CN104693345B - A kind of polymeric dispersions and preparation method thereof - Google Patents
A kind of polymeric dispersions and preparation method thereof Download PDFInfo
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- CN104693345B CN104693345B CN201510143573.4A CN201510143573A CN104693345B CN 104693345 B CN104693345 B CN 104693345B CN 201510143573 A CN201510143573 A CN 201510143573A CN 104693345 B CN104693345 B CN 104693345B
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Abstract
The present invention is a kind of polymeric dispersions and preparation method thereof.This polymeric dispersions is prepared from by soap-free silicone-acrylic emulsion technology, and raw material includes anionic monomers, non-ionic monomer, pH buffer agent, initiator, antalkali and water, and its raw material number proportioning is: anionic monomers: 3 10；Non-ionic monomer: 10 25；PH buffer agent: 0.3 1.0；Initiator: 0.3 2；Water: 100；Described raw material also includes antalkali, and the amount of antalkali is that the pH value of regulation reaction system is to 6.0 9.0.The polymeric dispersions that the present invention obtains, as dust suppressant, can form effective shell on micronic dust surface, and its working security and application security are higher.It is applied as chemical dust suppressant, it is possible to dilute with water sprays and uses, good combination property, safety and environmental protection.
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.
Background technology
City size constantly expands, job site is in full flourish, and motor vehicle number quickly increases, material stockyard, coagulation
Soil stirring, gurry are stacked and are seen everywhere.City dust pollutes and becomes increasingly conspicuous, and haze weather is constant.Air force in air
Learn diameter and be less than the fine particle (PM2.5) of 2.5 μm less than the pellet (PM10) of 10 μm and aerodynamic diameter
It is referred to as micronic dust in the present invention.They easy enriching heavy metal ions, organic oxygen compound, antibacterial and virus, PM2.5 granule is because of nose
Chamber and the unable stop of throat and be directly entered bronchioles, alveolar, very big to harm, outstanding behaviours be teratogenesis, carcinogenic, cause
Sudden change.
Hydraulic dust-removing with watering as form of construction work is simple, but because the surface tension of water is high, fine solid particle is difficult to profit
Wet, dust reduction rate typically only 28%, and easily freeze winter, evaporation in summer is fast, effect duration is short.Powder is simply shifted in dust removal by ventilation
Dirt, locally depositing dust, be not dust suppression.It is effective that paulin hides, but the most fundamentally solves the problem of dust from flying, is not suitable for
Large area uses.
In recent years, the dust Control effect of chemical dust suppressant is gradually paid attention to.According to action principle, chemical dust suppressant can
To be divided three classes: (1) humidity-preserving type.Sodium lauryl sulphate, fatty alcohol-polyoxyethylene ether, sodium alkyl benzene sulfonate, alkyl phenol polyoxy
Changing the wettability that vinyl Ether provides necessary, glycerol, ethylene glycol, diglycol, calcium chloride and magnesium chloride etc. provide to be inhaled
Wet, moistening effect.This dust suppressant often reduces the useful effect cycle because of volatilization and rain drop erosion.(2) binding type.Will be thin
Little dust granules is bonded to the granule that particle diameter is bigger, micronic dust can be suppressed to fly upward, reduce micronic dust enter pulmonary chance.Mainly
Raw material is papermaking and the waste liquid of alcohol industry, waste residue and surfactant etc., easily causes secondary pollution.(3) film-forming type.Natural
Macromolecule and synthesis macromolecule, on the basis of to micronic dust moistening, absorption, form the shell with some strength by cohesion
Layer, its Film Morphology is similar to tarpaulin, and anti-dust effect is better than other types.
Starch, cellulose and vegetable polysaccharides and various deep processing product thereof belong to natural polymer.Acrylic acid, third
The polymer of the monomers such as olefin(e) acid ester, vinylacetate and isocyanates, and the friendship of the oligomer such as epoxy resin and Lauxite
Co-product belongs to synthetic macromolecular compound.Macromolecular compound has the ability of film forming, cross-link, solidify after can show
Go out weather-proof effect.CN103265990, CN102585770 and CN103305187 etc. disclose starch, cellulose derivative, third
Olefin(e) acid copolymer is the dust suppressant of main film forming substance, with the use of sodium chloride, sodium pyrophosphate, copper sulfate, glycerol, dodecane
Base sodium sulfate or alkylphenol polyoxyethylene, while improving serviceability, also inherit the corrosivity of metal ion, low point
The shortcomings such as the organic volatility of son.
A kind of polymeric dispersions of invention and preparation method thereof.This dust suppressant by anionic monomers and non-from
Sub-property monomer is that starting monomer is prepared by soap-free silicone-acrylic emulsion technology, and working security and application security are better than traditional gathering
Compound emulsion system.Compared to water-soluble polymer dust suppressant, the shell that it is formed on dust particale surface has the most water-fast
Erosion property.
Summary of the invention
It is an object of the invention to provide a kind of polymeric dispersions and preparation method thereof.This polymeric dispersions with the moon from
Sub-property monomer and non-ionic monomer are that starting monomer is prepared by soap-free silicone-acrylic emulsion technology, and first, the low molecule of selection is former
Material all has reactivity, and final product does not contains volatility low molecule organic matter, does not has corrosivity high volence metal ion yet；Secondly,
Choose appropriate anionic monomers, nonionic starting monomer as reactive emulsifier, provide enough breasts for system
Change, stably dispersing effect, and by the selection of copolymerization temperature, so that system need not use traditional low molecule emulsifying agent,
The polymeric dispersions arrived, as dust suppressant, can form effective shell, its working security and application peace on micronic dust surface
Full property is higher.It is applied as chemical dust suppressant, it is possible to dilute with water sprays and uses, good combination property, safety and environmental protection.
The technical scheme is that
A kind of polymeric dispersions, this dispersion is prepared from by soap-free silicone-acrylic emulsion technology, and raw material includes anion
Property monomer, non-ionic monomer, pH buffer agent, initiator and water, its proportioning raw materials is:
Described raw material also includes antalkali, and the amount of antalkali is that the pH value of regulation reaction system is to 6.0-
9.0。
Described anionic monomers is unsaturated carboxylic acid monomer and unsaturated sulfonic acid or its sodium salt anionic monomers
In one or more.Described unsaturated carboxylic acid monomer is specially acrylic acid, methacrylic acid；Unsaturated sulfonic acid or its sodium salt
Anionoid monomer is specially sodium vinyl sulfonate, sodium allylsulfonate, 2-acrylamide-2-methyl propane sulfonic.
Described non-ionic monomer is butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, methacrylic acid
One or more in hydroxyl ethyl ester, methoxy polyoxyethylene ether metacrylic acid ester and styrene.
Described pH buffer agent is one or both in sodium bicarbonate, sodium carbonate and sodium acetate.
Described initiator is one or both in potassium peroxydisulfate, Ammonium persulfate. and hydrogen peroxide/sulfuric acid ferrous iron, with water
Solution form adds, and the mass percentage concentration of solution is 5～10%.
Described antalkali is one or both in ammonia, 2-methylol 2-aminopropane. 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) prepare material liquid: when anionic monomers is unsaturated carboxylic acid monomer, by unsaturated carboxylic acid monomer with non-from
Sub-property monomer mix homogeneously, standby as material liquid；When anionic monomers is unsaturated sulfonic acid or its sodium salt anionic property
During monomer, material liquid consist of only non-ionic monomer, unsaturated sulfonic acid or its sodium salt anionic monomers later
Step (3) in add；When anionic monomers is unsaturated carboxylic acid monomer and unsaturated sulfonic acid or its sodium salt anionic property
During monomer, unsaturated carboxylic acid monomer is mixed homogeneously with non-ionic monomer, standby as material liquid, unsaturated sulfonic acid or its sodium
Salt anionic monomers adds in step (3) below；
(2) in the reactor equipped with agitator, thermometer, Dropping funnel and nitrogen conduit, pH buffer agent and water are added,
Opening stirring, nitrogen or argon to replace 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 anionic monomers
Time, add initiator solution, unsaturated sulfonic acid or its sodium salt anionic monomers, be subsequently adding the material liquid in step (1)；
Or, when anionic monomers does not comprise unsaturated sulfonic acid or its sodium salt anionic monomers, add initiator solution, so
Material liquid in rear addition step (1)；
The feed postition of material liquid is for being dividedly in some parts or dripping continuously；
(4), after material liquid is added completely into, it is incubated 0.5-2.5 hour at 60-100 DEG C；
(5) be cooled to room temperature, with antalkali regulation reaction system pH value to 6.0-9.0, discharging, be the present invention
Polymeric dispersions.
In described step (3), the temperature of polyreaction, preferably 70-90 DEG C.
In described step (3), the time for adding of material liquid is 2.0-4.0 hour.
In described step (4), the temperature of insulation, preferably 80-95 DEG C.
In described step (5), the pH value of regulation reaction system, preferably 7.0-9.0.
The application process of described polymeric dispersions, as chemical dust suppressant, according to quality than polymeric dispersions: water
The ratio mixing of=1:10-1000 injects sprinkler or sprinkling wagon, according to 1.0-2.5kg/m2The consumption of road, by this dust suppressant
Diluent uniformly sprays to the surface of urban road, sidewalk.
The described mixed proportion with water is preferably polymeric dispersions and dilutes with water by 1:20-500.
The invention has the beneficial effects as follows:
(1) polymeric dispersions of the present invention is prepared by soap-free silicone-acrylic emulsion technology, without glycerol, ethylene glycol, residual oil
Etc. volatility low molecule organic matter, not having secondary pollution, environmental safety is good；Copolymerization temperature is suitable, has both been avoided that system was coagulated
Gel, prevents stability from declining, and can guarantee that again the composition of copolymer is stable, contributes to stable system and weathering quality.
(2) polymeric dispersions of the present invention is prepared by soap-free silicone-acrylic emulsion technology, without induced by alkyl hydroxybenzene emulsifying agent, executes
Work safety and application security are better than traditional polymer emulsion system.
(3) polymeric dispersions of the present invention does not contains the high volence metal ions such as copper, calcium, aluminum, to metal, vehicular traffic not
There is etching problem, working security and safety in utilization reliable.
(4) polymeric dispersions of the present invention forms shell on dust particale surface, and its impact water in corrosion resistance is better than water-soluble poly
Compound, can preferably meet different application requirements.
(5) polymeric dispersions of the present invention is used for urban road dust suppression, adds at resident's rubbish district, construction site, mineral
The places such as work the most effectively suppress dust from flying.
(6) preparation technology of the present invention is easy, is not related to High Temperature High Pressure, does not has three waste discharge, is suitable to large-scale promotion and makes
With.
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment:
Embodiment one
In gram, 3g acrylic acid is as anionic monomers, 18g butyl acrylate, 5g methyl methacrylate for mass fraction
Ester and 2g hydroxyethyl methylacrylate are as non-ionic monomer, standby as material liquid after mix homogeneously.To equipped with agitator,
The reactor of thermometer, Dropping funnel and nitrogen conduit adds 0.4g sodium bicarbonate and 100g distilled water, opens stirring, with argon
Gas is replaced 15 minutes.When heating in water bath is to 80 DEG C, add persulfate aqueous solution and 4g vinyl sulphur that 8g mass concentration is 5%
Acid sodium.After temperature stabilization, dripped aforesaid material liquid continuously by Dropping funnel, control rate of addition, dripped in 3 hours
Complete.System is warming up to 85 DEG C, is incubated 1.5 hours, under the effect of stirring, system is down to room temperature.Make in alkalescence with ammonia
Mediating recipe, regulation system pH value to 7.8.Stir, discharging, be a kind of polymeric dispersions of the present invention.During onsite application,
Dilute with water 1:50 in mass ratio, be then injected into sprinkler, carry out spraying dust suppression.
Measure film forming thickness: weigh the urban road micronic dust that 150 gram particle degree are 1500 mesh and add to the cultivation of a diameter of 12cm
Ware is compacted.The polymeric dispersions of the embodiment tap water of 50 times of quality is diluted, with 1.5kg/m2Consumption 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: weigh the urban road micronic dust that 150 gram particle degree are 1500 mesh and add to the cultivation of a diameter of 12cm
Ware is compacted, weighs.The polymeric dispersions of the embodiment tap water of 50 times of quality is diluted, with 1.5kg/m2Consumption spray
Spill to above-mentioned sample, weigh.Forced air drying in 40 DEG C of calorstats, evaluates moisture-retaining capacity with the forced air drying water retention of 3 hours.Protect
Wet ability strengthens, and the bulk density of dust increases, and the ability that suppression is flown upward improves.
Evaluate impact water in corrosion resistance energy: sample preparation is identical with the method for mensuration film forming thickness with spray method.Sample is at 25 DEG C of constant temperature
After being dried, in the way of spray, simulate natural precipitation, after soaking 12 hours, pour out excessive moisture, 25 DEG C of freeze-day with constant temperature 24
Hour to 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 is at 25 DEG C of constant temperature
It is dried, weighs.Mass loss rate after purging 1.0h the most continuously using simulation strong breeze power is as weathering quality evaluation index.
This index reflects the crust effect of dust suppressant, also embodies anti-dust effect.Mass loss rate is low, compactness is strong, film-formation result
Good shell, improves the dust suppressant sealing ability to dust, and anti-dust effect improves naturally.
Embodiment two
Implementing step with embodiment one, difference is: as non-ionic monomer, 2g hydroxyethyl methylacrylate is replaced
For 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
3g acrylic acid, 16g butyl acrylate and 4g styrene in gram, are mixed in proportion into material liquid standby by mass fraction
With.0.3g sodium carbonate and 100g distillation is added in the reactor equipped with agitator, thermometer, Dropping funnel and nitrogen conduit
Water, opens stirring, replaces 20 minutes with nitrogen.When heating in water bath is to 80 DEG C, adding 10g mass concentration is 5% potassium peroxydisulfate water
Solution, 2g sodium allylsulfonate and 2g2-acrylamide-2-methyl propane sulfonic.After temperature stabilization, continuous by Dropping funnel
Dropping material liquid, controls rate of addition, drips complete in 3 hours.System is warming up to 85 DEG C, is incubated 1.5 hours, in stirring
Effect under system is down to room temperature.With 2-methylol 2-aminopropane. regulation system pH value.Stir further, discharging, it is
A kind of polymeric dispersions of the present invention.During onsite application, press 1:50 dilution with water, be then injected into sprinkler, carry out sprinkling and press down
Dirt.
Method of evaluating performance is with embodiment one.
Embodiment four
Implementing step with embodiment three, difference is: anionic monomers acrylic acid such as replaces with at the methyl-prop of quality
Olefin(e) acid.
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 state | 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, mPa s) | 620 | 670 | 720 | 780 |
| Film forming thickness (cm) | 2.9 | 2.5 | 3.0 | 2.7 |
| Performance of keeping humidity (%) | 45 | 40 | 33 | 37 |
| Impact water in corrosion resistance energy | 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 to combine concrete preferred implementation further description made for the present invention, it is impossible to assert
The detailed description of the invention of the present invention is only limitted to this, for general technical staff of the technical field of the invention, is not taking off
On the premise of present inventive concept, it is also possible to make some simple deduction or replace, all should be considered as belonging to the present invention by institute
The claims submitted to determine scope of patent protection.
Unaccomplished matter of the present invention is known technology.
Claims (10)
1. a polymeric dispersions, is characterized by that this dispersion is prepared from by soap-free silicone-acrylic emulsion technology, and raw material includes
Anionic monomers, non-ionic monomer, pH buffer agent, initiator and water, its proportioning raw materials is:
Composition mass fraction
Anionic monomers 3-10,
Non-ionic monomer 10-25,
PH buffer agent 0.3-1.0,
Initiator 0.3-2,
Water 100；
Described raw material also includes antalkali, and the amount of antalkali is that the pH value of regulation reaction system is to 6.0-9.0；
Described anionic monomers is in unsaturated carboxylic acid monomer and unsaturated sulfonic acid or its sodium salt anionic monomers
One or more；
Described water is distilled water or tap water；
Described non-ionic monomer is butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, hydroxyethyl methacrylate second
One or more in ester, methoxy polyoxyethylene ether metacrylic acid ester and styrene.
2. polymeric dispersions as claimed in claim 1, it is characterized by described unsaturated carboxylic acid monomer be specially acrylic acid,
Methacrylic acid；Unsaturated sulfonic acid or its sodium salt anionic monomers are specially sodium vinyl sulfonate, sodium allylsulfonate, 2-
Acrylamide-2-methyl propane sulfonic.
3. polymeric dispersions as claimed in claim 1, it is characterized by described pH buffer agent be sodium bicarbonate, sodium carbonate and
One or both in sodium acetate.
4. polymeric dispersions as claimed in claim 1, it is characterized by described initiator be potassium peroxydisulfate, Ammonium persulfate. and
One or both in hydrogen peroxide/sulfuric acid ferrous iron, add as an aqueous solution, and the mass percentage concentration of solution is 5 ~ 10%.
5. polymeric dispersions as claimed in claim 1, is characterized by that described antalkali is that ammonia, 2-methylol are different
One or both in propylamine and 2-hydroxy ethoxy ethamine.
6. the preparation method of polymeric dispersions as claimed in claim 1, is characterized by comprise the following steps:
(1) material liquid is prepared: when anionic monomers is unsaturated carboxylic acid monomer, by unsaturated carboxylic acid monomer and nonionic
Monomer mix homogeneously, standby as material liquid；When anionic monomers is unsaturated sulfonic acid or its sodium salt anionic monomers
Time, material liquid consist of only non-ionic monomer, unsaturated sulfonic acid or its sodium salt anionic monomers in step below
Suddenly (3) add；When anionic monomers is unsaturated carboxylic acid monomer and unsaturated sulfonic acid or its sodium salt anionic monomers
Time, unsaturated carboxylic acid monomer is mixed homogeneously with non-ionic monomer, standby as material liquid, unsaturated sulfonic acid or its sodium salt
Anionic monomers adds in step (3) below；
(2) in the reactor equipped with agitator, thermometer, Dropping funnel and nitrogen conduit, add pH buffer agent and water, open
Stirring, nitrogen or argon are replaced 10～30 minutes, and 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 anionic monomers,
Add initiator solution, unsaturated sulfonic acid or its sodium salt anionic monomers, be subsequently adding the material liquid in step (1)；Or
Person, when anionic monomers does not comprise unsaturated sulfonic acid or its sodium salt anionic monomers, adds initiator solution, then
Add the material liquid in step (1)；
The feed postition of material liquid is for being dividedly in some parts or dripping continuously；
(4), after material liquid is added completely into, it is incubated 0.5-2.5 hour at 60-100 DEG C；
(5) it is cooled to room temperature, with the pH value of antalkali regulation reaction system to 6.0-9.0, discharging, is the poly-of the present invention
Compound dispersion.
7. the preparation method of polymeric dispersions as claimed in claim 6, is characterized by described step (3), material liquid
Time for adding be 2.0-4.0 hour.
8. the preparation method of polymeric dispersions as claimed in claim 6, is characterized by described step (4), insulation
Temperature is 80-95 DEG C.
9. the application process 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 sprinkler or sprinkling wagon, according to 1.0-2.5kg/m2Road
The consumption on road, uniformly sprays this dust suppressant diluent to the surface of urban road, sidewalk.
10. the application process of polymeric dispersions as claimed in claim 9, is characterized by that described and water mixed proportion is
Polymeric dispersions is pressed 1:20-500 and is diluted with 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 |
| CN105949368B (en) * | 2016-05-31 | 2018-05-25 | 西北师范大学 | A kind of multiple response amphipathic polymer particle 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 |
| 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 |
| CN107033276B (en) * | 2017-05-03 | 2019-02-22 | 上海巍盛化工科技有限公司 | A kind of dust Control agent using polymerisable emulsifier |
| 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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| CN102225982B (en) * | 2011-05-06 | 2013-08-28 | 华南理工大学 | Miniemulsion polymerization method of high-solid-content self-crosslinking type styrene-acrylate emulsion surface sizing agent |
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