop in the reactor, slowly be warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix.Slowly add terephthalic acid 200kg, stearic acid 200kg and methacrylic acid 150kg, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition.Cooling discharging namely gets the linking agent of agent for polyacrylic acid thickening special use.After measured, the gained linking agent is elementary composition to be C52.95, H7.78, O39.27.
The contrast application examples
Do not change the prescription of conventional acrylic thickening material and technique (take 1 product as example: aviation kerosene 170kg, vinylformic acid 230kg, two Methacrylamide 220g, acrylamide 25kg, Span-80 25kg, Potassium Persulphate 350g, ammonium persulphate 350g, OP-1025kg, all the other are deionized water and neutralization ammoniacal liquor), add above-mentioned each 3kg of linking agent 1-6 at emulsifying stage, six kinds of slurries after synthetic carried out thickening effectiveness and anti-salt property test, result's (following data record by rotational viscosimeter) as shown in the table with the blank sample that does not add linking agent:
The thickening of table 1 acrylic size and anti-salt property test result
Confirm that by above contrast application examples it is low that the linking agent that the present invention obtains has solved existing agent for polyacrylic acid thickening thickening multiple, anti-salt property is not good, can't be applicable to the difficult problem of the dye printings such as acidity, activity.The related linking agent of this invention is mainly reacted under 80-150 ℃ of condition by the catalyzer that comprises polyol 50-80%, multi-carboxy compound 20-50% and trace in its weight percent content and gets.On the basis that does not change original agent for polyacrylic acid thickening technique, by adding special-purpose linking agent kind, so as to the reactive force between the Reinforced Polypropylene acid chain, promote the quality of agent for polyacrylic acid thickening, reach the effect that improves its thickening multiple and saline-alkaline tolerance.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with technique can understand content of the present invention and according to this enforcement, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (6)
1. a special cross-linking agent for polyacrylic acid thickening agent is characterized in that described linking agent drops in the reactor for getting propylene glycol 400kg and low molecular weight polyethylene alcohol 200kg, slowly is warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix; Slowly add oleic acid 200kg and vinylformic acid 200kg, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition; Cooling discharging namely gets special cross-linking agent for polyacrylic acid thickening agent; Described catalyzer is tellurium oxide and zirconic pyroprocessing product, and wherein tellurium oxide and zirconic mol ratio are 1:1.
2. a special cross-linking agent for polyacrylic acid thickening agent is characterized in that described linking agent drops in the reactor for getting glycerol 500kg and tetramethylolmethane 200kg, slowly is warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix; Slowly add Succinic Acid 100kg and along (instead) maleic acid anhydride 200kg, after question response mixed, holding temperature was being reacted 2 hours at 80-100 ℃, again slaking 2 hours under 80-150 ℃ of condition; Cooling discharging namely gets special cross-linking agent for polyacrylic acid thickening agent; Described catalyzer is tellurium oxide and zirconic pyroprocessing product, and wherein tellurium oxide and zirconic mol ratio are 1:1.
3. a special cross-linking agent for polyacrylic acid thickening agent is characterized in that described linking agent drops in the reactor for getting this dish-20600kg and AEO-7150kg, slowly is warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix; Slowly add MALEIC ANHYDRIDE 200kg and methacrylic acid 50kg, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition; Cooling discharging namely gets special cross-linking agent for polyacrylic acid thickening agent; Described catalyzer is tellurium oxide and zirconic pyroprocessing product, and wherein tellurium oxide and zirconic mol ratio are 1:1.
4. a special cross-linking agent for polyacrylic acid thickening agent is characterized in that described linking agent drops in the reactor for getting 200kg soil temperature 20 and 600kg span 80, slowly is warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix; Slowly add maleic acid 200kg, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition; Cooling discharging namely gets special cross-linking agent for polyacrylic acid thickening agent; Described catalyzer is tellurium oxide and zirconic pyroprocessing product, and wherein tellurium oxide and zirconic mol ratio are 1:1.
5. a special cross-linking agent for polyacrylic acid thickening agent is characterized in that described linking agent drops in the reactor for getting stearyl alcohol 250kg, sorbyl alcohol 100kg and AEO-7350kg, slowly is warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix; Slowly add terephthalic acid 200kg and low-molecular-weight polypropylene acid 100kg, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition; Cooling discharging namely gets special cross-linking agent for polyacrylic acid thickening agent; Described catalyzer is tellurium oxide and zirconic pyroprocessing product, and wherein tellurium oxide and zirconic mol ratio are 1:1.
6. a special cross-linking agent for polyacrylic acid thickening agent is characterized in that described linking agent drops in the reactor for getting sorbyl alcohol 450kg, slowly is warmed up to 80-100 ℃, until the still material melts fully; The catalyzer that adds trace stirs until mix; Slowly add terephthalic acid 200kg, stearic acid 200kg and methacrylic acid 150kg, after question response mixed, holding temperature was in 80-100 ℃ of reaction 2 hours, again slaking 2 hours under 80-150 ℃ of condition; Cooling discharging namely gets special cross-linking agent for polyacrylic acid thickening agent; Described catalyzer is tellurium oxide and zirconic pyroprocessing product, and wherein tellurium oxide and zirconic mol ratio are 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110009723 CN102140267B (en) | 2011-01-18 | 2011-01-18 | Special cross-linking agent for polyacrylic acid thickening agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110009723 CN102140267B (en) | 2011-01-18 | 2011-01-18 | Special cross-linking agent for polyacrylic acid thickening agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102140267A CN102140267A (en) | 2011-08-03 |
| CN102140267B true CN102140267B (en) | 2013-04-03 |
Family
ID=44408070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110009723 Expired - Fee Related CN102140267B (en) | 2011-01-18 | 2011-01-18 | Special cross-linking agent for polyacrylic acid thickening agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102140267B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107119473A (en) * | 2017-06-26 | 2017-09-01 | 王蒙 | A kind of cross linking agent |
| CN107460746A (en) * | 2017-07-10 | 2017-12-12 | 纤化（上海）生物化工股份有限公司 | A kind of preparation method of crosslinking agent for pigment printing |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156717A (en) * | 1996-11-26 | 1997-08-13 | 厦门大学 | Process for producing n-butyl acetate |
| CN1810849A (en) * | 2005-01-24 | 2006-08-02 | 段吉文 | Modified monomer solution for polyester |
| CN1876751A (en) * | 2005-06-10 | 2006-12-13 | 中国石油天然气股份有限公司 | Braided comb-shaped salt-resistant polymer thickener |
| CN1962705A (en) * | 2006-11-30 | 2007-05-16 | 中国科学院长春应用化学研究所 | Preparation method of haloduric thickener |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001028306A2 (en) * | 1999-10-19 | 2001-04-26 | Akzo Nobel N.V. | Process for preparing an aqueous powder coating dispersion |
-
2011
- 2011-01-18 CN CN 201110009723 patent/CN102140267B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156717A (en) * | 1996-11-26 | 1997-08-13 | 厦门大学 | Process for producing n-butyl acetate |
| CN1810849A (en) * | 2005-01-24 | 2006-08-02 | 段吉文 | Modified monomer solution for polyester |
| CN1876751A (en) * | 2005-06-10 | 2006-12-13 | 中国石油天然气股份有限公司 | Braided comb-shaped salt-resistant polymer thickener |
| CN1962705A (en) * | 2006-11-30 | 2007-05-16 | 中国科学院长春应用化学研究所 | Preparation method of haloduric thickener |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102140267A (en) | 2011-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101328238B (en) | Pigment dispersants, their production process, and their use | |
| CN101792570A (en) | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application | |
| CN104718172B (en) | Hardening accelerator compositionss | |
| CN101633814A (en) | Water borne epoxy resin anticorrosive paint and preparation method thereof | |
| CN103517926B (en) | Polymkeric substance and composition thereof | |
| CN103319680B (en) | Preparation method of composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate | |
| CN104371073A (en) | Normal-temperature preparation method of slow-release polycarboxylate superplasticizer | |
| CN101959976A (en) | Pigment dispersant | |
| CN101899246A (en) | Metal surface protection paint and method for preparing same | |
| CN102140267B (en) | Special cross-linking agent for polyacrylic acid thickening agent and preparation method thereof | |
| CN103819623A (en) | Preparation method for cement auxiliary-grinding strengthener of polyethylene glycol amine ester carboxylic acid system | |
| CN1090528C (en) | Phosphate esters polyalkylene ether block copolymers and their use as dispersants | |
| CN101589104A (en) | Acrylic acid ester copolymer composition and redispersible powders | |
| CN100526356C (en) | Carboxylic acids graft copolymer concrete strengthening agent | |
| CN105968304A (en) | High-performance waterborne polyurethane curing agent and preparing method and application thereof | |
| CN103724556A (en) | Preparation method of resin, resin, ink and preparation method thereof | |
| CN106190652B (en) | A kind of environment-friendly low-temperature soaping agent | |
| CN105273113A (en) | Polyacrylic acid synthesis reaction apparatus and polyacrylic acid synthesis method | |
| CN104311728B (en) | Water transfer thermoplastic acrylic resin, preparation method and water transfer ink composition | |
| US20160102198A1 (en) | Novel polymer dispersants | |
| CN104640909A (en) | Hyperbranched phosphoric acid esters | |
| CN103210005A (en) | Viscosity regulating composition | |
| CN106632888A (en) | Polycarboxylate-series concrete water reducing agent | |
| CN110499218A (en) | A kind of efficient and environment-friendly type acid scouring agent and preparation method thereof | |
| CN101412864B (en) | Self-drying glass ink and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130403 Termination date: 20180118 |