CN105482046A - Method for preparing acrylic ester modified inorganic material-waterborne polyurethane emulsion - Google Patents
Method for preparing acrylic ester modified inorganic material-waterborne polyurethane emulsion Download PDFInfo
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- CN105482046A CN105482046A CN201511009993.XA CN201511009993A CN105482046A CN 105482046 A CN105482046 A CN 105482046A CN 201511009993 A CN201511009993 A CN 201511009993A CN 105482046 A CN105482046 A CN 105482046A
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- acrylic ester
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention provides a method for preparing acrylic ester modified inorganic material-waterborne polyurethane emulsion, and belongs to the technical field of emulsion for waterborne industrial paint. According to the preparation method, scientific and reasonable materials and proportion are screened, improved operation steps and process parameters are adopted, and emulsion with inorganic material-waterborne polyurethane-acrylic ester three-layer core-shell is formed by using acrylic ester as a shell and inorganic material modified waterborne polyurethane as a core by means of a core-shell polymerization process, high-hardness and fast dryness of the inorganic material, flexibility and chemical resistance of polyurethane and high-hardness and low cost of acrylic ester are organically combined to make up weakness and draw respective strengths to obtain the acrylic ester modified inorganic material-waterborne polyurethane emulsion with excellent performance. The emulsion is particularly suitable for waterborne wood lacquer, and has excellent adhesion and sealing property on wood materials.
Description
Technical field
The invention belongs to water-based industrial paint emulsion technology field, relate to a kind of preparation method of acrylate modified inorganic materials-aqueous polyurethane emulsion specifically.
Background technology
Along with domestic environmental regulation is strengthened day by day, solvent based coating is just at hydrotropismsization future development.The discharge organism that traditional oiliness wood lacquer is a large amount of, not only affects the healthy of people, also can in atmosphere with other chemical substance generation chemical reaction, formed PM2.5, cause topsoil.And by contrast, aqueous woodware paint have asepsis environment-protecting, odorlessness, volatilizable thing few, do not fire the advantages such as not quick-fried, can effectively solve solvent based coating form the emission problem of PM2.5, therefore the Water-borne modification of wood lacquer will be trend of the times.Application number is the synthetic method that application discloses a kind of high rigidity aqueous polyurethane of 201410498604.3, and by situ aggregation method, having synthesized take inorganic materials as core, and aqueous polyurethane is the aqueous polyurethane dispersion of shell.Aqueous polyurethane dispersion because of its paint film plentiful, beautiful, there is the advantages such as excellent chemical medicine, weathering resistance, water tolerance, receive an acclaim, but its difference of hardness, easily scratch, the dry shortcoming such as slow, significantly limit again the application of aqueous polyurethane dispersion in aqueous woodware paint.And ACRYLIC EMULSION to have hardness high, the advantages such as fast drying, but its water tolerance, chemical-resistant, poor toughness, glossiness is low.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of acrylate modified inorganic materials-aqueous polyurethane emulsion is provided, under the prerequisite not affecting Property of Waterborne Polyurethane, emulsion cost can be reduced further, improve hardness and the rate of drying of glued membrane.
In order to achieve the above object, by the following technical solutions, its preparation methods steps is as follows in the present invention:
(1) get the raw materials ready by following weight:
(2) alkyl methacrylate monomer of the alkyl acrylate monomer of the water of pre-emulsion material in step (1), emulsifying agent, C4-C12, C4-C20, functional monomer and inorganic material-modified aqueous polyurethane be sequentially added into obtaining pre-emulsion with 200-1000r/min rotating speed high speed dispersion in the emulsification container stirred;
(3) water of backing material in step (1) and emulsifying agent are joined with in the reaction vessel stirred, pre-emulsion and initiator solution is dripped after being heated to 80-90 DEG C with 20-120r/min rotating speed stirring at low speed, control dropping temperature is 80-90 DEG C, and time for adding is 2-4 hour;
(4) 80-90 DEG C of insulation 1-2 hour, is cooled to 65-75 DEG C, adds the Oxidizing and Reducing Agents aqueous solution and carry out aftertreatment, be cooled to 40 DEG C, regulates pH value 7-9 discharging with neutralizing agent.
Emulsifying agent in above-mentioned steps (1) is one or more in anionic emulsifier, nonionic emulsifying agent and reactive emulsifier, and wherein anionic emulsifier is at least one in succinic acid alkyl polyoxyethylene ether monoesters disodium sulfonate, alkyl phenol polyethenoxy ether sodium sulfate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate; Nonionic emulsifying agent is at least one in isomerous tridecanol polyoxyethylene ether, polyoxyethylene nonylphenol ether, ethoxylated dodecyl alcohol; Reactive emulsifier is at least one in allyloxy hydroxypropyl azochlorosulfonate acid sodium, alkane alkene amido alkyl sodium sulfonate, allyloxy polyoxyethylene nonylphenol ether ammonium sulfate; The alkyl acrylate monomer of the C4-C12 in step (1) is one or more in methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, decyl acrylate monomer; The alkyl methacrylate monomer of the C4-C20 in step (1) is one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, octadecyl methacrylate monomer; Functional monomer in step (1) by vinylformic acid, acrylamide, n-methylolacrylamide, diacetone-acryloamide(DAA), Viscoat 295, hydroxyethyl methylacrylate monomer at least two kinds form; Inorganic material-modified aqueous polyurethane in step (1) is the aqueous polyurethane dispersion of code name RC-7312; In step (1), oxygenant is tertbutyl peroxide, and reductive agent is sodium bisulfite; In step (1), initiator is one or more in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate; Neutralizing agent in step (1) is ammoniacal liquor, one or more in 2-amino-2-methyl-1-propanol (code name is AMP-95).
Illustrate: above-mentioned code name is that the product of RC-7312 is produced by Jiangsu Richu Chemical Industry Co., Ltd.
Preparation method of the present invention is by hud polymerization technique, take acrylate as shell, with inorganic material-modified aqueous polyurethane for core, form the emulsion of inorganic materials-aqueous polyurethane-acrylate three-layer nuclear shell, by the high rigidity of inorganic materials, quick-drying, the high rigidity of the snappiness of urethane, chemical-resistant and acrylate, the advantage of low cost three organically combine, three makes up for each other's deficiencies and learn from each other, reach effective performance complement, obtain the high rigidity acrylic ester modified water-soluble polyurethane emulsion of excellent performance.This emulsion is specially adapted to aqueous woodware paint, has good sticking power and closure to timber.The present invention adopts rationally perfect operation steps and processing parameter, inorganic materials is effectively distributed in water-base resin, improves the stability in storage of coating.The raw materials used price of the present invention is low, work simplification, and equipment requirements is not high yet, can reduce emulsion cost further.
Embodiment
The invention is further illustrated by the following examples, but described embodiment is only for illustration of the present invention instead of restriction the present invention.
Embodiment 1
(1) 80g water, 1g allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, 80g butyl acrylate, 400g methyl methacrylate, 2g vinylformic acid, 2g acrylamide, 1g hydroxyethyl methylacrylate and 100 grams of RC-7312 be sequentially added into obtaining pre-emulsion with 200r/min rotating speed high speed dispersion in the emulsification container stirred.
(2) by 8g succinic acid alkyl polyoxyethylene ether monoesters disodium sulfonate and 2g polyoxyethylene nonylphenol ether and 300g water, join with in the reaction vessel stirred, 84 DEG C are heated to 50r/min rotating speed stirring at low speed, drip pre-emulsion and add the aqueous solution of 120g water containing 2.5g Sodium Persulfate initiator, control dropping temperature is 83-86 DEG C, and time for adding is 3 hours.
(3) 85 DEG C of insulations 1 hour, are cooled to 70 DEG C, add the aqueous solution that 0.5g tertbutyl peroxide oxygenant and 0.5g sodium bisulfite reductive agent add 5g water and carry out aftertreatment, be cooled to 40 DEG C, regulate pH value 7-9 discharging with ammoniacal liquor.
Embodiment 2
(1) by 200g water, 3g allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, 2g alkane alkene amido alkyl sodium sulfonate, 150g ethyl acrylate, 280g butyl methacrylate, 6g vinylformic acid, 6g acrylamide, 6g Viscoat 295 and 150 grams of RC-7312 are sequentially added into obtaining pre-emulsion with 800r/min rotating speed high speed dispersion in the emulsification container stirred.
(2) by 3g succinic acid alkyl polyoxyethylene ether monoesters disodium sulfonate, 2g isomerous tridecanol polyoxyethylene ether, 250g water, join with in the reaction vessel stirred, 84 DEG C are heated to 50r/min rotating speed stirring at low speed, drip pre-emulsion and add the aqueous solution of 50g water containing 1g Potassium Persulphate initiator, control dropping temperature is 84-88 DEG C, and time for adding is 3.5 hours.
(3) 86 DEG C of insulations 1 hour, are cooled to 70 DEG C, add the aqueous solution that 0.8g tertbutyl peroxide oxygenant and 0.8g sodium bisulfite reductive agent add 10g water and carry out aftertreatment, be cooled to 40 DEG C, regulate pH value 8-9 discharging with AMP-95.
Be applied on sheet glass by aforesaid propylene acid esters modified aqueous polyurethane emulsion, film thickness is 20 microns, and surface drying time is 15 minutes, and the time of doing solid work is 24 hours.Its hardness >=3H, water-fast 120 hours non-whitenings, resistance to boiling water 15 minutes non-whitenings, alkaline-resisting, resistance to alcohol 1 hour is without exception, and coating transmittance is unchanged.Above performance index are compared with the prior art and are significantly increased.
Claims (9)
1. a preparation method for acrylate modified inorganic materials-aqueous polyurethane emulsion, is characterized in that this preparation method carries out according to the following steps:
(1) get the raw materials ready by following weight:
(2) alkyl methacrylate monomer of the alkyl acrylate monomer of the water of pre-emulsion material in step (1), emulsifying agent, C4-C12, C4-C20, functional monomer and inorganic material-modified aqueous polyurethane be sequentially added into obtaining pre-emulsion with 200-1000r/min rotating speed high speed dispersion in the emulsification container stirred;
(3) water of backing material in step (1) and emulsifying agent are joined with in the reaction vessel stirred, pre-emulsion and initiator solution is dripped after being heated to 80-90 DEG C with 20-120r/min rotating speed stirring at low speed, control dropping temperature is 80-90 DEG C, and time for adding is 2-4 hour;
(4) 80-90 DEG C of insulation 1-2 hour, is cooled to 65-75 DEG C, adds the Oxidizing and Reducing Agents aqueous solution and carry out aftertreatment, be cooled to 40 DEG C, regulates pH value 7-9 discharging with neutralizing agent.
2. preparation method according to claim 1, the emulsifying agent that it is characterized in that in step (1) is one or more in anionic emulsifier, nonionic emulsifying agent and reactive emulsifier, and wherein anionic emulsifier is at least one in succinic acid alkyl polyoxyethylene ether monoesters disodium sulfonate, alkyl phenol polyethenoxy ether sodium sulfate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate; Nonionic emulsifying agent is at least one in isomerous tridecanol polyoxyethylene ether, polyoxyethylene nonylphenol ether, ethoxylated dodecyl alcohol; Reactive emulsifier is at least one in allyloxy hydroxypropyl azochlorosulfonate acid sodium, alkane alkene amido alkyl sodium sulfonate, allyloxy polyoxyethylene nonylphenol ether ammonium sulfate.
3. preparation method according to claim 1, is characterized in that the alkyl acrylate monomer of the C4-C12 in step (1) is one or more in methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, decyl acrylate monomer.
4. preparation method according to claim 1, is characterized in that the alkyl methacrylate monomer of the C4-C20 in step (1) is one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, octadecyl methacrylate monomer.
5. preparation method according to claim 1, it is characterized in that functional monomer in step (1) by vinylformic acid, acrylamide, n-methylolacrylamide, diacetone-acryloamide(DAA), Viscoat 295, hydroxyethyl methylacrylate monomer at least two kinds form.
6. preparation method according to claim 1, the inorganic material-modified aqueous polyurethane that it is characterized in that in step (1) is the aqueous polyurethane dispersion of code name RC-7312.
7. preparation method according to claim 1, it is characterized in that in step (1), oxygenant is tertbutyl peroxide, reductive agent is sodium bisulfite.
8. preparation method according to claim 1, is characterized in that initiator in step (1) is one or more in Sodium Persulfate, Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate.
9. preparation method according to claim 1, is characterized in that the neutralizing agent in step (1) is ammoniacal liquor, one or more in 2-amino-2-methyl-1-propanol (code name is AMP-95).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201511009993.XA CN105482046A (en) | 2015-12-30 | 2015-12-30 | Method for preparing acrylic ester modified inorganic material-waterborne polyurethane emulsion |
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| CN201511009993.XA CN105482046A (en) | 2015-12-30 | 2015-12-30 | Method for preparing acrylic ester modified inorganic material-waterborne polyurethane emulsion |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106752503A (en) * | 2016-11-29 | 2017-05-31 | 青岛海之星生物科技有限公司 | A kind of anti-cracking stain-resistant emulsion paint and preparation method thereof |
| CN108822598A (en) * | 2018-06-20 | 2018-11-16 | 罗国球 | A kind of preparation method of washability aqueous polyurethane wood lacquer |
| CN110028629A (en) * | 2019-04-28 | 2019-07-19 | 南京林业大学 | A kind of preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves |
| CN113004469A (en) * | 2021-03-05 | 2021-06-22 | 威海金合思化工有限公司 | PVC product toughening agent for low-temperature environment and preparation method thereof |
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| CN101343341A (en) * | 2008-08-12 | 2009-01-14 | 无锡市虎皇漆业有限公司 | Preparation method for acrylic acid modified polyurethane water dispersion |
| CN101775106A (en) * | 2010-02-03 | 2010-07-14 | 江苏柏鹤涂料有限公司 | Waterborne acrylic ester-polyurethane resin emulsion and application thereof |
| CN102924664A (en) * | 2012-11-20 | 2013-02-13 | 江苏日出化工有限公司 | Preparation method for core-shell fluorinated polyurethane-acrylate latex |
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| CN104530321A (en) * | 2015-01-30 | 2015-04-22 | 合肥工业大学 | Preparation method of nanoparticle-modified polyurethane acrylate copolymer resin microemulsion |
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2015
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Patent Citations (5)
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| CN101343341A (en) * | 2008-08-12 | 2009-01-14 | 无锡市虎皇漆业有限公司 | Preparation method for acrylic acid modified polyurethane water dispersion |
| CN101775106A (en) * | 2010-02-03 | 2010-07-14 | 江苏柏鹤涂料有限公司 | Waterborne acrylic ester-polyurethane resin emulsion and application thereof |
| CN102924664A (en) * | 2012-11-20 | 2013-02-13 | 江苏日出化工有限公司 | Preparation method for core-shell fluorinated polyurethane-acrylate latex |
| CN104231209A (en) * | 2014-09-26 | 2014-12-24 | 江苏日出化工有限公司 | Preparation method for high-hardness waterborne polyurethane dispersion |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106752503A (en) * | 2016-11-29 | 2017-05-31 | 青岛海之星生物科技有限公司 | A kind of anti-cracking stain-resistant emulsion paint and preparation method thereof |
| CN108822598A (en) * | 2018-06-20 | 2018-11-16 | 罗国球 | A kind of preparation method of washability aqueous polyurethane wood lacquer |
| CN110028629A (en) * | 2019-04-28 | 2019-07-19 | 南京林业大学 | A kind of preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves |
| CN110028629B (en) * | 2019-04-28 | 2021-07-23 | 南京林业大学 | Preparation method of longifolene-based acrylate modified waterborne polyurethane |
| CN113004469A (en) * | 2021-03-05 | 2021-06-22 | 威海金合思化工有限公司 | PVC product toughening agent for low-temperature environment and preparation method thereof |
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