CN106349416A - Modified waterborne acrylic emulsion and preparation method thereof - Google Patents
Modified waterborne acrylic emulsion and preparation method thereof Download PDFInfo
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- CN106349416A CN106349416A CN201610738267.XA CN201610738267A CN106349416A CN 106349416 A CN106349416 A CN 106349416A CN 201610738267 A CN201610738267 A CN 201610738267A CN 106349416 A CN106349416 A CN 106349416A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
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- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a modified waterborne acrylic emulsion. The modified waterborne acrylic emulsion is characterized by, by weight, 20-45 parts of acrylic series monomer, 20-50 parts of functional modified monomer, 1-5 parts of initiator, 0.01-0.5 part of complexing agent, 1-7 parts of emulsifier, 0.01-0.1 part of buffering agent, 0.1-0.5 part of pH value regulator, 0.01-0.5 part of midlewproof and corrosion-resistant agent, 0.01-0.5 part of defoamer, 0.01-0.7 part of thickener and 25-55 parts of water serving as a solvent. Functional monomers like styrene and acrylamide are added and phenyl and acylamino are introduced onto acrylic resin to modify a waterborne acylic emulsion; by regulating molar proportion of soft and hard monomers, waterproofness, wear resistance and scratching resistance of a waterborne acrylic emulsion coating are improved effectively.
Description
Technical field
The present invention relates to a kind of modified aqueous acrylic acid emulsion and preparation method thereof.
Background technology
In solvent based coating, the emission hazard Environmental security of VOC (voc) and the mankind's is healthy,
Constantly strengthen with people's green living and eco-friendly consciousness, water paint will have vast potential for future development and economy
Benefit.
Aqueous acrylic emulsion has that anti-corrosion, alkaline-resisting, fast light, weather-proof, good film-forming property, colour retention are good, pollution-free, elongation percentage
Height, asepsis environment-protecting, workability strong, ageing-resistant to basic unit's deformation adaptive faculty are well so that it is in industrial coating and building coating
In extensively apply.But aqueous acrylic emulsion has resistance to water, less stable simultaneously, the deficiency such as hot sticky cold crisp, make aqueouss third
The further popularization and application of olefin(e) acid emulsion are restricted.It is therefore desirable to being modified to aqueous acrylic emulsion studying,
Typically can by the selection to comonomer type, change the approach such as the ratio of comonomer to improve the performance of emulsion.
Content of the invention
Instant invention overcomes shortcoming of the prior art, there is provided a kind of gel fraction is low, water-tolerant, and combination property is good
Modified aqueous acrylic acid emulsion and preparation method thereof.
In order to solve above-mentioned technical problem, the present invention is achieved by the following technical solutions:
A kind of modified aqueous acrylic acid emulsion, by weight, 100 parts of total amount, including acrylic monomer 20-45 part,
Function modified monomer 20-50 part, initiator 1-5 part, chelating agent 0.01-0.5 part, emulsifying agent 1-7 part, buffer agent 0.01-0.1
Part, ph value regulator 0.1-0.5 part, fungusproof anti-corrosion agent 0.01-0.5 part, defoamer 0.01-0.5 part, thickening agent 0.01-0.7
Part, aqueous solvent 25-55 part.
Further, in terms of mass fraction, described acrylic monomer includes 5-20% methacrylic acid, 10-45% methyl
Acrylic acid methyl ester. or methyl ester ethyl acrylate, 50-70% Isooctyl acrylate monomer or 2-Propenoic acid, 2-methyl-, isooctyl ester.
Further, in terms of mass fraction, described function modified monomer is 45-80% styrene, 20-55% acrylamide.
Further, methacrylic acid in described monomer, Isooctyl acrylate monomer, 2-Propenoic acid, 2-methyl-, isooctyl ester belongs to soft monomer；
Methyl methacrylate, methyl ester ethyl acrylate, styrene, acrylamide belongs to hard monomer.
Generally, soft monomer can give the certain pliability of film and adhesive force, makes emulsion have more preferably film forming
Performance；Hard monomer then can make coating film gloss good and hardness improves, and shock resistance strengthens.When soft monomer and hard monomer mole
Than larger when, emulsion film forming performance can more preferably, but hard monomer content is too small, hardness of film can be led to decline, surface dim.Therefore
Under suitable soft monomer and the mol ratio of hard monomer, optimal film performance can be obtained, in the present invention, soft monomer and hard monomer
Mol ratio is between 1:1-2.
Further, described initiator is tert-butyl hydroperoxide, Ammonium persulfate., at least one in potassium peroxydisulfate.
Further, described chelating agent is ethylenediaminetetraacetic acid, and described buffer agent is arbitrary in sodium carbonate or sodium bicarbonate
Kind, described ph value regulator be concentration for 25--35% ammonia or alcohol amine compound any one, described emulsifying agent is Laurel
Alcohol sulfuric ester sodium salt, sodium lauryl sulfate, any one in Triton X-100.
Further, described fungusproof anti-corrosion agent is Kazon (5- chloro- 2 methyl -4 isothiazoline -3 ketone (cit) or 2- methyl -4-
Isothiazoline -3- ketone (mit)), described defoamer is organosilicon compound, and described thickening agent selects Polyethylene Glycol, polyethylene
The mixture of alcohol apoplexy due to endogenous wind any one or the two.
A kind of preparation method of modified aqueous acrylic acid emulsion, comprises the steps:
1. the preparation of pre-emulsion
By formula by the water of 1/3 formula ratio, 3/5 emulsifying agent, whole acrylic monomer, function modified monomer adds anti-
Answer in container, quick stirring 25 40min, obtain stable pre-emulsion；
2. the preparation of modified aqueous acrylic acid emulsion
(1) water of 2/3 formula ratio, 2/5 emulsifying agent and buffer agent are sequentially added toward in container, stirring and dissolving post-heating is extremely
85-90 DEG C of constant temperature；.
(2) add the 1-2% mass fraction of pre-emulsion total amount in 1, after stirring, add 1/3 initiator and 3/5 network
Mixture, stirs to solution clarification；
(3) to the remaining pre-emulsion in Deca in system 1 and then in 2-3h, it is simultaneously introduced 1/3 initiator, continue to protect
Temperature reaction 30-45min；
(4) when system is cooled to 60 DEG C, it is supplemented with remaining 1/3 initiator and remaining 2/5 chelating agent, continue reaction
30-40min, naturally cools to 40 DEG C；
(5) ph regulator, regulation system ph to 8 8.5 are added；
(6) add fungusproof anti-corrosion agent, defoamer, thickening agent, after stirring, be cooled to room temperature；
(7) use colloid mill to grind 15-30min, discharging, obtain final product the aqueous acrylic emulsion of modification.
Compared with prior art, the invention has the beneficial effects as follows:
A kind of modified aqueous acrylic acid emulsion of the present invention and preparation method thereof, adds the work(such as styrene and acrylamide
Energy monomer, introduces phenyl and amide groups on acrylic resin, has carried out modification to aqueous acrylic emulsion, by soft or hard
The regulation and control of monomer molar ratio, improve resistance to water, wearability and the resistance to marring of aqueous acrylic emulsion film effectively.
Specific embodiment
Hereinafter the preferred embodiments of the present invention are illustrated it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1:
1. the preparation of pre-emulsion
By formula by 220g water, 9g dodecyl sodium sulfate, 45g methacrylic acid, 50g methyl methacrylate, 180g third
The different monooctyl ester of olefin(e) acid, 350g styrene, 5g acrylamide adds in reaction vessel, disperses at a high speed (rotating speed after stirring at low speed is uniform again
For 3000～4000r/min) 30min, obtain stable pre-emulsion.
2. the preparation of modified aqueous acrylic acid emulsion
(1) 440g water, the dodecyl sodium sulfate of 6g and 0.2g sodium carbonate, stirring and dissolving post-heating are sequentially added toward in container
To 85 DEG C of constant temperature；
(2) add 1.5% of pre-emulsion total amount in 1, after stirring, add 1.2g Ammonium persulfate. and the different Vitamin C of 0.6g
Acid, stirs to solution clarification；
(3) to the remaining pre-emulsion (98.5%) in Deca in system 1 and then in 2.5h, it is simultaneously introduced 1.2g over cure
Sour ammonium, continues insulation reaction 30min；
(4) when system is cooled to 60 DEG C, it is supplemented with 1.2g Ammonium persulfate. and 0.4g arabo-ascorbic acid, continue reaction
40min, naturally cools to 40 DEG C；
(5) 10g concentration is added to be 28% ammonia, regulation system ph to 8；
(6) fungusproof anti-corrosion agent 5 chlorine, 2 methyl, 4 isothiazoline 3 ketone (cit) 0.4g, organic silicon defoamer 0.5g are added,
Thickening agent Polyethylene Glycol 0.5g, is cooled to room temperature after stirring；
(7) use colloid mill to grind 20min (5000 8000r/min), discharging, obtain final product the aqueous acrylic emulsion of modification.
Embodiment 2:
1. the preparation of pre-emulsion
By formula by 250g water, 12g sodium lauryl sulfate, 25g methacrylic acid, 50g methyl methacrylate, 200g first
Base Isooctyl acrylate monomer, 400g styrene, 3g acrylamide adds in reaction vessel, disperses at a high speed after stirring at low speed is uniform again
(rotating speed is 3000～4000 revs/min of 40min, obtains stable pre-emulsion.
2. the preparation of modified aqueous acrylic acid emulsion
(1) 500g water, the sodium lauryl sulfate of 8g and 0.15g sodium bicarbonate are sequentially added toward in container, after stirring and dissolving
It is heated to 90 DEG C of constant temperature；
(2) add 2% of pre-emulsion total amount in 1, after stirring, add 2.5g tert-butyl hydroperoxide and 0.6g different anti-
Bad hematic acid, stirs to solution clarification；
(3) to the remaining pre-emulsion (98%) in Deca in system 1 and then in 3h, it is simultaneously introduced 2.5g tert-butyl group mistake
Hydrogen oxide, continues insulation reaction 45min；
(4) when system is cooled to 60 DEG C, it is supplemented with 2.5g tert-butyl hydroperoxide and 0.4g arabo-ascorbic acid, continue anti-
Answer 40min, naturally cool to 40 DEG C；
(5) add 3g triethanolamine regulation system ph to 8.5；
(6) add fungusproof anti-corrosion agent 2 methyl, 4 isothiazoline 3 ketone (mit) 0.6g, organic silicon defoamer 0.5g, increase
Thick dose of Polyethylene Glycol 0.7g, is cooled to room temperature after stirring；
(7) use colloid mill to grind 25min (5000 8000r/min), discharging, obtain final product the aqueous acrylic emulsion of modification.
Embodiment 3:
1. the preparation of pre-emulsion
By formula by 250g water, 24g Triton X-100,25g methacrylic acid, 55g ethyl methacrylate,
200g Isooctyl acrylate monomer, 400g styrene, 5g acrylamide adds in reaction vessel, disperses at a high speed after stirring at low speed is uniform again
(rotating speed is 3000～4000 revs/min of 40min, obtains stable pre-emulsion.
2. the preparation of modified aqueous acrylic acid emulsion
(1) 500g water, 16g Triton X-100, and 0.2g sodium carbonate, stirring and dissolving are sequentially added toward in container
Post-heating is to 85 DEG C of constant temperature；
(2) add 2% of pre-emulsion total amount in 1, after stirring, add 1.5g potassium peroxydisulfate and the different Vitamin C of 0.6g
Acid, stirs to solution clarification；
(3) to the remaining pre-emulsion (98%) in Deca in system 1 and then in 3h, it is simultaneously introduced 1.5g persulfuric acid
Potassium, continues insulation reaction 45min；
(4) when system is cooled to 60 DEG C, it is supplemented with 1.5g potassium peroxydisulfate and 0.4g arabo-ascorbic acid, continue reaction
30min, naturally cools to 40 DEG C；
(5) add ammonia regulation system ph that 12g concentration is 18% to 8.5；
(6) add fungusproof anti-corrosion agent 2 methyl, 4 isothiazoline 3 ketone (mit) 0.6g, organic silicon defoamer 0.5g, increase
Thick dose of polyvinyl alcohol 0.7g, is cooled to room temperature after stirring；
(7) use colloid mill to grind 25min (5000 8000r/min), discharging, obtain final product the aqueous acrylic emulsion of modification.
Performance detection data: performance detection is carried out to the modified aqueous acrylic acid emulsion of embodiment 1-3, testing result sees below
Table 1.
Table 1
Finally it is noted that these are only the preferred embodiments of the present invention, it is not limited to the present invention, although
With reference to embodiment, the present invention is described in detail, for a person skilled in the art, it still can be to aforementioned
Technical scheme described in each embodiment is modified, or carries out equivalent to wherein some technical characteristics, but all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvement made etc., should be included in the protection of the present invention
Within the scope of.
Claims (8)
1. a kind of modified aqueous acrylic acid emulsion it is characterised in that by weight, including acrylic monomer 20-45 part, work(
Energy modified monomer 20-50 part, initiator 1-5 part, chelating agent 0.01-0.5 part, emulsifying agent 1-7 part, buffer agent 0.01-0.1 part,
Ph value regulator 0.1-0.5 part, fungusproof anti-corrosion agent 0.01-0.5 part, defoamer 0.01-0.5 part, thickening agent 0.01-0.7 part is molten
Agent water 25-55 part.
2. according to claim 1 a kind of modified aqueous acrylic acid emulsion it is characterised in that in terms of mass fraction, described third
Alkene acrylic monomer includes 5-20% methacrylic acid, 10-45% methyl methacrylate or methyl ester ethyl acrylate, 50-70%
Isooctyl acrylate monomer or 2-Propenoic acid, 2-methyl-, isooctyl ester.
3. according to claim 2 a kind of modified aqueous acrylic acid emulsion it is characterised in that in terms of mass fraction, described work(
Can modified monomer be 45-80% styrene, 20-55% acrylamide.
4. according to claim 3 a kind of modified aqueous acrylic acid emulsion it is characterised in that metering system in described monomer
Acid, Isooctyl acrylate monomer, 2-Propenoic acid, 2-methyl-, isooctyl ester belongs to soft monomer；Methyl methacrylate, methyl ester ethyl acrylate, benzene second
Alkene, acrylamide belongs to hard monomer, and the mol ratio of soft monomer and hard monomer is between 1:1-2.
5. according to claim 1 a kind of modified aqueous acrylic acid emulsion it is characterised in that described initiator be tert-butyl group mistake
Hydrogen oxide, Ammonium persulfate., at least one in potassium peroxydisulfate.
6. according to claim 1 a kind of modified aqueous acrylic acid emulsion it is characterised in that described chelating agent be ethylenediamine tetraacetic
Acetic acid, described buffer agent is any one in sodium carbonate or sodium bicarbonate, and described ph value regulator is 25--35% ammonia for concentration
Water or alcohol amine compound any one, described emulsifying agent is sodium lauryl sulfate salt, sodium lauryl sulfate, Polyethylene Glycol
Any one in octyl phenyl ether.
7. according to claim 1 a kind of modified aqueous acrylic acid emulsion it is characterised in that described fungusproof anti-corrosion agent be card
Pine, described defoamer is organosilicon compound, and described thickening agent selects Polyethylene Glycol, polyvinyl alcohol apoplexy due to endogenous wind any one or the two
Mixture.
8. a kind of preparation method of modified aqueous acrylic acid emulsion is it is characterised in that comprise the steps:
1. the preparation of pre-emulsion
By formula by the water of 1/3 formula ratio, 3/5 emulsifying agent, whole acrylic monomer, function modified monomer adds reaction to hold
In device, quick stirring 25 40min, obtain stable pre-emulsion；
2. the preparation of modified aqueous acrylic acid emulsion
(1) water of 2/3 formula ratio, 2/5 emulsifying agent and buffer agent, stirring and dissolving post-heating to 85- are sequentially added toward in container
90 DEG C of constant temperature；
(2) add the 1-2% mass fraction of pre-emulsion total amount in 1, after stirring, add 1/3 initiator and 3/5 complexation
Agent, stirs to solution clarification；
(3) to the remaining pre-emulsion in Deca in system 1 and then in 2-3h, it is simultaneously introduced 1/3 initiator, continue insulation anti-
Answer 30-45min；
(4) when system is cooled to 60 DEG C, it is supplemented with remaining 1/3 initiator and remaining 2/5 chelating agent, continue reaction 30-
40min, naturally cools to 40 DEG C；
(5) ph regulator, regulation system ph to 8 8.5 are added；
(6) add fungusproof anti-corrosion agent, defoamer, thickening agent, after stirring, be cooled to room temperature；
(7) use colloid mill to grind 15-30min, discharging, obtain final product the aqueous acrylic emulsion of modification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610738267.XA CN106349416A (en) | 2016-08-26 | 2016-08-26 | Modified waterborne acrylic emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610738267.XA CN106349416A (en) | 2016-08-26 | 2016-08-26 | Modified waterborne acrylic emulsion and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106349416A true CN106349416A (en) | 2017-01-25 |
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| CN201610738267.XA Pending CN106349416A (en) | 2016-08-26 | 2016-08-26 | Modified waterborne acrylic emulsion and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107355282A (en) * | 2017-08-22 | 2017-11-17 | 芜湖恒耀汽车零部件有限公司 | A kind of processing method of the particulate filter of Vehicle Exhaust Particulate filter |
| CN114196276A (en) * | 2021-12-23 | 2022-03-18 | 三棵树(上海)新材料研究有限公司 | Waterproof exterior wall coating and preparation method thereof |
-
2016
- 2016-08-26 CN CN201610738267.XA patent/CN106349416A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107355282A (en) * | 2017-08-22 | 2017-11-17 | 芜湖恒耀汽车零部件有限公司 | A kind of processing method of the particulate filter of Vehicle Exhaust Particulate filter |
| CN114196276A (en) * | 2021-12-23 | 2022-03-18 | 三棵树(上海)新材料研究有限公司 | Waterproof exterior wall coating and preparation method thereof |
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Application publication date: 20170125 |