CN102250275B - Method for preparing waterborne anticorrosion coating resin vinylidene chloride-acrylate - Google Patents
Method for preparing waterborne anticorrosion coating resin vinylidene chloride-acrylate Download PDFInfo
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Abstract
The invention discloses a method for preparing waterborne anticorrosion coating resin vinylidene chloride-acrylate. In the method, vinylidene chloride, acrylate and different compounded emulsifiers are pre-emulsified, and azodiisobutyronitrile is used for initiating polymerization reaction. The method comprises the following steps of: adding partial pre-emulsion into a reactor; heating to temperature higher than the initiation temperature of an initiator, adding the initiator, and performing polymerization reaction at constant temperature to obtain seeded emulsion; and dripping the rest pre-emulsion into the reactor and continuously performing the reaction at constant temperature. The emulsion has high stability, uniform particle size, high resin adhesion and high film and anticorrosion properties, is environment-friendly and nontoxic, and can provide good corrosion protection for carbon steel matrixes.
Description
Technical field
The present invention relates to the coating science and technology field, specifically, relate to a kind of copolymer emulsion and preparation method thereof.
Background technology
The synthetic copolymer latex of vinylidene chloride (VDC) is the coated material of a kind of choke, moisture barrier property excellence, has formed abroad series product, and has been widely used, and domestic coating level VDC copolymer latex is developed.The coating of being prepared take the Vinylidene Chloride Copolymers water miscible liquid as main film forming substance is called Aqueous Vinylidene Chloride Copolymerizing Resin Emulsion Paints or Vinylidene Chloride Copolymers emulsion paint.Water milk type coating is emulsion paint usually, and it is the mixture of the water dispersion (pigment slurry) of the water dispersion (water miscible liquid) of synthetic resins particle and pigment particles.
The advantage of water milk type coating is without organic solvent, odorless, and Environment protection and safety is good, and is cheap, is the developing direction of environmentally friendly solvent type coating.Aqueous Vinylidene Chloride Copolymerizing Resin Emulsion Paints has the excellent properties such as good wear resistance, moistureproofness, oil resistant, chemical-resistant resistance etch, barrier and flame retardant resistance, is widely used as hard floor paint, damp-proof paint, antifouling paste, flame retardant paint and the egg fresh-keeping coating of the aspects such as building, food product pack, precision instrument packing, automobile.But domestic research report to water-based vinylidene chloride-acrylic ester emulsion is also less, especially product that can practical application does not also come into the market, it mainly is that stability of emulsion after its polymerization is bad, the very easy breakdown of emulsion of emulsion, coalescent after long-term placement the, the simultaneously sticking power of film, the index request that salt spray resistance does not reach coating.
Summary of the invention
Vinylidene chloride-acrylic ester emulsion that provides a kind of good stability and preparation method thereof is provided the object of the invention, and the filming of vinylidene chloride-acrylic ester emulsion of utilizing this invention technical scheme to obtain has excellent resistance to impact shock, water tolerance, weathering resistance, salt fog resistance.
Technical purpose of the present invention is achieved by following technical proposals:
A kind of preparation method of waterborne anticorrosion coating resin vinylidene chloride-acrylate, carry out according to following step:
At first; under protection of inert gas; vinylidene chloride, acrylate, emulsifying agent and water are added in the reactor; the mass percent example of wherein said vinylidene chloride and acrylate is (60～95): (5～40); the consumption of described emulsifying agent is 0.5～3.5% of monomer vinylidene chloride and acrylate quality; the add-on of described water is 85～230% of monomer vinylidene chloride and acrylate quality, stirs under ice bath and carries out emulsification, obtains pre-emulsion.
Secondly, 10～50% of pre-emulsion quality is added in the reactor, be filled with rare gas element to get rid of oxygen, be warming up to kick off temperature, to wherein adding initiator, behind the constant temperature initiated polymerization, drip remaining pre-emulsion, constant temperature continues reaction, makes vinylidene chloride-acrylic ester emulsion.
The mass percent example of wherein said vinylidene chloride and acrylate is preferably (75～90): (10～30), optimum is (86-87): (13-14), namely described mass percent example is " vinylidene chloride accounts for the per-cent of vinylidene chloride and acrylate monomer total mass: acrylate accounts for the per-cent of vinylidene chloride and acrylate monomer total mass ".
Described acrylate is that soft monomer and hard monomer form, and wherein soft monomer is butyl acrylate, ethyl propenoate, and hard monomer is methyl acrylate, methyl methacrylate.
In technical scheme of the present invention, preferably 30～50% of pre-emulsion quality is added in the reactor, be more preferably 40-50%.
Described emulsifying agent is any one in the non-ionic Gemini tensio-active agent of anionic Gemini surfactant, Anionic-nonionic Gemini tensio-active agent, asymmetric anion-nonionic Gemini tensio-active agent, part.
Described initiator is Diisopropyl azodicarboxylate.
The present invention passes through vinylidene chloride, acrylate and be compounded with different types of emulsifying agent and carry out pre-emulsification, adopt the Diisopropyl azodicarboxylate initiated polymerization, first the part pre-emulsion is added in the reactor, be warming up to more than the initiator kick off temperature and (can determine actual temp according to the initiator of selecting, and it is constant to keep constant temperature within the reaction times, for example will maintain 55～100 ℃ the reaction times, be preferably 60～85 ℃), add again initiator (for example being dissolved in the Diisopropyl azodicarboxylate in the ethanol), behind the constant temperature initiated polymerization (for example 15～30min), after forming seed emulsion, to wherein dripping the residue pre-emulsion, continue isothermal reaction again.It should be noted that when dripping the residue emulsion in the seed emulsion, need the control rate of addition, unsuitable too fast, be preferably in half an hour and drip off, continue to react at least 5h.
Compared with prior art, the invention has the beneficial effects as follows:
(1) system adopts different sorts Gemini Gemini surfactant, remedied simple single based surfactants as the shortcoming of emulsifying agent: the more emulsifying effectiveness that just can play of amount that single based surfactants needs, but unnecessary free surfactant easily causes the sticking power of film to reduce, simultaneously, even the simple very large emulsifying effect that can not play of nonionogenic tenside add-on, emulsion is unstable.The use of Gemini Gemini surfactant both can reduce the add-on of emulsifying agent, the emulsifying effect that can play again.
(2) good stability, particle diameter are little: by its particle diameter of emulsion little (about 150nm) after the polymerization of this kind scheme and be evenly distributed, overcome the contradiction between particle diameter, viscosity, stability in storage and the film forming properties.
(3) by regulating different types of acrylate monomer (soft, hard monomer ratio) ratio, can change over film strength and toughness, thereby improve the over-all properties of filming.Adopt the propylene glycol phenylate as film coalescence aid, (add-on is the 2-5wt% of quality of the emulsion in the emulsion of adding preparation, be preferably the 3.5wt% of quality of the emulsion): on the steel plate that surface process sand papering was processed, coating thickness is the thick emulsion in the 120um left and right sides, film forming behind 60 ℃ of baking and curing 30min, take out the water-fast and salt spray resistance ability of investigating, the coating performance index of the coating of the present invention's preparation is as shown in the table.
Table 1 integrated performance index of filming
| Project | Detected result | Detection method |
| Hardness | 1H | GB/T 6739-1996 |
| Sticking power | 1 | GB/T 1720-1979 |
| Shock-resistance/kgcm | 50 | GB/T 1732-1993 |
| Snappiness | 1 | GB/T 1731-1993 |
| Water tolerance | 1000 | GB10834-89 |
| Salt fog resistance (5wt%NaCl)/h | The plate face is without foaming, non-corrosive behind the 800h | GB/T 1771-91 |
(4) improved film-forming properties: the present invention prepares the emulsion that system belongs to strong acid type, can can react with metal substrates such as steel plates, be conducive to emulsion in film process breakdown of emulsion and with the combination of base material, improved compactness, water tolerance and the chemical resistance of film.
(5) can adopt the vinylidene chloride that utilizes the present invention to prepare-acrylic ester emulsion to add in the pigment slurry, further prepare watery anti-corrosion paint, and environmental protection.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment.At first according to document record preparation method synthetic emulsifier, as follows with routine its concrete synthetic route of explanation of synthesizing of two (2-ammonium sulphonate-4-dodecylphenyl) ethane and technique:
The dodecylbenzene of getting the 40.00g drying places the 250ml four-hole boiling flask with the hydrogen chloride absorption device, add respectively aluminum trichloride (anhydrous) 4.39g, reflux condensation mode, water-bath, under the mechanical stirring, dropwise add 8.05g 1 by constant pressure funnel, the 2-ethylene dichloride is after dropwising, the rising temperature also is controlled at 80 ℃, reacted 6 hours, stopped reaction gets pale yellow solution.Filter catalyzer, in the isopyknic frozen water of reaction solution impouring, leave standstill, divide oil-yielding stratum.Water layer with the anhydrous diethyl ether extraction repeatedly merges to oil reservoir.Oil reservoir is repeatedly extremely neutral with 7% sodium bicarbonate aqueous solution washing.Be spin-dried for solvent with Rotary Evaporators again, obtain yellow oily liquid.35.70g dimer intermediate product is placed there-necked flask with the hydrogen chloride absorption device, add the 70ml methylene dichloride, start magnetic agitation, the 15.20g oleum is dissolved in the 50ml methylene dichloride, the frozen water condition dropwises in lower 1 hour, continues reaction after 4 hours, stopped reaction.Revolve steaming with rotary film evaporator and remove methylene chloride, get sulfonated products.Under the normal temperature, sulfonated bodies is neutralized to about pH to 7 with trolamine, namely gets deep yellow viscous liquid product.Several different Gemini surfactants have been synthesized according to above-described step
(1) synthetic route of anionic Gemini surfactant
(2) Soxylat A 25-7 connects the synthetic route of basic Gemini tensio-active agent
(3) synthetic route of asymmetric anion-nonionic Gemini tensio-active agent
(4) synthetic route of the non-ionic Gemini tensio-active agent of part
The different sorts Gemini Gemini surfactant that recycles above-mentioned preparation is implemented technical scheme of the present invention, the mass percent example that need to prove the vinylidene chloride that adopts among the following embodiment and acrylate is best proportion, and the change in initiator amount, temperature of reaction, monomer concentration and reaction times can both realize technical scheme of the present invention.
Embodiment 1
2.6g is dissolved in the 276g deionized water such as (3) synthetic asymmetric anion-nonionic Gemini tensio-active agent, after the whole dissolvings of emulsifying agent, add the 28.8g butyl acrylate under the condition of ice bath, 16.8g methyl methacrylate, 278.4g vinylidene chloride, high-speed stirring emulsification is 1 hour under the ice bath, obtains pre-emulsion.
Be that the 242g pre-emulsion adds in the reactor with quality, vacuumize, the inflated with nitrogen triplicate, be warming up to 78 ℃, add the 1.95g Diisopropyl azodicarboxylate that is dissolved in the 5mL ethanol, constant temperature 15～30min begins to drip the residue pre-emulsion, and drip off half an hour, isothermal reaction 5h makes vinylidene chloride-acrylic ester emulsion: solid content is about 55%.This emulsion has fabulous stability in storage, and hardness of film is high, and water-fast, chemical-resistant resistance, salt spray resistance are good, can be applicable to water-borne coatings.
Use the vinylidene chloride-acrylic ester emulsion among the embodiment 1, preparation water-borne coatings prescription sees Table 2.The preparation method is as follows: first 2～No. 6 raw materials are joined in the stirring tank, disperse 30～60min with high speed dispersor, then the emulsion with preparation among the embodiment 1 slowly joins in the stirring tank, and middling speed stirs 20～40min, then filtration, discharging, packing.Prepare the water-borne coatings performance: outward appearance: black, machinery-free impurity, pH are 1.5～3.5, solid content is 45%, viscosity 60 seconds (being coated with-4 glasss).On the steel plate that surface process sand papering was processed, coating thickness is the thick coating in the 120um left and right sides, and film forming behind 60 ℃ of baking and curing 30min is taken out, and investigates water-fast and salt spray resistance ability according to GB described in the literary composition.Film properties: pencil hardness: 1H; Sticking power: 1 grade; Impact strength: 50Kgcm; Snappiness: 1 grade.
Table 2 water-borne coatings prescription
| Sequence number | Form | Mass percent/% |
| 1 | Emulsion among the embodiment 1 | 65 |
| 2 | Pigment slurry | 18 |
| 3 | Wetting dispersing agent | 0.2 |
| 4 | Flow agent | 0.1 |
| 5 | Defoamer | 0.05 |
| 6 | Deionized water | 16.65 |
| Amount to | 100 |
Embodiment 2
2.6g is connected basic Gemini tensio-active agent such as (2) synthetic Soxylat A 25-7 to be dissolved in the 276g deionized water, after the whole dissolvings of emulsifying agent, add the 31.0g butyl acrylate under the condition of ice bath, 14.6g methyl methacrylate, 278.4g vinylidene chloride, high-speed stirring emulsification is 1 hour under the ice bath, obtains pre-emulsion.
Be that the 302g pre-emulsion adds in the reactor with quality, vacuumize, the inflated with nitrogen triplicate, be warming up to 75 ℃, add the 1.95g Diisopropyl azodicarboxylate that is dissolved in the 5mL ethanol, constant temperature 15～30min begins to drip the residue pre-emulsion, and drip off half an hour, isothermal reaction 5h makes vinylidene chloride-acrylic ester emulsion: solid content is about 55%.This emulsion has fabulous stability in storage, and hardness of film is high, and water-fast, chemical-resistant resistance, salt spray resistance are good, can be applicable to water-borne coatings.
Embodiment 3
2.6g is connected basic Gemini tensio-active agent such as (2) synthetic Soxylat A 25-7 to be dissolved in the 276g deionized water, after the whole dissolvings of emulsifying agent, add the 27.0g butyl acrylate under the condition of ice bath, 15.0g methyl methacrylate, 282.0g vinylidene chloride, high-speed stirring emulsification is 1 hour under the ice bath, obtains pre-emulsion.
Be that the 280g pre-emulsion adds in the reactor with quality, vacuumize, the inflated with nitrogen triplicate, be warming up to 75 ℃, add the 1.95g Diisopropyl azodicarboxylate that is dissolved in the 5mL ethanol, constant temperature 15～30min begins to drip the residue pre-emulsion, and drip off half an hour, isothermal reaction 5h makes vinylidene chloride-acrylic ester emulsion: solid content is about 55%.This emulsion has fabulous stability in storage, and hardness of film is high, and water-fast, chemical-resistant resistance, salt spray resistance are good, can be applicable to water-borne coatings.
Embodiment 4
2.6g is dissolved in the 276g deionized water such as (4) synthetic non-ionic Gemini tensio-active agent of part, after the whole dissolvings of emulsifying agent, add the 28.8g butyl acrylate under the condition of ice bath, 16.8g methyl methacrylate, 278.4g vinylidene chloride, high-speed stirring emulsification is 1 hour under the ice bath, obtains pre-emulsion.Be that the 182g pre-emulsion adds in the reactor with quality, vacuumize, the inflated with nitrogen triplicate, be warming up to 75 ℃, add the 1.95g Diisopropyl azodicarboxylate that is dissolved in the 5mL ethanol, constant temperature 15～30min begins to drip the residue pre-emulsion, and drip off half an hour, isothermal reaction 5h makes vinylidene chloride-acrylic ester emulsion: solid content is about 55%.This emulsion has fabulous stability in storage, and hardness of film is high, and water-fast, chemical-resistant resistance, salt spray resistance are good, can be applicable to water-borne coatings.
Embodiment 5
2.6g is dissolved in the 276g deionized water such as (1) synthetic anionic Gemini surfactant, after the whole dissolvings of emulsifying agent, add the 28.8g butyl acrylate under the condition of ice bath, 16.8g methyl methacrylate, 278.4g vinylidene chloride, high-speed stirring emulsification is 1 hour under the ice bath, obtains pre-emulsion.Be that the 280g pre-emulsion adds in the reactor with quality, vacuumize, the inflated with nitrogen triplicate, be warming up to 75 ℃, add the 1.95g Diisopropyl azodicarboxylate that is dissolved in the 5mL ethanol, constant temperature 15～30min begins to drip the residue pre-emulsion, and drip off half an hour, isothermal reaction 5h makes vinylidene chloride-acrylic ester emulsion: solid content is about 55%.This emulsion has fabulous stability in storage, and hardness of film is high, and water-fast, chemical-resistant resistance, salt spray resistance are good, can be applicable to water-borne coatings.
Embodiment 6
2.6g is dissolved in the 276g deionized water such as (4) synthetic non-ionic Gemini tensio-active agent of part, after the whole dissolvings of emulsifying agent, add the 26g butyl acrylate under the condition of ice bath, 19.6g methyl methacrylate, 278.4g vinylidene chloride, high-speed stirring emulsification is 1 hour under the ice bath, obtains pre-emulsion.Be that the 242g pre-emulsion adds in the reactor with quality, vacuumize, the inflated with nitrogen triplicate, be warming up to 75 ℃, add the 1.95g Diisopropyl azodicarboxylate that is dissolved in the 5mL ethanol, constant temperature 15～30min begins to drip the residue pre-emulsion, and drip off half an hour, isothermal reaction 5h makes vinylidene chloride-acrylic ester emulsion: solid content is about 55%.This emulsion has fabulous stability in storage, and hardness of film is high, and water-fast, chemical-resistant resistance, salt spray resistance are good, can be applicable to water-borne coatings.
Embodiment 7
2.6g is dissolved in the 276g deionized water such as (1) synthetic anionic Gemini surfactant, waits emulsifying agent all after the dissolving, add the 27g butyl acrylate under the condition of ice bath, the 15g methyl methacrylate, the 282g vinylidene chloride, high-speed stirring emulsification is 1 hour under the ice bath, obtains pre-emulsion.Be that the 242g pre-emulsion adds in the reactor with quality, vacuumize, the inflated with nitrogen triplicate, be warming up to 75 ℃, add the 1.95g Diisopropyl azodicarboxylate that is dissolved in the 5mL ethanol, constant temperature 15～30min begins to drip the residue pre-emulsion, and drip off half an hour, isothermal reaction 5h makes vinylidene chloride-acrylic ester emulsion: solid content is about 55%.This emulsion has fabulous stability in storage, and hardness of film is high, and water-fast, chemical-resistant resistance, salt spray resistance are good, can be applicable to water-borne coatings.
Need to prove can be in the invention technical scheme mass percent (60～95) of vinylidene chloride and acrylate: in the scope of (5～40), adjust both actual functional quality proportioning, initiator amount, temperature of reaction and time, all can realize technical scheme of the present invention.
Above the present invention has been done exemplary description; should be noted that; in the situation that do not break away from core of the present invention, the replacement that is equal to that any simple distortion, modification or other those skilled in the art can not spend creative work all falls into protection scope of the present invention.
Claims (8)
1. the preparation method of a waterborne anticorrosion coating resin vinylidene chloride-acrylate is characterized in that, carries out according to following step:
At first, under protection of inert gas, vinylidene chloride, acrylate, emulsifying agent and water are added in the reactor, the mass percent example of wherein said vinylidene chloride and acrylate is (60～95): (5～40), the consumption of described emulsifying agent is 0.5～3.5% of monomer vinylidene chloride and acrylate quality, the add-on of described water is 85～230% of monomer vinylidene chloride and acrylate quality, stirs under ice bath and carries out emulsification, obtains pre-emulsion;
Secondly, 10～50% of pre-emulsion quality is added in the reactor, be filled with rare gas element to get rid of oxygen, be warming up to kick off temperature, to wherein adding initiator, behind the constant temperature initiated polymerization, drip remaining pre-emulsion, constant temperature continues reaction, makes vinylidene chloride-acrylic ester emulsion;
Described acrylate is that soft monomer and hard monomer form, and wherein soft monomer is butyl acrylate, ethyl propenoate, and hard monomer is methyl acrylate, methyl methacrylate;
Described emulsifying agent is any one in anionic Gemini surfactant, Anionic-nonionic Gemini tensio-active agent, asymmetric anion-nonionic Gemini tensio-active agent, the non-ionic Gemini tensio-active agent of part.
2. the preparation method of a kind of waterborne anticorrosion coating resin vinylidene chloride-acrylate according to claim 1 is characterized in that, described initiator is Diisopropyl azodicarboxylate.
3. the preparation method of a kind of waterborne anticorrosion coating resin vinylidene chloride-acrylate according to claim 1 is characterized in that, the mass percent example of described vinylidene chloride and acrylate is (75～90): (10～30).
4. the preparation method of a kind of waterborne anticorrosion coating resin vinylidene chloride-acrylate according to claim 3 is characterized in that, the mass percent example of described vinylidene chloride and acrylate is (86-87): (13-14).
5. the preparation method of a kind of waterborne anticorrosion coating resin vinylidene chloride-acrylate according to claim 1 is characterized in that, secondly 30～50% of pre-emulsion quality is added in the reactor.
6. the preparation method of a kind of waterborne anticorrosion coating resin vinylidene chloride-acrylate according to claim 5 is characterized in that, secondly the 40-50% with the pre-emulsion quality adds in the reactor.
7. the preparation method of a kind of waterborne anticorrosion coating resin vinylidene chloride-acrylate according to claim 1 is characterized in that, when the preparation pre-emulsion, temperature of reaction is maintained 60～85 ℃, constant temperature initiated polymerization 15～30min.
8. the preparation method of a kind of waterborne anticorrosion coating resin vinylidene chloride-acrylate according to claim 1 is characterized in that, dripping the residue pre-emulsion time spent is half an hour, and constant temperature continues reaction at least 5 hours.
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| CN103254700B (en) * | 2013-05-17 | 2015-04-08 | 康跃金 | Water-based coating |
| CN105153833A (en) * | 2015-09-23 | 2015-12-16 | 南通瑞普埃尔生物工程有限公司 | Low baking water-based environment-friendly dip-coating primer for motor tricycle and preparation method of primer |
| CN106995635A (en) * | 2016-01-26 | 2017-08-01 | 淄博坤瀚精细化工有限公司 | A kind of metallic paint is with aqueous high adhesion force high abrasion emulsion |
| CN106749833A (en) * | 2016-11-23 | 2017-05-31 | 江苏十松新材料科技有限公司 | Vinylidene chloride acrylate Organosiliconcopolymere latex and preparation method thereof |
| CN108727545B (en) * | 2018-06-13 | 2021-07-06 | 鲁东大学 | Anticorrosive antifouling coating resin and preparation method thereof |
| CN110183902B (en) * | 2019-06-04 | 2022-08-02 | 云浮市金莱昊化工有限公司 | Water-based gravure printing ink and preparation method and application thereof |
| CN111704689B (en) * | 2020-06-29 | 2022-04-26 | 天津城建大学 | High-adhesion water-based vinylidene chloride copolymer emulsion for metal surface and preparation method thereof |
| CN111518235A (en) * | 2020-06-29 | 2020-08-11 | 天津城建大学 | Water-based vinylidene chloride copolymer resin and preparation method thereof |
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| CN100497408C (en) * | 2007-03-27 | 2009-06-10 | 中山大学 | Self-deposition coating based on vinylidene chloride-acrylate copolymer latex and preparing method |
| DE102007034456A1 (en) * | 2007-07-20 | 2009-01-22 | Evonik Röhm Gmbh | Coating formulation with improved metal adhesion |
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