CN104693345A - Polymer dispersion and preparation method thereof - Google Patents
Polymer dispersion and preparation method thereof Download PDFInfo
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- CN104693345A CN104693345A CN201510143573.4A CN201510143573A CN104693345A CN 104693345 A CN104693345 A CN 104693345A CN 201510143573 A CN201510143573 A CN 201510143573A CN 104693345 A CN104693345 A CN 104693345A
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Abstract
The invention discloses a polymer dispersion and a preparation method thereof. The polymer dispersion is obtained through the soap-free emulsion copolymerization technology. The polymer dispersion comprises a negative ion monomer, a non-ionic monomer, a pH buffering agent, an initiator, an antalkali and water, wherein the negative ion monomer accounts for 3-10 parts of the raw materials, the non-ionic monomer accounts for 10-25 parts of the raw materials, the pH buffering agent accounts for 0.3-1.0 part of the raw materials, the initiator accounts for 0.3-2 parts of the raw materials, and the water accounts for 100 parts of the raw materials. A proper amount of the antalkali is used for adjusting the pH value of a reaction system to range from 6.0 to 9.0. The obtained polymer dispersion is used as a dust depressor, an effective shell can be formed on the surface of dust, and the construction safety and application safety of the polymer dispersion are higher. The polymer dispersion is applied as the chemical dust depressor, can be diluted with water to be sprayed for use, and is good in overall performance, safe and environmentally friendly.
Description
Technical field
The present invention relates to the chemical dust suppressant in urban road treating flour dust field, particularly a kind of polymeric dispersions and preparation method thereof.
Background technology
City size constantly expands, working-yard is in full flourish, and motor vehicle number increases fast, and material stockyard, concrete-agitating, gurry are stacked and be seen everywhere.City dust pollutes and becomes increasingly conspicuous, and haze weather is constant.In air, aerodynamic diameter is less than the fine particle (PM2.5) that the pellet (PM10) of 10 μm and aerodynamic diameter be less than 2.5 μm and is referred to as micronic dust in the present invention.Their easy enriching heavy metal ions, organic oxygen compound, bacterium and virus, PM2.5 particle directly enters bronchiole, alveolar because of nasal cavity and the unable stop of throat, and very big to harm, outstanding behaviours is teratogenesis, carcinogenic, mutagenesis.
The hydraulic dust-removing taking watering as form of construction work is simple, but because of the surface tension of water high, fine solid particle not easily soaks, and dust reduction rate generally only has 28%, and winter easily freezes, and evaporation in summer is fast, validity period is short.Dust, local depositing dust are just shifted in dust removal by ventilation, are not dust suppressions.It is effective that paulin hides, but fundamentally do not solve the problem of dust from flying, is not suitable for big area and uses.
In recent years, the dust Control effect of chemical dust suppressant is paid attention to gradually.According to action principle, chemical dust suppressant can be divided three classes: (1) humidity-preserving type.Sodium lauryl sulphate, fatty alcohol-polyoxyethylene ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene ether provide necessary wetting ability, and glycerol, ethylene glycol, glycol ether, calcium chloride and magnesium chloride etc. provide moisture absorption, humidity-holding effect.This dust-inhibitor often reduces the useful effect cycle because of volatilization and rain drop erosion.(2) binding type.Tiny dust granules is bonded to the larger particle of particle diameter, micronic dust can be suppressed to fly upward, reduce the chance that micronic dust enters lung.Main raw material is the waste liquid of papermaking and alcohol industry, waste residue and industrial slag wet goods, easily causes secondary pollution.(3) film-forming type.Natural polymer and synthesis polymer are soaking micronic dust, on the basis of adsorbing, and formed the shell with some strength by cohesion, its Film Morphology is similar to tarpaulin, and anti-dust effect is better than other types.
Starch, Mierocrystalline cellulose and vegetable polysaccharides and various deep processing product thereof belong to natural high moleculer eompound.The polymkeric substance of the monomers such as vinylformic acid, acrylate, vinyl acetate and isocyanic ester, and the cross-linking products of the oligopolymer such as epoxy resin and urea-formaldehyde resin all belongs to synthetic macromolecular compound.Macromolecular compound has the ability of film forming, can show weather-proof effect after crosslinked, solidification.CN103265990, CN102585770 and CN103305187 etc. disclose starch, derivatived cellulose, acrylic copolymer are the dust-inhibitor of main film forming substance, with the use of sodium-chlor, trisodium phosphate, copper sulfate, glycerine, sodium lauryl sulphate or alkylphenol polyoxyethylene, while improving use properties, also inherit the shortcoming such as the corrodibility of metal ion, the volatility of low molecule organic matter.
A kind of polymeric dispersions of invention and preparation method thereof.This dust-inhibitor is that starting monomer is prepared by soap-free silicone-acrylic emulsion technology by anionic monomers and non-ionic monomer, and working security and application security are better than traditional polymer emulsion system.Compared to water-soluble polymers dust-inhibitor, the shell that it is formed on dust particale surface has better resistance to erodible.
Summary of the invention
The object of the present invention is to provide a kind of polymeric dispersions and preparation method thereof.This polymeric dispersions with anionic monomers and non-ionic monomer for starting monomer is prepared by soap-free silicone-acrylic emulsion technology, first, the equal tool of the low molecule raw material selected is reactive, and final product containing volatility low molecule organic matter, does not have corrodibility high volence metal ion yet; Secondly, choose appropriate anionic monomers, nonionic starting monomer as reactive emulsifier, for system provides enough emulsification, stably dispersing effect, and by the selection of copolymerization temperature, thus make system need not use traditional low molecule emulsifying agent, the polymeric dispersions obtained as dust-inhibitor, can micronic dust surface formed effective shell, its working security and application security higher.Be applied as chemical dust suppressant, use can be sprayed, good combination property, safety and environmental protection by dilute with water.
Technical scheme of the present invention is:
A kind of polymeric dispersions, this dispersion is prepared from by soap-free silicone-acrylic emulsion technology, and raw material comprises anionic monomers, non-ionic monomer, pH buffer reagent, initiator and water, and its proportioning raw materials is:
Described raw material also comprises alkaline neutraliser, and the amount of alkaline neutraliser is regulate the pH value of reaction system to 6.0-9.0.
Described anionic monomers is one or more in unsaturated carboxylic acid monomer and unsaturated sulfonic acid or its sodium salt anionoid monomer.Described unsaturated carboxylic acid monomer is specially vinylformic acid, methacrylic acid; Unsaturated sulfonic acid or its sodium salt anionoid monomer are specially sodium vinyl sulfonate, sodium allyl sulfonate, 2-acrylamide-2-methyl propane sulfonic.
Described non-ionic monomer is one or more in butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, hydroxyethyl methylacrylate, methoxy polyoxyethylene ether metacrylic acid ester and vinylbenzene.
Described pH buffer reagent is one or both in sodium bicarbonate, sodium carbonate and sodium-acetate.
Described initiator is one or both in Potassium Persulphate, ammonium persulphate and hydrogen peroxide/sulfuric acid ferrous iron, and add as an aqueous solution, the mass percentage concentration of solution is 5 ~ 10%.
Described alkaline neutraliser is one or both in ammoniacal liquor, 2-methylol Isopropylamine and 2-hydroxy ethoxy ethamine.
Described water is distilled water or tap water.
The preparation method of described polymeric dispersions, comprises the following steps:
(1) stock liquid is prepared: when anionic monomers is unsaturated carboxylic acid monomer, mixed with non-ionic monomer by unsaturated carboxylic acid monomer, for subsequent use as stock liquid; When anionic monomers be unsaturated sulfonic acid or its sodium salt anionoid monomer time, consisting of of stock liquid is only non-ionic monomer, adds in unsaturated sulfonic acid or its step of sodium salt anionoid monomer below (3); When anionic monomers be unsaturated carboxylic acid monomer and unsaturated sulfonic acid or its sodium salt anionoid monomer time, unsaturated carboxylic acid monomer is mixed with non-ionic monomer, for subsequent use as stock liquid, add in unsaturated sulfonic acid or its step of sodium salt anionoid monomer below (3);
(2) in the reactor that agitator, thermometer, dropping funnel and nitrogen conduit be housed, add pH buffer reagent and water, open and stir, nitrogen or argon replaces 10 ~ 30 minutes, heating in water bath heats up;
(3) when being warming up to 60-90 DEG C, when anionic monomers comprises unsaturated sulfonic acid or its sodium salt anionoid monomer, add initiator solution, unsaturated sulfonic acid or its sodium salt anionoid monomer, then add the stock liquid in step (1); Or, when anionic monomers does not comprise unsaturated sulfonic acid or its sodium salt anionoid monomer, add initiator solution, then add the stock liquid in step (1);
The feed postition of stock liquid is for adding or drip continuously in batches;
(4) after stock liquid adds completely, at 60-100 DEG C of insulation 0.5-2.5 hour;
(5) be cooled to room temperature, regulate the pH value of reaction system to 6.0-9.0 with alkaline neutraliser, discharging, is polymeric dispersions of the present invention.
In described step (3), the temperature of polyreaction, preferred 70-90 DEG C.
In described step (3), the time for adding of stock liquid is 2.0-4.0 hour.
In described step (4), the temperature of insulation, preferred 80-95 DEG C.
In described step (5), regulate the pH value of reaction system, preferred 7.0-9.0.
The application method of described polymeric dispersions, as chemical dust suppressant, according to quality than polymeric dispersions: the ratio mixing of water=1:10-1000 injects sprinker or spraying vehicle, according to 1.0-2.5kg/m
2the consumption of road, sprays the surface uniform of this dust-inhibitor diluent to urban road, sidewalk.
Described be preferably polymeric dispersions with the blending ratio of water and dilute by 1:20-500 and water.
The invention has the beneficial effects as follows:
(1) polymeric dispersions of the present invention is prepared by soap-free silicone-acrylic emulsion technology, and not containing volatility low molecule organic matters such as glycerine, ethylene glycol, residual oil, do not have secondary pollution, environmental safety is good; Copolymerization temperature is suitable, can avoid system gelation, prevent stability from declining, and can ensure that again the composition of multipolymer is stablized, contribute to stable system and weathering quality.
(2) polymeric dispersions of the present invention is prepared by soap-free silicone-acrylic emulsion technology, and not containing induced by alkyl hydroxybenzene emulsifying agent, working security and application security are better than traditional polymer emulsion system.
(3) polymeric dispersions of the present invention is not containing the high volence metal ion such as copper, calcium, aluminium, there is not etching problem to metal, vehicular traffic, working security and safety in utilization reliable.
(4) polymeric dispersions of the present invention forms shell on dust particale surface, and it is resistance to is erodiblely better than water-soluble polymers, can meet different application requiring better.
(5) polymeric dispersions of the present invention is used for urban road dust suppression, effectively can suppress dust from flying equally in places such as resident's rubbish district, construction site, mineral processing.
(6) preparation technology of the present invention is easy, does not relate to High Temperature High Pressure, does not have three waste discharge, is suitable for large-scale promotion and uses.
Embodiment
The present invention is further illustrated below in conjunction with embodiment:
Embodiment one
Mass fraction in gram, 3g vinylformic acid is as anionic monomers, and 18g butyl acrylate, 5g methyl methacrylate and 2g hydroxyethyl methylacrylate, as non-ionic monomer, mix rear for subsequent use as stock liquid.In the reactor that agitator, thermometer, dropping funnel and nitrogen conduit be housed, add 0.4g sodium bicarbonate and 100g distilled water, open and stir, with argon replaces 15 minutes.During heating in water bath to 80 DEG C, add persulfate aqueous solution and 4g sodium vinyl sulfonate that 8g mass concentration is 5%.After temperature-stable, drip aforesaid stock liquid continuously by dropping funnel, control rate of addition, dropwised in 3 hours.System is warming up to 85 DEG C, is incubated 1.5 hours, under the effect of stirring, system is down to room temperature.Alkaline neutraliser is made, regulation system pH value to 7.8 with ammoniacal liquor.Stir, discharging, be a kind of polymeric dispersions of the present invention.During onsite application, with water in mass ratio 1:50 dilute, then inject sprinker, carry out sprinkling dust suppression.
Measure film forming thickness: taking 150 gram particle degree is that to add to diameter be compacting in the culture dish of 12cm to 1500 object urban road micronic dusts.The tap water of the polymeric dispersions of embodiment by 50 times of quality is diluted, with 1.5kg/m
2consumption be sprayed to above-mentioned sample, 25 DEG C of freeze-day with constant temperature.Shell is peeled off, measures film forming layer thickness with slide calliper rule.
Evaluate performance of keeping humidity: taking 150 gram particle degree is that 1500 object urban road micronic dusts add to diameter and are compacting in the culture dish of 12cm, weigh.The tap water of the polymeric dispersions of embodiment by 50 times of quality is diluted, with 1.5kg/m
2consumption be sprayed to above-mentioned sample, weigh.Forced air drying in 40 DEG C of thermostat containers, evaluates moisture-retaining capacity with the forced air drying water retention of 3 hours.Moisture-retaining capacity strengthens, and the tap density of dust increases, and suppresses the ability of flying upward to improve.
Evaluate resistance to water erosion performance: sample preparation is identical with the method for mensuration film forming thickness with spray method.Sample is after 25 DEG C of freeze-day with constant temperature, and with the mode simulating nature precipitation sprayed, after soaking 12 hours, incline and excessive moisture, 25 DEG C of freeze-day with constant temperature 24 are little of sample surfaces substantially dry.Observe, record film-forming state now, using without visible crack as criterion up to standard.
Evaluate resistance to weathering: sample preparation is identical with the method for mensuration film forming thickness with spray method.Sample at 25 DEG C of freeze-day with constant temperature, weigh.The mass loss rate after 1.0h is closely purged continuously as weathering quality evaluation index to simulate strong breeze power.This index reflects the crust effect of dust-inhibitor, also embodies anti-dust effect.The shell that mass loss rate is low, compactness is strong, film-formation result is good, improve the sealing ability of dust-inhibitor to dust, anti-dust effect improves naturally.
Embodiment two
Implementation step is with embodiment one, and difference is: as non-ionic monomer, and 2g hydroxyethyl methylacrylate replaces with 2g methoxy polyoxyethylene ether metacrylic acid ester (pfpe molecule amount 500); Polymeric reaction temperature is 85 DEG C.
Method of evaluating performance is with embodiment one.
Embodiment three
Mass fraction in gram, it is for subsequent use 3g vinylformic acid, 16g butyl acrylate and 4g vinylbenzene to be mixed in proportion into stock liquid.In the reactor that agitator, thermometer, dropping funnel and nitrogen conduit be housed, add 0.3g sodium carbonate and 100g distilled water, open and stir, with nitrogen replacement 20 minutes.During heating in water bath to 80 DEG C, adding 10g mass concentration is 5% persulfate aqueous solution, 2g sodium allyl sulfonate and 2g2-acrylamide-2-methyl propane sulfonic.After temperature-stable, drip stock liquid continuously by dropping funnel, control rate of addition, dropwised in 3 hours.System is warming up to 85 DEG C, is incubated 1.5 hours, under the effect of stirring, system is down to room temperature.With 2-methylol Isopropylamine regulation system pH value.Stir further, discharging, is a kind of polymeric dispersions of the present invention.During onsite application, press 1:50 with water and dilute, then inject sprinker, carry out sprinkling dust suppression.
Method of evaluating performance is with embodiment one.
Embodiment four
Implementation step is with embodiment three, and difference is: anionic monomers vinylformic acid such as to replace with at the methacrylic acid of quality.
Method of evaluating performance is with embodiment one.
The character of subordinate list Inventive polymers dispersion and performance
| Embodiment one | Embodiment two | Embodiment three | Embodiment four | |
| Physical condition | Milky white liquid | Milky white liquid | Milky white liquid | Milky white liquid |
| PH value | 7.8 | 7.8 | 7.5 | 7.7 |
| Viscosity (25 DEG C, mPas) | 620 | 670 | 720 | 780 |
| Film forming thickness (cm) | 2.9 | 2.5 | 3.0 | 2.7 |
| Performance of keeping humidity (%) | 45 | 40 | 33 | 37 |
| Resistance to water erosion performance | Without visible crack | Without visible crack | Without visible crack | Without visible crack |
| Resistance to weathering (%) | 1.7 | 1.9 | 2.2 | 2.6 |
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention is only limitted to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to the present invention by submitted to claims determination scope of patent protection.
Unaccomplished matter of the present invention is known technology.
Claims (10)
1. a polymeric dispersions, be is characterized by this dispersion and is prepared from by soap-free silicone-acrylic emulsion technology, and raw material comprises anionic monomers, non-ionic monomer, pH buffer reagent, initiator and water, and its proportioning raw materials is:
Described raw material also comprises alkaline neutraliser, and the amount of alkaline neutraliser is regulate the pH value of reaction system to 6.0-9.0;
Described anionic monomers is one or more in unsaturated carboxylic acid monomer and unsaturated sulfonic acid or its sodium salt anionoid monomer;
Described water is distilled water or tap water;
Described non-ionic monomer is one or more in butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, hydroxyethyl methylacrylate, methoxy polyoxyethylene ether metacrylic acid ester and vinylbenzene.
2. polymeric dispersions as claimed in claim 1, is characterized by described unsaturated carboxylic acid monomer and is specially vinylformic acid, methacrylic acid; Unsaturated sulfonic acid or its sodium salt anionoid monomer are specially sodium vinyl sulfonate, sodium allyl sulfonate, 2-acrylamide-2-methyl propane sulfonic.
3. polymeric dispersions as claimed in claim 1, it is characterized by described pH buffer reagent is one or both in sodium bicarbonate, sodium carbonate and sodium-acetate.
4. polymeric dispersions as claimed in claim 1, it is characterized by described initiator is one or both in Potassium Persulphate, ammonium persulphate and hydrogen peroxide/sulfuric acid ferrous iron, and add as an aqueous solution, the mass percentage concentration of solution is 5 ~ 10%.
5. polymeric dispersions as claimed in claim 1, it is characterized by described alkaline neutraliser is one or both in ammoniacal liquor, 2-methylol Isopropylamine and 2-hydroxy ethoxy ethamine.
6. the preparation method of polymeric dispersions as claimed in claim 1, is characterized by and comprise the following steps:
(1) stock liquid is prepared: when anionic monomers is unsaturated carboxylic acid monomer, mixed with non-ionic monomer by unsaturated carboxylic acid monomer, for subsequent use as stock liquid; When anionic monomers be unsaturated sulfonic acid or its sodium salt anionoid monomer time, consisting of of stock liquid is only non-ionic monomer, adds in unsaturated sulfonic acid or its step of sodium salt anionoid monomer below (3); When anionic monomers be unsaturated carboxylic acid monomer and unsaturated sulfonic acid or its sodium salt anionoid monomer time, unsaturated carboxylic acid monomer is mixed with non-ionic monomer, for subsequent use as stock liquid, add in unsaturated sulfonic acid or its step of sodium salt anionoid monomer below (3);
(2) in the reactor that agitator, thermometer, dropping funnel and nitrogen conduit be housed, add pH buffer reagent and water, open and stir, nitrogen or argon replaces 10 ~ 30 minutes, heating in water bath heats up;
(3) when being warming up to 60-90 DEG C, when anionic monomers comprises unsaturated sulfonic acid or its sodium salt anionoid monomer, add initiator solution, unsaturated sulfonic acid or its sodium salt anionoid monomer, then add the stock liquid in step (1); Or, when anionic monomers does not comprise unsaturated sulfonic acid or its sodium salt anionoid monomer, add initiator solution, then add the stock liquid in step (1);
The feed postition of stock liquid is for adding or drip continuously in batches;
(4) after stock liquid adds completely, at 60-100 DEG C of insulation 0.5-2.5 hour;
(5) be cooled to room temperature, regulate the pH value of reaction system to 6.0-9.0 with alkaline neutraliser, discharging, is polymeric dispersions of the present invention.
7. the preparation method of polymeric dispersions as claimed in claim 6, it is characterized by described step (3), the time for adding of stock liquid is 2.0-4.0 hour.
8. the preparation method of polymeric dispersions as claimed in claim 6, is characterized by described step (4), the temperature of insulation, preferred 80-95 DEG C.
9. the application method of polymeric dispersions as claimed in claim 1, is characterized by as chemical dust suppressant, according to quality than polymeric dispersions: the ratio mixing of water=1:10-1000 injects sprinker or spraying vehicle, according to 1.0-2.5kg/m
2the consumption of road, sprays the surface uniform of this dust-inhibitor diluent to urban road, sidewalk.
10. the application method of polymeric dispersions as claimed in claim 9, is characterized by and be describedly preferably polymeric dispersions with blending ratio that is water and dilute by 1:20-500 and water.
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| CN105037613A (en) * | 2015-08-20 | 2015-11-11 | 陈燕 | Polymer dispersion |
| CN105504130A (en) * | 2016-01-21 | 2016-04-20 | 山西大学 | Compound type dust inhibiting and sand solidifying agent and preparation method thereof |
| CN105949368A (en) * | 2016-05-31 | 2016-09-21 | 西北师范大学 | Multi-responsiveness amphiphilic polymer microparticle and preparation method thereof |
| CN106008791A (en) * | 2016-06-22 | 2016-10-12 | 加翎加（天津）环境科技有限公司 | Mineral powder suppressant and preparing method thereof |
| CN106008851A (en) * | 2016-06-22 | 2016-10-12 | 加翎加（天津）环境科技有限公司 | Construction dust depressor and preparation method thereof |
| CN107033276A (en) * | 2017-05-03 | 2017-08-11 | 上海巍盛化工科技有限公司 | A kind of dust Control agent of use polymerisable emulsifier |
| CN108929657A (en) * | 2018-08-20 | 2018-12-04 | 加翎加（天津）环境科技有限公司 | A kind of miberal powder dust suppressant and preparation method thereof |
| CN109666465A (en) * | 2017-10-17 | 2019-04-23 | 中石化石油工程技术服务有限公司 | A kind of preparation method and drilling fluid of drilling fluid latex sealing agent |
| CN113185631A (en) * | 2021-04-28 | 2021-07-30 | 甘肃五环公路工程有限公司 | Pavement dust suppressant and preparation method thereof |
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| CN105037613A (en) * | 2015-08-20 | 2015-11-11 | 陈燕 | Polymer dispersion |
| CN105504130A (en) * | 2016-01-21 | 2016-04-20 | 山西大学 | Compound type dust inhibiting and sand solidifying agent and preparation method thereof |
| CN105949368A (en) * | 2016-05-31 | 2016-09-21 | 西北师范大学 | Multi-responsiveness amphiphilic polymer microparticle and preparation method thereof |
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| CN106008791A (en) * | 2016-06-22 | 2016-10-12 | 加翎加（天津）环境科技有限公司 | Mineral powder suppressant and preparing method thereof |
| CN106008851A (en) * | 2016-06-22 | 2016-10-12 | 加翎加（天津）环境科技有限公司 | Construction dust depressor and preparation method thereof |
| CN106008851B (en) * | 2016-06-22 | 2018-07-13 | 加翎加（天津）环境科技有限公司 | A kind of construction dust suppressant and preparation method thereof |
| CN107033276A (en) * | 2017-05-03 | 2017-08-11 | 上海巍盛化工科技有限公司 | A kind of dust Control agent of use polymerisable emulsifier |
| CN109666465A (en) * | 2017-10-17 | 2019-04-23 | 中石化石油工程技术服务有限公司 | A kind of preparation method and drilling fluid of drilling fluid latex sealing agent |
| CN109666465B (en) * | 2017-10-17 | 2021-06-15 | 中石化石油工程技术服务有限公司 | Preparation method of latex plugging agent for drilling fluid and drilling fluid |
| CN108929657A (en) * | 2018-08-20 | 2018-12-04 | 加翎加（天津）环境科技有限公司 | A kind of miberal powder dust suppressant and preparation method thereof |
| CN113185631A (en) * | 2021-04-28 | 2021-07-30 | 甘肃五环公路工程有限公司 | Pavement dust suppressant and preparation method thereof |
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