CN104877141A - Preparation method of polymerizable modifier - Google Patents
Preparation method of polymerizable modifier Download PDFInfo
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- CN104877141A CN104877141A CN201510320867.XA CN201510320867A CN104877141A CN 104877141 A CN104877141 A CN 104877141A CN 201510320867 A CN201510320867 A CN 201510320867A CN 104877141 A CN104877141 A CN 104877141A
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Abstract
The invention belongs to the technical field of coating, and discloses a preparation method of a polymerizable modifier. The polymerizable modifier is prepared from the following raw materials: phosphorus pentoxide, hydroxyalkyl (meth)acrylate, alkyl cyclosiloxane, water and polymerization inhibitor. According to the preparation method, the prepared polymerizable modifier contains silicone phosphate monomer, so that a film formed by acrylic acid-synthesized polymer emulsion prepared from the polymerizable modifier has excellent water resistance, adhesion and stability; the polymerizable modifier can significantly improve the adhesion, corrosion resistance and rust resistance of waterborne coatings, and is simple in preparation method and wide in application prospect.
Description
Technical field
The present invention relates to technical field of coatings, be specifically related to a kind of preparation method of polymerizable properties-correcting agent.
Background technology
Water-borne coatings take water as dispersion medium, nontoxic, nonflammable, be beneficial to environmental protection, and cost is low, is the important directions that current industrial coating comprises protective system development.Water-based anticorrosive paint comprises water soluble acrylic acid, aqueous epoxy resins, aqueous polyurethane etc., wherein water-borne acrylic coatings has good weathering resistance, erosion resistance, contamination resistance etc., but compared with solvent based coating sticking power, wear-resisting, rustless property is not enough, generally need to carry out modification to it.Phosphoric acid ester is a kind of important function monomer, forms fine and close phosphate coating between bound phosphate groups energy and metal base, has good rust-proof effect; simultaneously; phosphorus hydroxyl and metallic substrate surface have sequestering action, form complex compound with polyvalent metal effect, can improve the sticking power of coating.In addition, by introducing vinyl, hydroxyl isoreactivity functional group, obtaining reactive phosphorus acid esters function monomer, improving the over-all properties of water-borne acrylic coatings further.
At present, the main manufacturer of reactive phosphorus acid esters function monomer is French Rhodia, its product is used widely, but it is expensive, limit its application in water-based anticorrosive paint and popularization, and due to the wetting ability of phosphoric acid ester, there is negative impact in water-fast, the salt spray resistance of excessive addition to coating, in the urgent need to developing new high-performance reactive phosphorus acid esters function monomer, to adapt to the fast-developing requirement of water-based anticorrosive paint.
Summary of the invention
In order to solve above-mentioned prior art Problems existing, the invention provides a kind of preparation method of polymerizable properties-correcting agent, properties-correcting agent prepared by the method contains organophosphorus ester monomer, can significantly improve the sticking power of vinylformic acid synthetic polymer emulsion, protection against corrosion, water-fast and rustless property.
The technical solution used in the present invention is:
A kind of preparation method of polymerizable properties-correcting agent, the raw material that described preparation method adopts comprises (methyl) hydroxyalkyl acrylates, stopper, Vanadium Pentoxide in FLAKES, cyclosiloxane and water, and the mol ratio of described Vanadium Pentoxide in FLAKES and alkyl-cyclosiloxanes is (0.2-5): 1;
Described preparation method comprises the following steps:
(1) mixed with stopper by (methyl) hydroxyalkyl acrylates, stir and be warming up to 60 ~ 65 DEG C, gradation adds Vanadium Pentoxide in FLAKES, and control temperature, at 65-85 DEG C, obtains mixed solution;
(2) mixed solution is warming up to 90 ~ 120 DEG C of reaction 1-2h, drips alkyl-cyclosiloxanes, or drip alkyl-cyclosiloxanes and (methyl) hydroxyalkyl acrylates, water is added after being added dropwise to complete, at 90 ~ 120 DEG C of reaction 1-3h, cooling, obtains polymerizable properties-correcting agent.
Preferably, the structural formula of described alkyl-cyclosiloxanes is:
wherein, m=4-6, R identical or different are selected from C
1-C
3alkyl.
The present invention prepares the properties-correcting agent containing organophosphorus ester function monomer by the acrylate monomer of hydroxyl, alkyl-cyclosiloxanes and Vanadium Pentoxide in FLAKES, can improve the water tolerance of coating, sticking power and rustless property for the preparation of coating.
Described (methyl) hydroxyalkyl acrylates is hydroxyalkyl acrylates and/or haloalkylacrylates, and described alkyl is the alkyl of C1-C3, and preferably, described alkyl is methyl.
Preferably, in described step (1), the mol ratio of (methyl) hydroxyalkyl acrylates and Vanadium Pentoxide in FLAKES is (1-4): 1.
Preferably, in step (1), described Vanadium Pentoxide in FLAKES is divided into several equal portions before use, is placed in the moisture eliminator of 25-50 DEG C.Described gradation is that gradation adds portion at every turn, to reduce the water-intake rate of Vanadium Pentoxide in FLAKES, is beneficial to control temperature of reaction simultaneously.
Preferably, in step (1), described in add Vanadium Pentoxide in FLAKES and add at 1 ~ 2h.
Preferably, in step (1), described stopper to be selected from p methoxy phenol, tert-butyl catechol, Resorcinol one or both.
Preferably, be 100 parts in the total mass of Vanadium Pentoxide in FLAKES, (methyl) hydroxyalkyl acrylates, alkyl-cyclosiloxanes, water and stopper, the consumption of described stopper is 0.1 ~ 0.3 part.
Preferably, in step (2), the time of described dropping is 1.5 ~ 3h.
Preferably, in step (2), drip alkyl-cyclosiloxanes and (methyl) hydroxyalkyl acrylates, and the quality of (methyl) hydroxyalkyl acrylates dripped in this step is more than 3% of alkyl-cyclosiloxanes quality, is more preferably 5% ~ 10%.
In step (2), the dropping mode of described dropping alkyl-cyclosiloxanes and (methyl) hydroxyalkyl acrylates adopts the mode simultaneously dripping alkyl-cyclosiloxanes and (methyl) hydroxyalkyl acrylates, or adopt the 60-80% first simultaneously dripping (methyl) hydroxyalkyl acrylates in alkyl-cyclosiloxanes and step (2), drip the mode of remaining (methyl) hydroxyalkyl acrylates in step (2) again, or adopt and first drip alkyl-cyclosiloxanes, drip the mode of (methyl) hydroxyalkyl acrylates again, dropping mode preferably adopts one of latter two mode.
Preferably, in step (2), described water is deionized water or distilled water.
Preferably, the quality adding water in described step (2) is 2 ~ 5% of (methyl) hydroxyalkyl acrylates and Vanadium Pentoxide in FLAKES quality sum in step (1).
Described cooling is cooled to room temperature.
The technique effect that the present invention is useful: the present invention is by alkyl-cyclosiloxanes ring-opening polymerization in acid condition and the reaction of (methyl) hydroxyalkyl acrylates and Vanadium Pentoxide in FLAKES, by in polysiloxane segment and phosphate-based introducing acrylate monomer, obtain the mixture of reactive organophosphorus ester monomer, as polymerizable properties-correcting agent, the application performances such as it is water-fast, antirust, sticking power can be improved for the preparation of vinylformic acid synthetic polymer emulsion and coating thereof, preparation method is simple, and application prospect is wide.
Embodiment
Below provide specific embodiment to be further detailed the present invention.
Embodiment 1
Polymerizable properties-correcting agent is prepared by following steps:
(1) get 234.4g Vanadium Pentoxide in FLAKES, be divided into five equal portions, be placed in 50 DEG C of drying ovens stand-by; Being mixed with 2g p methoxy phenol by 536.5g hydroxyethyl methylacrylate drops in reactor, stirs and is warming up to 65 DEG C, and accelerate stirring velocity, add a Vanadium Pentoxide in FLAKES successively, control temperature is at 80 DEG C, and 2h adds, and obtains mixed solution at every turn;
(2) mixed solution is warming up to 100 DEG C of reaction 2h, drip 191.1g octamethylcyclotetrasiloxane and 9.6g hydroxyethyl methylacrylate, 2h is added dropwise to complete simultaneously, add 37.6g deionized water, at 100 DEG C of reaction 2h, be cooled to room temperature, obtain polymerizable properties-correcting agent, be designated as 1# properties-correcting agent.
Embodiment 2
Polymerizable properties-correcting agent is prepared by following steps:
(1) get 179g Vanadium Pentoxide in FLAKES, be divided into five equal portions, be placed in 50 DEG C of drying ovens stand-by; Being mixed with 2g p methoxy phenol by 409.8g hydroxyethyl methylacrylate drops in reactor, stirs and is warming up to 65 DEG C, and accelerate stirring velocity, add a Vanadium Pentoxide in FLAKES successively, control temperature is at 75 DEG C, and 1.5h adds, and obtains mixed solution at every turn;
(2) mixed solution is warming up to 90 DEG C of reaction 2h, drips 347.1g octamethylcyclotetrasiloxane, then drip 24.4g hydroxyethyl methylacrylate, 2h drips, and adds 23.6g deionized water, at 90 DEG C of reaction 3h, be cooled to room temperature, obtain polymerizable properties-correcting agent, be designated as 2# properties-correcting agent.
Embodiment 3
Polymerizable properties-correcting agent is prepared by following steps:
(1) get 179g Vanadium Pentoxide in FLAKES, be divided into five equal portions, be placed in 50 DEG C of drying ovens stand-by; Being mixed with 2g p methoxy phenol by 409.8g hydroxyethyl methylacrylate drops in reactor, stirs and is warming up to 65 DEG C, and accelerate stirring velocity, add a Vanadium Pentoxide in FLAKES successively, control temperature is at 75 DEG C, and 1.5h adds, and obtains mixed solution at every turn;
(2) mixed solution is warming up to 90 DEG C of reaction 1h, drip 347.1g octamethylcyclotetrasiloxane and 17.1g hydroxyethyl methylacrylate simultaneously, 2h drips, drip 7.3g hydroxyethyl methylacrylate again, 0.5h drips, and finally adds 23.6g deionized water, at 90 DEG C of reaction 3h, be cooled to room temperature, obtain polymerizable properties-correcting agent, be designated as 3# properties-correcting agent.
Embodiment 4
Polymerizable properties-correcting agent is prepared by following steps:
(1) get 112.6g Vanadium Pentoxide in FLAKES, be divided into five equal portions, be placed in 50 DEG C of drying ovens stand-by; Being mixed with 2g p methoxy phenol by 257.8g hydroxyethyl methylacrylate drops in reactor, stirs and is warming up to 65 DEG C, and accelerate stirring velocity, add a Vanadium Pentoxide in FLAKES successively, control temperature is at 75 DEG C, and 1h adds, and obtains mixed solution at every turn;
(2) mixed solution is warming up to 110 DEG C of reaction 1h, drips 555.6g octamethylcyclotetrasiloxane, then drip 55.6g hydroxyethyl methylacrylate, 3h is added dropwise to complete, and adds 11.2g deionized water, at 110 DEG C of reaction 2h, be cooled to room temperature, obtain polymerizable properties-correcting agent, be designated as 4# properties-correcting agent.
Embodiment 5
Polymerizable properties-correcting agent is prepared by following steps:
(1) get 234.4g Vanadium Pentoxide in FLAKES, be divided into five equal portions, be placed in 50 DEG C of drying ovens stand-by; Being mixed with 2g p methoxy phenol by 536.5g hydroxyethyl methylacrylate drops in reactor, stirs and is warming up to 65 DEG C, and accelerate stirring velocity, add a Vanadium Pentoxide in FLAKES successively, control temperature is at 80 DEG C, and 2h adds, and obtains mixed solution at every turn;
(2) mixed solution is warming up to 95 DEG C of reaction 2h, drip 160g octamethylcyclotetrasiloxane, 2h is added dropwise to complete, and adds 37.6g deionized water, at 95 DEG C of reaction 3h, is cooled to room temperature, obtains polymerizable properties-correcting agent, be designated as 5# properties-correcting agent.
Embodiment 6
The 1-5# properties-correcting agent prepared by the embodiment of the present invention respectively and conventional monomeric prepare 1-5# vinylformic acid synthetic polymer emulsion, and preparation process is as follows:
Get 2.5g ammonium persulphate to be dissolved in 40g deionized water, obtain initiation solution;
Get 0.5g sodium lauryl sulphate, 1.0g polyoxyethylene nonylphenol ether (NP-10) and 130g deionized water mix and blend 20min, add vinylbenzene 275g, butyl acrylate 125g, vinylformic acid 6g, polymerizable properties-correcting agent 20g and 30g initiation solution successively, continue rapid stirring 20min, obtain pre-emulsion;
Get 1.5g sodium p styrene sulfonate, 1.0g polyoxyethylene nonylphenol ether (NP-10), 1.0g sodium lauryl sulphate mix with 370g deionized water, rapid stirring is also warming up to 85 DEG C, add 10g initiation solution and 62g pre-emulsion, be incubated 10min after stirring reaction to general obvious blue light, drip remaining pre-emulsion, drip off in 3h, be warming up to 85 ~ 88 DEG C, after insulation reaction 1h, be cooled to 45 DEG C, with ammoniacal liquor adjust pH to 7 ~ 8, filter discharging, obtain vinylformic acid synthetic polymer emulsion.
The preparation process of existing vinylformic acid synthetic polymer emulsion (being designated as 0# water-based emulsion) is as follows:
Get 2.5g ammonium persulphate to be dissolved in 40g deionized water, obtain initiation solution;
Get 0.5g sodium lauryl sulphate, 1.0g polyoxyethylene nonylphenol ether (NP-10) and 130g deionized water mix and blend 20min, add vinylbenzene 285g, butyl acrylate 135g, vinylformic acid 6g and 30g initiation solution, continue rapid stirring 20min, obtain pre-emulsion;
Get 1.5g sodium p styrene sulfonate, 1.0g polyoxyethylene nonylphenol ether (NP-10), 1.0g sodium lauryl sulphate mix with 370g deionized water, rapid stirring is also warming up to 85 DEG C, add remaining 10g initiation solution and 62g pre-emulsion, 10min is incubated after stirring reaction to general obvious blue light, drip remaining pre-emulsion, control to drip off in 3h, be warming up to 85 ~ 88 DEG C, 45 DEG C are cooled to after continuing insulation reaction 1.5h, with ammoniacal liquor adjust pH to 7 ~ 8, filter discharging, obtain 0# vinylformic acid synthetic polymer emulsion.
Testing example
Mixed with water-soluble silicon oil by 0-5# vinylformic acid synthetic polymer emulsion respectively, obtain test filming emulsion, wherein, the mass ratio of emulsion and film coalescence aid is 11:1, and carry out performance test respectively to filming emulsion, method is as follows:
Measure the surface drying of the paint film that filming emulsion is formed according to GB 1728-79 paint film, putty membrane assay method time of drying and do solid work the time;
Mechanical stability and the Calcium ion stability of filming emulsion is tested according to GB/T 20623-2006;
The sticking power after filming emulsion film forming is measured according to GB9286-98 hundred lattice testing standard;
Water resistance test: filming emulsion is spread evenly across on glass with film preparing device, room temperature leaves standstill one day, then puts into 50 DEG C of loft drier inner dryings 6 hours, takes out and is dipped in water after being cooled to room temperature, the latex film of 2/3 is dipped in water, observes the time that film turns white and comes off.
Test result is in table 1.
Table 1
From table 1 data, the present invention is by the reaction of alkyl-cyclosiloxanes, (methyl) hydroxyalkyl acrylates and Vanadium Pentoxide in FLAKES, obtain the polymerizable properties-correcting agent comprised with polysiloxane segment and phosphate-based acrylate reactions monomer, after vinylformic acid synthetic polymer emulsion film forming prepared therefrom, there is good water tolerance, sticking power and stability, preparation method is simple, for alternative import response type phosphate ester monomer, significantly can reduce costs, have a extensive future.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.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 protection scope of the present invention.
Claims (8)
1. the preparation method of a polymerizable properties-correcting agent, the raw material that described preparation method adopts comprises (methyl) hydroxyalkyl acrylates, stopper, Vanadium Pentoxide in FLAKES, alkyl-cyclosiloxanes and water, and the mol ratio of described Vanadium Pentoxide in FLAKES and alkyl-cyclosiloxanes is (0.2-5): 1;
Described preparation method comprises the following steps:
(1) mixed with stopper by (methyl) hydroxyalkyl acrylates, stir and be warming up to 60 ~ 65 DEG C, gradation adds Vanadium Pentoxide in FLAKES, and control temperature, at 65-85 DEG C, obtains mixed solution;
(2) mixed solution is warming up to 90 ~ 120 DEG C of reaction 1-2h, drips alkyl-cyclosiloxanes, or drip alkyl-cyclosiloxanes and (methyl) hydroxyalkyl acrylates, water is added after being added dropwise to complete, at 90 ~ 120 DEG C of reaction 1 ~ 3h, cooling, obtains polymerizable properties-correcting agent.
2. the preparation method of polymerizable properties-correcting agent as claimed in claim 1, it is characterized in that, the structural formula of described alkyl-cyclosiloxanes is:
wherein, m=4-6, R identical or different are selected from C
1~ C
3alkyl.
3. the preparation method of polymerizable properties-correcting agent as claimed in claim 1 or 2, it is characterized in that, in described step (1), the mol ratio of (methyl) hydroxyalkyl acrylates and Vanadium Pentoxide in FLAKES is (1-4): 1.
4. the preparation method of the polymerizable properties-correcting agent as described in any one of claim 1-3, it is characterized in that, in step (2), drip alkyl-cyclosiloxanes and (methyl) hydroxyalkyl acrylates, and the quality of (methyl) hydroxyalkyl acrylates dripped in this step is 5% ~ 10% of alkyl-cyclosiloxanes quality.
5. the preparation method of polymerizable properties-correcting agent as claimed in claim 4, it is characterized in that, in step (2), dropping mode adopts and first drips 60 ~ 80% of (methyl) hydroxyalkyl acrylates in alkyl-cyclosiloxanes and this step simultaneously, then drips the mode of remaining in this step (methyl) hydroxyalkyl acrylates.
6. the preparation method of polymerizable properties-correcting agent as claimed in claim 4, it is characterized in that, in step (2), dropping mode adopts and first drips alkyl-cyclosiloxanes, then drips the mode of (methyl) hydroxyalkyl acrylates.
7. the preparation method of the polymerizable properties-correcting agent as described in any one of claim 1-3, it is characterized in that, the quality adding water in described step (2) is 2 ~ 5% of (methyl) hydroxyalkyl acrylates and Vanadium Pentoxide in FLAKES quality sum in step (1).
8. the preparation method of the polymerizable properties-correcting agent as described in any one of claim 1-3, is characterized in that, in step (2), the time of described dropping is 1.5 ~ 3h.
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| CN105859921A (en) * | 2016-04-12 | 2016-08-17 | 湖南省金海科技有限公司 | Ultraviolet-curing phosphate ester modified acrylic resin and preparation method thereof |
| CN111620583A (en) * | 2020-06-18 | 2020-09-04 | 十堰长江造型材料有限公司 | Preparation method of natural efficient synthetic sand for precoated sand |
| CN112724406A (en) * | 2020-12-17 | 2021-04-30 | 深圳市安品有机硅材料有限公司 | Water-based organic silicon resin and preparation method thereof |
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| CN1613882A (en) * | 2004-09-14 | 2005-05-11 | 上海市建筑科学研究院有限公司 | High performance silicon emulsion and its preparation |
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