CN104277172B - Water-based waterproof acrylate emulsion and preparation method thereof - Google Patents
Water-based waterproof acrylate emulsion and preparation method thereof Download PDFInfo
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- CN104277172B CN104277172B CN201410509042.8A CN201410509042A CN104277172B CN 104277172 B CN104277172 B CN 104277172B CN 201410509042 A CN201410509042 A CN 201410509042A CN 104277172 B CN104277172 B CN 104277172B
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Abstract
The invention discloses a water-based waterproof acrylate emulsion and a preparation method thereof. The water-based waterproof acrylate emulsion is of a core-shell structure, wherein the core is prepared from the following components in percentage by mass: 40%-60% of styrene, 31%-51% of acrylate, 1%-5% of methacrylic acid, 0.1%-2% of methacrylate, and 0.1%-2% of acrylamide; and the shell is prepared from the following components in percentage by mass: 40-60% of styrene, 30%-50% of acrylate, 1%-5% of methacrylic acid, 0.1%-2% of methacrylate, 0.1%-2% of acrylamide and 1%-8% of a waterproof functional monomer. The particle sizes of the waterproof acrylate emulsion are 100-150nm; the glass temperature is 0-40 DEG C; the emulsion molecular weight is 10<5>-10<6>; the water-based waterproof acrylate emulsion is solidified at 20-80 DEG C to form a film; and a film with high waterproofness and chemical resistance is formed after cooling; therefore, the water-based waterproof acrylate emulsion can be widely used as a water-proofing finishing agent for main film-forming substances and fabric of water-based thermosetting coatings such as glass, metal and buildings.
Description
Technical field
The present invention relates to a kind of Waterproof acrylic acid ester emulsion and preparation method thereof.
Technical background
There is very big pollution to environment after the solvent volatilization used by traditional solvent based coating, in construction, storage, transport
During there is inflammable and explosive potential safety hazard, and the disperse medium used in water paint is water, so having green, peace
Entirely, effect is the features such as facilitate, and water paint paint film has, and higher adhesive force, anti-wear performance, drying time is short, fire-retardant effect
Really good the advantages of.Relative to solvent based coating, no matter water paint is from the feature of environmental protection, economy, safety.Efficient and convenient property all has
There is very big advantage.Water-borne Acrylic Coating development is very fast, and acrylate paint is due to abundant raw material source, film property
Can be good, therefore have been widely used for the film forming matter of coating.In common acrylic acid ester emulsion, molecular resin is not due to having
There is the shortcomings of poor compactness, vapor and OTR oxygen transmission rate are high, minimum film formation temperature is higher in crosslinking, the film forming matter of emulsion, especially
, when for anticorrosive coating, these shortcomings are even more and are doubled amplification for which, it is difficult to reach the requirement such as resistance to water to coating.In order to
Improve emulsion performance, introduce in the molecule thereof the hydrophobic functional groups such as silica or fluorine carbon cause with good hydrophobicity,
Water proofing property, soil resistance etc..Typically greater than 90 degree of the water contact angle of the paint film for preparing, water is unable to its surface of moistening, can only
Slide.By the modified of organosilicon or Organic fluoride hydrophobic monomer, acrylic polymer emulsion paint film can be greatly improved
Resistance to water.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided a kind of Waterproof acrylic acid ester emulsion and its preparation
Method.
The object of the invention is achieved through the following technical solutions:
A kind of Waterproof acrylic acid ester emulsion, is nucleocapsid structure, and the core is made up of the component of following percetage by weight:
40-60% styrene, 31-51% acrylate, the methacrylic acid of 1-5%, 0.1-2% methacrylates, 0.1-2% acryloyls
Amine;The shell is made up of the component of following percetage by weight:40-60% styrene, 30-50% acrylate, the methyl-prop of 1-5%
Olefin(e) acid, 0.1-2% methacrylates, 0.1-2% acrylamides, the water-proof function monomer of 1-8%.
In above-mentioned Waterproof acrylic acid ester emulsion, described water-proof function monomer is preferably
Vinyltrimethoxy silane or vinyl silane triisopropoxide or VTES or γ-methyl
Acryloxypropyl trimethoxy silane or vinyl silicone oil or perfluorooctylethyl group acrylate or 2- (perfluoro capryl) second
Methyl acrylate or N- ethylperfluoro octyl group sulfoamido ethyl propylene acid esters.
In above-mentioned Waterproof acrylic acid ester emulsion, described acrylate is preferably acrylic acid methyl ester., acrylic acid second
Any one or a few mixture in ester, butyl acrylate, 2- methyl methacrylates, ethyl 2-methacrylate.
In above-mentioned Waterproof acrylic acid ester emulsion, described methacrylate is preferably hydroxyethyl methacrylate second
Ester, Hydroxypropyl methacrylate, methyl methacrylate, butyl methacrylate or Hydroxypropyl methacrylate.
In above-mentioned Waterproof acrylic acid ester emulsion, described acrylamide is preferably N hydroxymethyl acrylamide, N-
Hydroxyethyl acrylamide or N, N'- methylene-bisacrylamide.
A kind of preparation method of Waterproof acrylic acid ester emulsion, comprises the steps and process conditions:
(1)The premixing of nuclear monomer
By 40-60% styrene, 31-51% acrylate, the methacrylic acid of 1-5%, 0.1-2% methacrylates and
0.1-2% acrylamides are dispersed in water in the presence of emulsifying agent, obtain pre-emulsification monomer mixture.
(2)The premixing of shell monomer
By 40-60% styrene, 30-50% acrylate, the methacrylic acid of 1-5%, 0.1-2% methacrylates,
The water-proof function monomer of 0.1-2% acrylamides and 1-8% is dispersed in water in the presence of emulsifying agent, obtains pre-emulsification list
Body mixture.
(3)Polyreaction
Buffer agent and emulsifying agent are added in reaction medium water, are sufficiently stirred in reaction vessel and are warmed up to 80-100
DEG C, after reaction temperature to be achieved, first with the premix and initiator of 1-3h Deca nuclear monomers, used after isothermal reaction 0.5-2h again
The premix and initiator of 1-3h Deca shell monomers, continues isothermal reaction 0.5-2h, has been incubated rear terminating reaction after dripping.
Relative to prior art, the invention has the advantages that and beneficial effect:
Through the acrylic acid ester emulsion being modified, the anti-aqueous monomer of feature of addition causes to produce crosslinking knot between polymer chain
Structure, so that increase the hardness of latex film, resistance to water and weatherability.Have surface energy low using the anti-aqueous monomer of feature for adding,
It is easy to the characteristic to film surface migration, improves the structural behaviour on film surface, gives film coated surface hydrophobicity and water proofing property.But also
Can play and improve the glossiness of film, adhesive force, corrosion resistance, thermostability, resistance to soiling, mechanical performance, ageing-resistant performance etc..Institute
The particle diameter of Waterproof acrylic acid ester emulsion is 100-150nm, between 0-40 DEG C, emulsion molecular weight is vitrification point
105-106。
Specific embodiment
The present invention will be further described with reference to embodiments, but the scope of protection of present invention is not limited to reality
Apply within the scope of example expression.
Embodiment 1
A kind of Waterproof acrylic acid ester emulsion and its preparation:
(1)The sodium lauryl sulphate of the sodium bicarbonate of 0.5g, the alkylphenol polyoxyethylene of 0.5g, 0.11g is added
80 DEG C are sufficiently stirred for and are heated to in the distilled water of 40g, obtain kettle liquid;
(2)7g distilled water is taken, adds the alkylphenol polyoxyethylene of 0.4g, the sodium lauryl sulphate of 0.08g fully to stir
Mix uniform, weigh nuclear monomer:11.0g styrene(55%), 8g butyl acrylate(40%), 0.3g methacrylic acids(1.5%)、
0.3g hydroxyethyl methylacrylates(1.5%), 0.4gN- n-methylolacrylamide(2%)And be sufficiently mixed uniformly, it is slowly dropped to
Pre-emulsification in the above-mentioned water containing emulsifying agent, and stir 0.5h and obtain stable pre-emulsion;
(3)The initiator potassium persulfate for weighing 0.2g is dissolved in the distilled water of 10g;
(4)By step(2)With(3)Each 20% mass content is added to(1)The middle reaction through 1h obtains seed emulsion;
(5)By step(2)With(3)Remaining amount is slowly dropped to by 2.5h(4)In, 1.5h is incubated after being added dropwise to complete;
(6)7g distilled water is taken, adds the alkylphenol polyoxyethylene of 0.04g, the sodium lauryl sulphate of 0.08g fully to stir
Mix uniform, weigh shell monomer:9.2g styrene(46%), 9g butyl acrylate(45%), 0.4g methacrylic acids(2%), 0.1g first
Base 2-(Acryloyloxy)ethanol(0.5%), 0.1gN- n-methylolacrylamide(0.5%)And 1.2g vinyl silane triisopropoxides(6%)
And it is sufficiently mixed uniform, pre-emulsification in the above-mentioned water containing emulsifying agent is slowly dropped to, and stirs 0.5h and obtain stable pre- breast
Change liquid;
(7)The initiator ammonium persulfate for weighing 0.2g is dissolved in the distilled water of 10g;
(8)By step(6)With(7)The liquid for obtaining is slowly dropped to by 2.5h(5)In, after being incubated 1.5h after being added dropwise to complete
Prepare organosilicon-modified acrylate emulsion;
Embodiment 2
A kind of Waterproof acrylic acid ester emulsion and its preparation:
(1)The sodium lauryl sulphate of the sodium bicarbonate of 0.2g, the alkylphenol polyoxyethylene of 0.08g, 0.11g is added
80 DEG C are sufficiently stirred for and are heated to in the distilled water of 40g, obtain kettle liquid;
(2)7g distilled water is taken, adds the alkylphenol polyoxyethylene of 0.04g, the sodium lauryl sulphate of 0.05g fully to stir
Mix uniform, weigh nuclear monomer:10.2g styrene(51%), 8g ethyl acrylate(40%), 1.0g methacrylic acid(5%)、
0.4g hydroxyethyl methylacrylates(2%), 0.4gN- hydroxyethyl acrylamides(2%)And be sufficiently mixed uniformly, it is slowly dropped to
Pre-emulsification in the water containing emulsifying agent is stated, and stirs 0.5h and obtain stable pre-emulsion;
(3)The initiator potassium persulfate for weighing 0.2g is dissolved in the distilled water of 10g;
(4)By step(2)With(3)Each 5% mass content is added to(1)The middle reaction through 1h obtains seed emulsion;
(5)By step(2)With(3)Remaining amount is slowly dropped to by 2.0h(4)In, 0.5h is incubated after being added dropwise to complete;
(6)7g distilled water is taken, adds the alkylphenol polyoxyethylene of 0.04g, the sodium lauryl sulphate of 0.08g fully to stir
Mix uniform, weigh shell monomer:9.7g styrene(48.5%), 7.5g butyl acrylate(37.5%), 0.5g methacrylic acid
(2.5%), 0.4g hydroxyethyl methylacrylates(2%), 0.4gN- hydroxyethyl acrylamides(2%)And 1.5g vinyl silicone oils
(7.5%)And be sufficiently mixed uniformly, pre-emulsification in the above-mentioned water containing emulsifying agent is slowly dropped to, and stirs 0.5h and stablized
Pre-emulsion;
(7)The initiator ammonium persulfate for weighing 0.2g is dissolved in the distilled water of 10g;
(8)By step(6)With(7)The liquid for obtaining is slowly dropped to by 2.0h(5)In, after being incubated 0.5h after being added dropwise to complete
Prepare organosilicon-modified acrylate emulsion;
Embodiment 3
A kind of Waterproof acrylic acid ester emulsion and its preparation:
(1)The sodium lauryl sulphate of the sodium carbonate of 0.2g, the alkylphenol polyoxyethylene of 0.05g, 0.11g is added to
80 DEG C are sufficiently stirred for and are heated in the distilled water of 40g, obtain kettle liquid;
(2)7g distilled water is taken, adds the alkylphenol polyoxyethylene of 0.4g, the sodium lauryl sulphate of 0.8g to be sufficiently stirred for
Uniformly, weigh nuclear monomer:11.5g styrene(57.5%), 7.9g ethyl acrylate(39.5%), 0.25g methacrylic acids
(1.25%), 0.2g hydroxyethyl methylacrylate(1%), 0.15gN- n-methylolacrylamide(0.75%)And be sufficiently mixed
It is even, pre-emulsification in the above-mentioned water containing emulsifying agent is slowly dropped to, and stirs 0.5h and obtain stable pre-emulsion;
(3)The initiator potassium persulfate for weighing 0.2g is dissolved in the distilled water of 10g;
(4)By step(2)With(3)Each 10% mass content is added to(1)The middle reaction through 0.5h obtains seed breast
Liquid;
(5)By step(2)With(3)Remaining amount is slowly dropped to by 3.0h(4)In, 1.0h is incubated after being added dropwise to complete;
(6)7g distilled water is taken, adds the alkylphenol polyoxyethylene of 0.04g, the sodium lauryl sulphate of 0.08g fully to stir
Mix uniform, weigh shell monomer:11.5g styrene(57.5%), 7g ethyl acrylate(35%), 0.25g methacrylic acids
(1.25%), 0.2g hydroxyethyl methylacrylate(1%), 0.15gN- n-methylolacrylamide(0.75%)And 0.9g perfluoro capryls
Ethyl propylene acid esters(4.5%)And be sufficiently mixed uniformly, pre-emulsification in the above-mentioned water containing emulsifying agent is slowly dropped to, and is stirred
0.5h obtains stable pre-emulsion;
(7)The initiator ammonium persulfate for weighing 0.2g is dissolved in the distilled water of 10g;
(8)By step(6)With(7)The liquid for obtaining is slowly dropped to by 3.0h(5)In, after being incubated 1.0h after being added dropwise to complete
Prepare organosilicon-modified acrylate emulsion;
Embodiment 4
Application of the water-proof emulsion on fabric:Three kinds of water-proof emulsions are prepared by three above embodiment, by its point
It is not diluted to admittedly containing 25%, impregnated in above emulsion with the bafta of 3cm*3cm respectively, be positioned over after being drawn off after 1 minute
80 degree of drying in oven, prepare waterproof fabric, then determine its water resistance, determine water in its table by contact angle tester
The contact angle in face, by impregnated in the water absorption rate in water after 6 hours.Determine its water-proof acrylic acid ester emulsion property for respectively obtaining
With waterproof fabric performance such as table 1:
1 water-proof emulsion performance of table and waterproof fabric performance
Index name | 1 emulsion of embodiment | 2 emulsion of embodiment | 3 emulsion of embodiment | Remarks |
Outward appearance | Milky band blue light | Milky band blue light | Milky band blue light | Range estimation |
Molecular weight | 1.54×106 | 4.48×105 | 5.25×105 | Gel permeation chrommatograph PL-GPC 50 |
Particle diameter | 112 | 117 | 113 | Malvern ParticleSizer ZS Nano ZS 90, |
Solid content(%) | 35.01 | 35.05 | 35.04 | Determine by GB/T 1725-1979 |
PH value | 7.4 | 7.5 | 7.4 | Accurate pH test paper |
Contact angle | 109.4 | 112.7 | 125.2 | Dynamic Contact angle tester OCA40 Micro |
Water absorption rate(%) | 105.7 | 81.6 | 60.2 | Determine by GB1738-79 |
Claims (5)
1. a kind of Waterproof acrylic acid ester emulsion, it is characterised in that be nucleocapsid structure, the core is by following percetage by weight
Component is made:40-60% styrene, 31-51% acrylate, the methacrylic acid of 1-5%, 0.1-2% methacrylates,
0.1-2% acrylic amide materials;The shell is made up of the component of following percetage by weight:40-60% styrene, 30-50% propylene
Acid esters, the methacrylic acid of 1-5%, 0.1-2% methacrylates, 0.1-2% acrylic amide materials, the water-proof function of 1-8%
Monomer;
Described water-proof function monomer is vinyl silicone oil;
Described acrylic amide material is N hydroxymethyl acrylamide, N- hydroxyethyl acrylamides or N, N'- di-2-ethylhexylphosphine oxide third
Acrylamide.
2. Waterproof acrylic acid ester emulsion according to claim 1, it is characterised in that described acrylate is propylene
In sour methyl ester, ethyl acrylate, butyl acrylate, 2- methyl methacrylates, ethyl 2-methacrylate any one or
Several mixture.
3. Waterproof acrylic acid ester emulsion according to claim 1, it is characterised in that described methacrylate is
Hydroxyethyl methylacrylate, methyl methacrylate, butyl methacrylate or Hydroxypropyl methacrylate.
4. the preparation method of Waterproof acrylic acid ester emulsion described in claim 1, it is characterised in that comprise the steps:
(1)The premixing of nuclear monomer:
By 40-60% styrene, 31-51% acrylate, the methacrylic acid of 1-5%, 0.1-2% methacrylates and 0.1-
2% acrylic amide material is dispersed in water in the presence of emulsifying agent, obtains pre-emulsification monomer mixture;
(2)The premixing of shell monomer:
By 40-60% styrene, 30-50% acrylate, the methacrylic acid of 1-5%, 0.1-2% methacrylates, 0.1-2%
The water-proof function monomer of acrylic amide material and 1-8% is dispersed in water in the presence of emulsifying agent, obtains pre-emulsification list
Body mixture;
(3)Polyreaction:
Buffer agent and emulsifying agent are added in reaction medium water, 80-100 DEG C is sufficiently stirred for and is warmed up in reaction vessel,
After reaction temperature to be achieved, first with the premix and initiator of 1-3h Deca nuclear monomers, 1- after isothermal reaction 0.5-2h, is used again
The premix and initiator of 3h Deca shell monomers, continues isothermal reaction 0.5-2h, has been incubated rear terminating reaction after dripping.
5. the preparation method of Waterproof acrylic acid ester emulsion according to claim 4, it is characterised in that the initiator
It is potassium peroxydisulfate or sodium peroxydisulfate or the mixture of one or more in Ammonium persulfate..
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