CN1587285A - Process for preparing polymer powder capable of being redispersed - Google Patents
Process for preparing polymer powder capable of being redispersed Download PDFInfo
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- CN1587285A CN1587285A CN 200410069567 CN200410069567A CN1587285A CN 1587285 A CN1587285 A CN 1587285A CN 200410069567 CN200410069567 CN 200410069567 CN 200410069567 A CN200410069567 A CN 200410069567A CN 1587285 A CN1587285 A CN 1587285A
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Abstract
The present invention relates to cement base material modifier, and discloses a kind of polymer powder capable of being re-dispersed and its preparation process. The polymer powder capable of being re-dispersed is copolymer prepared with water insoluble hard monomer, water insoluble soft monomer and hydroxyl containing water sensitive monomer and through emulsion polymerization in the presence of high molecular weight emulsifier. The polymer powder may be dispersed in water in pH not lower than 5. By means of high molecular weight emulsifier and water sensitive monomer, the polymer emulsion may be demulsified chemically, and this omits the investment for apparatus and power consumption of spray drying and results in improved re-dispersing capacity of the polymer powder and raised polymer powder quality.
Description
Technical field
The present invention relates to the research field of cement-based material properties-correcting agent, particularly a kind of preparation method who can be used as the redispersible polymer powder of cement-based material properties-correcting agent.
Background technology
Cement-based material is present most important material of construction, its good mechanical performance and cheap price guarantee its in quite long from now on period, will be main material of construction.But also there are two big defectives in cement-based material itself: one, to compare with its good ultimate compression strength, and cement-based material has low tensile strength and very little breaking strain, shows sizable fragility; They are two years old, cement easily shrank and the generation tiny crack at the aquation initial stage, in addition in order to guarantee newly to mix the works fine performance of cement-based material, the amount of mixing water is considerably beyond the required water yield of hydrated cementitious, and excessive evaporation of water stays many pores in cement-based material, the existence of tiny crack and pore causes the sepage of cement-based material ventilative, the infiltration of Carbon Dioxide in Air produces carboniogenesis, the weather resistance of grievous injury cement-based material to the cement-based material that is alkalescence.The existence of above problem; quality to construction work has caused serious harm; the infiltration of for example civilian and commercial building, the daily life that seepy question is perplexing the people; so the work-ing life that the seepage of special waterproofing works such as reservoir, rivers,lakes and seas bank protection, tunnel, colliery has been damaged engineering is the subject matter that the ventilative problem of the sepage of cement-based material is its widespread use of restriction.
Cement material fragility is big in order to solve, the difficult problem of easy to leak, Chinese scholars has been carried out a large amount of theoretical investigation work for this reason, some feasible terms of settlement have also been proposed, mainly contain: (1) uses fiber reinforced cement-based material, for example steel fiber, glass fibre and synthon (polypropylene, polyacrylonitrile and vinylon etc.) refinforced cement sill.Fiber mix the folding strength that has improved cement-based material significantly, shrink the limited in one's ability of the tiny crack that produces but suppress hydrated cementitious, the leakage problems of cement-based material is not improved; (2) in the proportioning of cement-based material, mix inorganic superfine powders such as wollastonite powder, flyash, plan is stopped up pore with inorganic superfine powder, but the workability that the more mixing water of need keeps newly mixing cement-based material that mixes because of inorganic superfine powder, and inorganic superfine powder mix the contraction that has increased cement-based material, cause that tiny crack increases in the cement-based material, the ventilative problem of cement-based material sepage is not effectively solved; (3) mix inorganic salt such as aluminum chloride, intend utilizing the inorganic salt that mix under the alkaline environment of cement, metal ion in the inorganic salt and hydroxide radical reaction generate hydroxide gel and stop up pore, because the oxyhydroxide of aluminium is amphoteric hydroxide, and the existence of chlorion can be quickened the corrosion of reinforcing bar in the cement-based material, so the application of this method is subjected to limiting greatly; (4) at cement-based material external coating polymer protective layer, and polymkeric substance and cement-based material belong to organism and inorganics respectively, and the reactive force between the two is very little; cohesive strength is low; and the polymeric coating long-term exposure outside, easily produces and wear out, and is difficult to keep permanence.Therefore, aforesaid method does not fundamentally solve the inherent defect of cement-based material.
From the fifties in last century, Japan material scholar Yoshihiko Ohama is applied to polymer latex in the cement material, not only improved the folding strength of cement-based material significantly, also because the plasticizing and the bleed effect of polymer latex Ruzhong emulsifying agent, flowability of newly mixing cement-based material and the freeze-thaw resistance that hardens the back cement-based material have been improved significantly, form network structure with cement-hydrate after the polymer latex film forming, suppressed the contraction of cement-based material, reduced the existence of tiny crack, eliminated the existence that connects pore, change the aperture structure of cement-based material, reduced the sepage ventilation property of cement-based material significantly.The excellent properties of polymer latex modified cement sill, caused the great attention of the researcher of being engaged in cement material research, now the polymer latex of successful Application has polyethylene vinyl acetate ester gum breast (EVA), styrene-butadiene latex (SB) and styrene-acrylic latex etc., mainly is used as concrete repair mortar, common mending mortar, terrace mortar, gravity flow self-leveling floor mortar, wall and floor tile adhesive agent, jointing agent, plaster material and sealing mortar etc.The successful Application of polymer latex has enlarged the use range of cement-based material, and improved some performance of cement-based material significantly, but utilize polymer latex modified cement sill in use to have following problem: at first to show and use inconvenience and proportioning to be difficult to accurate control, utilize polymer latex preparation cement-based material, need buy polymer latex and cement-based material respectively, be mixed in proportion during use, but the solid content of polymer latex is uncertain, so the proportioning of each component is difficult to accurate control; Next is that polymer latex Ruzhong at least 50% is a water, brings many inconvenience for transportation and storage, and has increased Packing Fee.
Therefore, the premium properties that people wish have a kind of single-component system to obtain polymer mortar more easily and had, the appearance of redispersible polymer powder comes true this hope.The triumphant chemical company of Germany's prestige takes the lead in developing first-generation vinyl acetate between to for plastic homopolymer redispersible powder, has released the vinyl acetate-ethylene copolymer redispersible powder subsequently again.Along with the market requirement, how tame world-renowned chemical company such as national starch, the triumphant chemical company of prestige have all been carried out the research of redispersible polymer powder, the redispersible polymer powder of the multiple different performances such as acrylic acid series, styrene-propene acid system that released one after another.Redispersible polymer powder is meant the polymer latex that obtains by letex polymerization, the polymer powder that obtains through super-dry or other means, when with it with after water mixes by a certain percentage, can form stable polymer latex once more, and have the performance of original synthetic polymer latex.The application of redispersible polymer powder has solved the problem that polymer latex brought of using, it is mixed by a certain percentage with each component of cement-based material, only needing to add a certain proportion of water at the construction field (site) gets final product, both simplified construction process, reduced cost again, for wide prospect has been opened up in the application of polymkeric substance in cement-based material.
The main method for preparing redispersible polymer powder from polymer latex is a spray-drying process, but owing to the second-order transition temperature of the polymkeric substance that is applied to the modified cement sill is lower, under the spraying drying temperature, the emulsion particle in polymer latex Ruzhong is clamminess, easily bond together, be difficult to obtain having the redispersible polymer powder of desirable particle size size and size distribution.For this reason, scientist has carried out number of research projects both at home and abroad, a certain amount of antisticking agent (inorganic mineral powders such as clay, silicon-dioxide and lime carbonate) is mixed in discovery in the polymer latex Ruzhong, reduce the bonding chance of emulsion particle, and, can obtain redispersible polymer powder by improving spray drying device.But because technical difficulty is big, only have in the world at present Japan, Germany, Italy and the U.S. can production application in the redispersible polymer powder of cement-based material.In addition because in spray-drying process, admixture the antisticking agent of a certain amount of (＞10%), make the redispersibility of resulting polymers powder poor, the over-all properties of latex has been compared certain gap with original copolymer latex behind the redispersion.
China is started in last century end to the research of polymer latex modified cement sill, because domestic polymer latex kind is limited, the polymer latex that can be applicable to cement-based material is phoenix feathers and unicorn horns especially.Limited report about redispersible polymer powder research, mainly concentrate on the mensuration of external product being mixed performance behind the cement material, and a piece of only having the Liu Yong of material of construction scientific research institution, Tianjin to attain etc. to deliver about the paper of redispersible polymer powder preparation, what adopt is spray-drying process, the verified laboratory result that still is in also has suitable distance from industrialization.
At present, adopt chemical process that polymer emulsion is implemented breakdown of emulsion, the technology through grinding the preparation redispersible polymer powder yet there are no report.
Summary of the invention
One object of the present invention is to provide a kind of redispersible polymer powder, and its redispersion ability height can be used as the properties-correcting agent of cement-based material.
Another object of the present invention is to provide a kind of preparation method of redispersible polymer powder, utilize macromolecule emulsifier and water sensitivity monomer, thereby can implement breakdown of emulsion to polymer emulsion by chemical process.
According to one aspect of the present invention, the present invention discloses a kind of redispersible polymer powder, it is characterized in that, it is that water sensitivity monomer by water-insoluble hard monomer, water-insoluble soft monomer and hydroxyl forms by emulsion polymerization prepared in the presence of macromolecule emulsifier, wherein, described redispersible polymer powder can be at pH 〉=5 o'clock redispersion in water.
Described macromolecule emulsifier is cationic or anionic, described water-insoluble hard monomer is selected from vinylbenzene or methyl methacrylate, described water-insoluble soft monomer is selected from butyl acrylate or vinyl acetate between to for plastic, and described water sensitivity monomer is selected from vinylformic acid hydroxyl methyl esters, hydroxy methyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester or methacrylic acid hydroxy butyl ester.
Described macromolecule emulsifier is polyene propyl sulfonic acid sodium, poly-2-acrylamide-2-methyl propane sulfonic acid sodium, sodium polystyrene sulfonate, polyene propoxy-benzene sulfonic acid sodium salt, sodium polyacrylate, Poly Dimethyl Diallyl Ammonium Chloride or polymethyl acrylic acid trimethyl ammonium chloride.
The present invention also discloses a kind of preparation method of this redispersible polymer powder, it is characterized in that, it may further comprise the steps:
(1) macromolecule emulsifier is synthetic: by solution polymerization, adopt water soluble starter, positively charged ion or anionic monomer polymerization are obtained macromolecule emulsifier;
(2) preparation of polymer emulsion: by letex polymerization, adopt water soluble starter, under the condition that the macromolecule emulsifier that obtains in step (1) exists, water-insoluble hard monomer, water-insoluble soft monomer and water sensitivity monomer polymerization are obtained polymer emulsion, wherein, the content of macromolecule emulsifier is 5～20% of water-insoluble hard monomer, water-insoluble soft monomer and water sensitivity monomer content summation, and the monomeric content of water sensitivity accounts for 5～20% of water-insoluble hard monomer, water-insoluble soft monomer content and water sensitivity monomer summation;
(3) breakdown of emulsion: add metal-salt or acid in the emulsion that in step (2), obtains, it is carried out breakdown of emulsion and obtains redispersible polymer powder.
In the described step (1), monomer is a sodium allyl sulfonate, 2-acrylamide-2-methyl propane sulfonic acid sodium, Sodium styrene sulfonate, the allyloxy benzene sulfonic acid sodium salt, sodium acrylate, dimethyl diallyl ammonium chloride or methacrylic acid trimethyl ammonium chloride, in the described step (2), water-insoluble hard monomer is selected from vinylbenzene or methyl methacrylate, water-insoluble soft monomer is selected from butyl acrylate or vinyl acetate between to for plastic, and the water sensitivity monomer is selected from vinylformic acid hydroxyl methyl esters, hydroxy methyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester or methacrylic acid hydroxy butyl ester.
In the described step (2), the content of macromolecule emulsifier is 8～17% of water-insoluble hard monomer, water-insoluble soft monomer and the monomeric content summation of water sensitivity, and the monomeric content of described water sensitivity accounts for 8～17% of water-insoluble hard monomer, water-insoluble soft monomer and water sensitivity monomer summation.
In the described step (2), the content of macromolecule emulsifier is 10～15% of water-insoluble hard monomer, water-insoluble soft monomer and the monomeric content summation of water sensitivity, and the monomeric content of described water sensitivity accounts for 10～15% of water-insoluble hard monomer, water-insoluble soft monomer and water sensitivity monomer summation.
Described step (2) further comprises, with 3～6 hours time, water-insoluble hard monomer, water-insoluble soft monomer and the monomeric mixing solutions of water sensitivity is splashed in the macromolecule emulsion agent solution gradually.
In the described step (3), described metal-salt is selected from aluminium salt, magnesium salts or molysite, and described acid is selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or acetate.
Adopt preparation method of the present invention not only to save equipment input and energy consumption that spraying drying is brought, the more important thing is to utilize in the resulting redispersible polymer powder of chemical method and do not contain any inorganics, improve the redispersibility ability of polymer powder, improved the quality of polymer powder.Therefore, redispersible polymer disclosed by the invention has boundless application prospect in the cement-based material field.
Embodiment
Comparative Examples 1:
In the reactor that stirring, reflux condensing tube and thermometer are housed, add 800 weight parts (to call " part " in the following text) water, 10 parts of sodium lauryl sulphate and 0.5 part of Potassium Persulphate, under nitrogen protection, be warming up to 80 ℃.Then, in 3 hours, the mixed solution that will contain 35 parts of vinylbenzene, 50 parts of butyl acrylates, 15 parts of Hydroxyethyl acrylates, 0.1 part of Dodecyl Mercaptan adds in the reactor of constant temperature to 80 ℃ gradually, continues reaction 3 hours.Add ammoniacal liquor in the product that obtains, the pH value of regulating emulsion is 9.
Under the room temperature, 5% aqueous sulfuric acid being added in the above-mentioned resulting emulsion, is 2.5 until pH, and do not generate floss in the emulsion this moment, still is stabilising system.Emulsion after the drying, is ground and obtained polymer powder in baking oven.
Embodiment 1
In the reactor that stirring, reflux condensing tube and thermometer are housed, add 800 parts of water and 150 parts of Sodium styrene sulfonate, under nitrogen protection, be warming up to 75 ℃.After treating that Sodium styrene sulfonate is all dissolved, add 2.25 parts of ammonium persulphates, reacted 7 hours down at 75 ℃.Add ammoniacal liquor in the product that obtains, the pH value of regulating institute's synthetic macromolecule emulsifying agent sodium polystyrene sulfonate is 7, resin content about 15%.
In the reactor that stirring, reflux condensing tube and thermometer are housed, add 800 parts of water, 10 parts of macromolecule emulsifier sodium polystyrene sulfonates and 0.5 part of Potassium Persulphate, under nitrogen protection, be warming up to 80 ℃.Then, in 3 hours, the mixed solution that will contain 35 parts of polystyrene, 50 parts of butyl acrylates, 15 parts of Hydroxyethyl acrylates, 0.1 part of Dodecyl Mercaptan adds in the reactor of constant temperature to 80 ℃ gradually, continues reaction 3 hours.
Under the room temperature, 5% aqueous sulfuric acid being added in the above-mentioned resulting emulsion, is 2.5 until pH, generates floss this moment.After solid-liquid is separated, under 80 ℃, carry out the dry water yield until remnants less than 2%.At last, with dried product grind into powder, promptly obtain redispersible polymer powder.
Embodiment 2
In the reactor that stirring, reflux condensing tube and thermometer are housed, add 800 parts of water and 150 parts of methacrylic acid trimethyl ammonium chlorides, under nitrogen protection, be warming up to 75 ℃.After treating that the methacrylic acid trimethyl ammonium chloride all dissolves, add 2.25 parts of ammonium persulphates, reacted 7 hours down at 75 ℃.Add ammoniacal liquor in the product that obtains, the pH value of regulating institute's synthetic macromolecule emulsifying agent polymethyl acrylic acid trimethyl ammonium chloride is 7, resin content about 15%.
In the reactor that stirring, reflux condensing tube and thermometer are housed, add 800 parts of water, 5 parts of macromolecule emulsifier polymethyl acrylic acid trimethyl ammonium chlorides and 0.5 part of Potassium Persulphate, under nitrogen protection, be warming up to 80 ℃.Then, in 3 hours, the mixed solution that will contain 50 parts of polystyrene, 42 parts of butyl acrylates, 8 parts of Hydroxyethyl acrylates, 0.1 part of Dodecyl Mercaptan adds in the reactor of constant temperature to 80 ℃ gradually, continues reaction 3 hours.
Under the room temperature, the 5% aluminum chloride aqueous solution is added in the above-mentioned resulting emulsion, generate floss this moment.After solid-liquid is separated, under 80 ℃, carry out the dry water yield until remnants less than 2%.At last, with dried product grind into powder, promptly obtain redispersible polymer powder.
Embodiment 3
In the reactor that stirring, reflux condensing tube and thermometer are housed, add 800 parts of water and 150 parts of sodium allyl sulfonates, under nitrogen protection, be warming up to 75 ℃.After treating that sodium allyl sulfonate all dissolves, add 2.25 parts of ammonium persulphates, reacted 7 hours down at 75 ℃.Add ammoniacal liquor in the product that obtains, the pH value of regulating institute's synthetic macromolecule emulsifying agent polyene propyl sulfonic acid sodium is 7, resin content about 15%.
In the reactor that stirring, reflux condensing tube and thermometer are housed, add 800 parts of water, 15 parts of macromolecule emulsifier polyene propyl sulfonic acid sodium and 0.5 part of Potassium Persulphate, under nitrogen protection, be warming up to 80 ℃.Then, in 3 hours, the mixed solution that will contain 40 parts of polystyrene, 40 parts of vinyl acetate between to for plastics, 20 parts of hydroxyethyl methylacrylates, 0.1 part of Dodecyl Mercaptan adds in the reactor of constant temperature to 80 ℃ gradually, continues reaction 3 hours.
Under the room temperature, the 5% aluminum chloride aqueous solution is added in the above-mentioned resulting emulsion, generate floss this moment.After solid-liquid is separated, under 80 ℃, carry out the dry water yield until remnants less than 2%.At last, with dried product grind into powder, promptly obtain redispersible polymer powder.
Embodiment 4
In the reactor that stirring, reflux condensing tube and thermometer are housed, add 800 parts of water and 150 parts of sodium acrylates, under nitrogen protection, be warming up to 75 ℃.After treating that sodium acrylate all dissolves, add 2.25 parts of ammonium persulphates, reacted 7 hours down at 75 ℃.Add ammoniacal liquor in the product that obtains, the pH value of regulating institute's synthetic macromolecule emulsifying agent sodium polyacrylate is 7, resin content about 15%.
In the reactor that stirring, reflux condensing tube and thermometer are housed, add 800 parts of water, 20 parts of macromolecule emulsifier sodium polyacrylates and 0.5 part of Potassium Persulphate, under nitrogen protection, be warming up to 80 ℃.Then, in 3 hours, the mixed solution that will contain 55 parts of polymethylmethacrylates, 30 parts of butyl acrylates, 15 parts of vinylformic acid hydroxyl methyl esters, 0.1 part of Dodecyl Mercaptan adds in the reactor of constant temperature to 80 ℃ gradually, continues reaction 3 hours.Add ammoniacal liquor in the product that obtains, the pH value of regulating emulsion is 9.
Under the room temperature, 5% ferric chloride aqueous solutions is added in the above-mentioned resulting emulsion, generate floss this moment.After solid-liquid is separated, under 80 ℃, carry out the dry water yield until remnants less than 2%.At last, with dried product grind into powder, promptly obtain redispersible polymer powder.
Comparing embodiment 1 and Comparative Examples 1 can be found, adopt macromolecule emulsifier to replace common emulsifying agent, add 5% aqueous sulfuric acid and can obtain redispersible polymer powder, can save equipment input and energy consumption that the spraying drying of prior art is brought like this, the more important thing is to utilize in the resulting redispersible polymer powder of chemical method not contain any inorganics, improved the redispersibility ability of polymer powder.
The redispersible ability of the polymer powder that will obtain embodiment 1～4 and Comparative Examples 1 compares below.
The polymer powder that embodiment 1～4 and Comparative Examples 1 are obtained all grinds to form the particle of size less than 1mm, and the redispersible polymer powder after will grinding then adds in the 1%NaOH aqueous solution, and making its solid content is 10%.Mixture was stirred 30 minutes, left standstill then 24 hours.Cross 300 order filter clothes to remove throw out, collect filtered liquid, promptly get the redispersion emulsion, measure its solid content.
According to the solid content of redispersion emulsion, can calculate the redispersible degree of polymer powder with following formula:
Redispersible degree (%)=[solid content of redispersion emulsion (%)/10] * 100
Redispersible degree can be divided into following grade:
A level: 100% 〉=redispersible degree (%) 〉=80%
B level: 80%＞redispersible degree (%) 〉=40%
C level: 40%＞redispersible degree (%) 〉=10%
D level: 10%＞redispersible degree (%) 〉=0%
After measured, the redispersible degree of the polymer powder that obtains among the embodiment 1～4 all belongs to the A level, and the redispersible degree of the polymer powder that obtains in the Comparative Examples 1 belongs to the D level.Therefore, the present invention's redispersible of obtaining polymer powder obviously is better than Comparative Examples 1.The redispersible polymer powder that embodiment 1～4 obtains all can have boundless application prospect in the cement-based material field at pH 〉=5 o'clock redispersion in water.
Claims (9)
1. redispersible polymer powder, it is characterized in that, it is that water sensitivity monomer by water-insoluble hard monomer, water-insoluble soft monomer and hydroxyl forms by emulsion polymerization prepared in the presence of macromolecule emulsifier, wherein, described redispersible polymer powder can be at pH 〉=5 o'clock redispersion in water.
2. redispersible polymer powder as claimed in claim 1, it is characterized in that, described macromolecule emulsifier is cationic or anionic, described water-insoluble hard monomer is selected from vinylbenzene or methyl methacrylate, described water-insoluble soft monomer is selected from butyl acrylate or vinyl acetate between to for plastic, and described water sensitivity monomer is selected from vinylformic acid hydroxyl methyl esters, hydroxy methyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester or methacrylic acid hydroxy butyl ester.
3. redispersible polymer powder as claimed in claim 2, it is characterized in that described macromolecule emulsifier is polyene propyl sulfonic acid sodium, poly-2-acrylamide-2-methyl propane sulfonic acid sodium, sodium polystyrene sulfonate, polyene propoxy-benzene sulfonic acid sodium salt, sodium polyacrylate, Poly Dimethyl Diallyl Ammonium Chloride or polymethyl acrylic acid trimethyl ammonium chloride.
4. preparation method as any described redispersible polymer powder of claim 1-3 is characterized in that it may further comprise the steps:
(1) macromolecule emulsifier is synthetic: by solution polymerization, adopt water soluble starter, positively charged ion or anionic monomer polymerization are obtained macromolecule emulsifier;
(2) preparation of polymer emulsion: by letex polymerization, adopt water soluble starter, under the condition that the macromolecule emulsifier that obtains in step (1) exists, water-insoluble hard monomer, water-insoluble soft monomer and water sensitivity monomer polymerization are obtained polymer emulsion, wherein, the content of macromolecule emulsifier is 5～20% of water-insoluble hard monomer, water-insoluble soft monomer and water sensitivity monomer content summation, and the monomeric content of water sensitivity accounts for 5～20% of water-insoluble hard monomer, water-insoluble soft monomer content and water sensitivity monomer summation;
(3) breakdown of emulsion: add metal-salt or acid in the emulsion that in step (2), obtains, it is carried out breakdown of emulsion and obtains redispersible polymer powder.
5. preparation method as claimed in claim 4, it is characterized in that, in the described step (1), monomer is a sodium allyl sulfonate, 2-acrylamide-2-methyl propane sulfonic acid sodium, Sodium styrene sulfonate, the allyloxy benzene sulfonic acid sodium salt, sodium acrylate, dimethyl diallyl ammonium chloride or methacrylic acid trimethyl ammonium chloride, in the described step (2), water-insoluble hard monomer is selected from vinylbenzene or methyl methacrylate, water-insoluble soft monomer is selected from butyl acrylate or vinyl acetate between to for plastic, and the water sensitivity monomer is selected from vinylformic acid hydroxyl methyl esters, hydroxy methyl methacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester or methacrylic acid hydroxy butyl ester.
6. preparation method as claimed in claim 4, it is characterized in that, in the described step (2), the content of macromolecule emulsifier is 8～17% of water-insoluble hard monomer, water-insoluble soft monomer and the monomeric content summation of water sensitivity, and the monomeric content of described water sensitivity accounts for 8～17% of water-insoluble hard monomer, water-insoluble soft monomer and water sensitivity monomer summation.
7. preparation method as claimed in claim 6, it is characterized in that, in the described step (2), the content of macromolecule emulsifier is 10～15% of water-insoluble hard monomer, water-insoluble soft monomer and the monomeric content summation of water sensitivity, and the monomeric content of described water sensitivity accounts for 10～15% of water-insoluble hard monomer, water-insoluble soft monomer and water sensitivity monomer summation.
8. preparation method as claimed in claim 4, it is characterized in that, described step (2) further comprises, in 3～6 hours time, water-insoluble hard monomer, water-insoluble soft monomer and the monomeric mixed solution of water sensitivity is splashed in the macromolecule emulsion agent solution gradually.
9. preparation method as claimed in claim 4 is characterized in that, in the described step (3), described metal-salt is selected from aluminium salt, magnesium salts or molysite, and described acid is selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid or acetate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500794C (en) * | 2006-04-24 | 2009-06-17 | 淄博永麒化工技术开发有限公司 | Gas channeling preventing cement slurry for cementing oil field |
| CN101367899B (en) * | 2008-10-17 | 2010-09-08 | 广东同步化工股份有限公司 | Preparation method for silver drop-proof thermoplastic acrylic resin |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
| CN108570121A (en) * | 2017-03-07 | 2018-09-25 | 常州市五洲环保科技有限公司 | A kind of preparation method of the polymer support of pre-dispersed rubber chemicals |
| CN110627952A (en) * | 2019-09-19 | 2019-12-31 | 湖北工业大学 | Preparation method of high-adhesion hydroxyalkyl soap-free emulsion polymer |
-
2004
- 2004-07-09 CN CN 200410069567 patent/CN1279066C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500794C (en) * | 2006-04-24 | 2009-06-17 | 淄博永麒化工技术开发有限公司 | Gas channeling preventing cement slurry for cementing oil field |
| CN101367899B (en) * | 2008-10-17 | 2010-09-08 | 广东同步化工股份有限公司 | Preparation method for silver drop-proof thermoplastic acrylic resin |
| CN108570121A (en) * | 2017-03-07 | 2018-09-25 | 常州市五洲环保科技有限公司 | A kind of preparation method of the polymer support of pre-dispersed rubber chemicals |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
| CN110627952A (en) * | 2019-09-19 | 2019-12-31 | 湖北工业大学 | Preparation method of high-adhesion hydroxyalkyl soap-free emulsion polymer |
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| Publication number | Publication date |
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| CN1279066C (en) | 2006-10-11 |
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