CN105330796A - Method for preparing super-hydrophilicity two-component polyurethane modified acrylic resins - Google Patents
Method for preparing super-hydrophilicity two-component polyurethane modified acrylic resins Download PDFInfo
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- CN105330796A CN105330796A CN201510936929.XA CN201510936929A CN105330796A CN 105330796 A CN105330796 A CN 105330796A CN 201510936929 A CN201510936929 A CN 201510936929A CN 105330796 A CN105330796 A CN 105330796A
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- hydrophilicity
- acrylic resins
- polyurethane
- super
- component polyurethane
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/147—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
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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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a method for preparing super-hydrophilicity two-component polyurethane modified acrylic resins, which combines excellent mechanical property of polyurethane and hydrophilicity of acrylic resins, andmodifies through sodium allyloxy hydroxypropyl sulfonate to compound a super-hydrophilicity resin. The method for preparing the super-hydrophilicity two-component polyurethane modified acrylic resins supplies hydrophilicity by using hydrophilic carboxyl of acrylic monomers and sulfonic groups with strong hydrophilic on the tail end of the sodium allyloxy hydroxypropyl sulfonate, uses hexamethylene diisocyanate as polyurethane components, supplies mechanical property and leads in the hydroxyl groups for solidifying. The super-hydrophilicity two-component polyurethane modified acrylic resins further adopts isocyanate as another one component to thermally cure and film, and has excellent adhesive force, hardness and curing speed and the like and also endows modified coatings with excellent hydrophilicity at the same time after being filmed through the polyurethane.
Description
Technical field
The invention belongs to the preparation field of anti misting materials, be specifically related to the preparation method that a kind of super hydrophilic dual-component polyurethane is acrylic resin modified.
Background introduction
Transparent material has purposes widely in industrial and agricultural production and daily life and military field, the camera lens of such as glasses, laser light protective goggles, visual telescope and various picture pick-up device, mechanical viewing window, swimming goggle, bathroom glass and mirror, vehicle windscreen and rear vision mirror, the helmet, solar panel, the viewing window of surveying instrument, the glass wall in greenhouse etc.But fogging problem brings many inconvenience to the production of people and life, even cause great loss.The concern of the research and development of antifog technology and anti misting materials extremely scientific circles and business circles.Current existing a lot of experts and scholars obtain important breakthrough at this plate, and main antifog mechanism is as follows:
The condition that atomization produces can be divided into two aspects simply:
(1) outside atmosphere: the existence of certain humidity and certain temperature difference, when only having dew point lower than around steam of temperature when substrate surface, the steam in air just can be condensed into water droplet.
(2) wetting property of substrate surface: whether atomization produces, and depends on the surface tension between gas-liquid-solid three-phase.When surface tension is enough large, droplet is easily sprawled, and not easily ties mist; Enough hour of surface tension, droplet is easy to tumble and is also not easy to tie mist.
Based on above feature, synthesize a kind of super hydrophilic resin with premium properties particularly important in antifog field.When water contact angle is less than 10 °, the globule just can sprawl formation moisture film very well on ground, embodies anti-fog performance.
Hydroxyl, carboxyl, sulfonic group and oxyethyl group etc. are often used as and improve hydrophilic group, on the basis ensureing resin mechanical property, introduce these groups and greatly will promote wetting ability.The present invention combines the wetting ability of the mechanical property of urethane excellence and acrylic resin, and with the modification of allyloxy hydroxypropyl azochlorosulfonate acid sodium, synthesizes a kind of super hydrophilic resin.Invent the hydrophilic carboxyl of main Acrylic Acid Monomer, and the sulfonic group that allyloxy hydroxypropyl azochlorosulfonate acid sodium terminal hydrophilic is extremely strong, wetting ability is provided, makes polyurethane component with hexamethylene diisocyanate trimer, mechanical property is provided and introduces the required hydroxyl of solidification.This polymkeric substance makes another component thermofixation film forming with isocyanic ester again, and acrylic resin polyurethane-modified after film forming imparts again the excellent wetting ability of modification film while having excellent sticking power, hardness, solidification rate etc.
Summary of the invention
The object of the present invention is to provide the preparation method that a kind of super hydrophilic dual-component polyurethane is acrylic resin modified.Vinylformic acid used in the present invention and allyloxy hydroxypropyl azochlorosulfonate acid sodium monomer, can introduce a large amount of carboxyl and sulfonic acid group, improve wetting ability on main chain.Simultaneously polyurethane component can also provide excellent mechanical property, can give again modification film like this and surpass hydrophilic antifogging performance while ensureing the performances such as the excellent sticking power of urethane resin, hardness and scratch resistance.
Technical scheme of the present invention is:
The preparation method that super hydrophilic dual-component polyurethane is acrylic resin modified, comprises the steps:
(1) preparation of polyaminoester emulsion: a certain amount of hexamethylene diisocyanate (HDI) tripolymer, ricinolic acid, solvent and catalyst mix are added in 250ml four-hole boiling flask; under nitrogen protection; be warming up to 60 DEG C of isothermal reactions; when hydroxyl value reaches theoretical value; add hydroxyethyl methylacrylate (HEMA); when hydroxyl value reaches theoretical value, add a certain amount of tetramethylolmethane, be cooled to room temperature stand-by.
(2) preparation of polyurethane acroleic acid emulsion: add Acrylic Acid Monomer and allyloxy hydroxypropyl azochlorosulfonate acid sodium (AHPS) improves mixing speed in the first step product, adds the neutralization of a certain amount of neutralizing agent, and adds emulsifying water.Again system being heated to 50 DEG C after emulsification, adding initiator, to reacting complete.
Catalyzer described in step (1) is at least one in dibutyl tin laurate, stannous octoate;
Described in step (2), neutralizing agent is triethylamine;
Described in step (1), solvent is at least one in acetone, 2-butanone and DMF.
The invention has the beneficial effects as follows: by above reaction, synthesis obtains wear-resisting, hydrophilic heat-setting water-borne acrylic resin coating.This resin can be used for the water tolerance, weathering resistance, didirtresistance, the thermotolerance that improve coating, can be widely used in the antifog environment such as glasses, laser light protective goggles, bathroom glass and mirror, vehicle windscreen and rear vision mirror, the helmet, solar panel, the viewing window of surveying instrument and the glass wall in greenhouse.
Embodiment
Embodiment 1
(1) process of Acrylic Acid Monomer: get 10g Acrylic Acid Monomer, uses neutral alumina to cross post and removes stopper in monomer, seal up for safekeeping stand-by.
(2) preparation of polyaminoester emulsion: 11.61g hexamethylene diisocyanate (HDI) tripolymer, catalyzer 0.1g dibutyl tin laurate (DBTDL) and 5ml solvent orange 2 A are added and is equipped with in the dry four-hole boiling flask of agitator, prolong, constant pressure funnel and nitrogen conduit, stirring at room temperature is even, logical nitrogen protection, progressively be warming up to 50 DEG C, controlling to drip speed with constant pressure funnel is 1 second/, dropwise drip 5.97g ricinolic acid, by infrared spectra, reaction 3h, sees that hydroxyl peak all disappears; It is 3 seconds/that continuation constant pressure funnel controls to drip speed, dropwise drip 2.6g hydroxyethyl methylacrylate (HEMA), reaction 1h, till all disappearing by infrared spectra detection hydroxyl peak, after use ice bath speed cold, pour another constant pressure funnel into and seal up for safekeeping stand-by; Separately get the dry four-hole boiling flask that agitator, prolong, constant pressure funnel and nitrogen conduit are housed, add 2.7g tetramethylolmethane and 5mlN, dinethylformamide; Be warming up to 65 DEG C, drip second step products therefrom with the speed of 3 seconds/, reaction 1.5h, till detecting the disappearance of different isocyanate peak; Add 2.02g triethylamine (TEA), rapid stirring 30min, add 34.3g deionized water and continue to stir 10min;
(3) preparation of polyurethane-modified acrylic acid emulsion: when the 3rd step emulsification not yet completes, drips 8.6g vinylformic acid with dropping funnel, and 3.9g allyloxy hydroxypropyl azochlorosulfonate acid sodium (AHPS).Continue to stir 1h, complete to emulsion-stabilizing dispersion; Add 0.71g Potassium Persulphate (KPS), be warming up to 70 DEG C, reaction 3h can obtain product.
Claims (1)
1. the preparation method that super hydrophilic dual-component polyurethane is acrylic resin modified, its characterization step is:
(1) preparation of polyaminoester emulsion: hexamethylene diisocyanate (HDI) tripolymer, ricinolic acid, solvent and catalyst mix are added in 250ml four-hole boiling flask, under nitrogen protection, be warming up to 60 DEG C of isothermal reactions, when hydroxyl value reaches theoretical value, add hydroxyethyl methylacrylate (HEMA), when hydroxyl value reaches theoretical value, add tetramethylolmethane, be cooled to room temperature stand-by;
(2) preparation of polyurethane acroleic acid emulsion: add Acrylic Acid Monomer and allyloxy hydroxypropyl azochlorosulfonate acid sodium (AHPS) improves mixing speed in the first step product, adds neutralizing agent neutralization, and adds emulsifying water; Again system being heated to 50 DEG C after emulsification, adding initiator, to reacting complete.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510936929.XA CN105330796A (en) | 2015-12-16 | 2015-12-16 | Method for preparing super-hydrophilicity two-component polyurethane modified acrylic resins |
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| CN201510936929.XA CN105330796A (en) | 2015-12-16 | 2015-12-16 | Method for preparing super-hydrophilicity two-component polyurethane modified acrylic resins |
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| CN105330796A true CN105330796A (en) | 2016-02-17 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243886A (en) * | 2016-07-29 | 2016-12-21 | 安徽昌发实业有限公司 | A kind of environment-friendly water-based paint of wooden chair |
| CN106752623A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of heat curing-type polyacrylate hydrophilic antifogging coating |
| CN107141988A (en) * | 2017-03-21 | 2017-09-08 | 河北晨阳工贸集团有限公司 | A kind of aqueous anti-fogging ophthalmic len varnish and preparation method thereof |
| CN110760180A (en) * | 2018-07-26 | 2020-02-07 | 浙江华峰热塑性聚氨酯有限公司 | Waterproof moisture-permeable thermoplastic polyurethane polymer and preparation method thereof |
| CN112574383A (en) * | 2020-12-14 | 2021-03-30 | 上海华峰超纤科技股份有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN113416338A (en) * | 2021-07-05 | 2021-09-21 | 海南赛诺实业有限公司 | Antifogging easy-to-tear coating film and preparation method thereof |
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| CN1544500A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院广州化学研究所 | Core-shell particles with acroleic acid esterified polyurethane as main body of core and making method and use thereof |
| CN101481451A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | High solid content latent curing polyurethane acroleic acid hybrid emulsion |
| CN101792570A (en) * | 2010-02-10 | 2010-08-04 | 汤汉良 | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application |
| CN102703015A (en) * | 2012-05-25 | 2012-10-03 | 常州大学 | Preparation method of low monomer-residual acrylic ester modified aqueous polyurethane pressure-sensitive adhesive |
| CN102850512A (en) * | 2011-07-01 | 2013-01-02 | 湖南晟通科技集团有限公司 | Multifunctional hydrophilic light-curing resin and its preparation method |
| CN102964559A (en) * | 2012-12-19 | 2013-03-13 | 江南大学 | Preparation and application methods of high-branched polyester polyol for UV (Ultraviolet) curing waterborne polyurethane coating |
-
2015
- 2015-12-16 CN CN201510936929.XA patent/CN105330796A/en active Pending
Patent Citations (6)
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| CN1544500A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院广州化学研究所 | Core-shell particles with acroleic acid esterified polyurethane as main body of core and making method and use thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243886A (en) * | 2016-07-29 | 2016-12-21 | 安徽昌发实业有限公司 | A kind of environment-friendly water-based paint of wooden chair |
| CN106752623A (en) * | 2016-11-28 | 2017-05-31 | 江南大学 | A kind of preparation method of heat curing-type polyacrylate hydrophilic antifogging coating |
| CN106752623B (en) * | 2016-11-28 | 2018-11-16 | 江南大学 | A kind of preparation method of heat curing type polyacrylate hydrophilic antifogging coating |
| CN107141988A (en) * | 2017-03-21 | 2017-09-08 | 河北晨阳工贸集团有限公司 | A kind of aqueous anti-fogging ophthalmic len varnish and preparation method thereof |
| CN110760180A (en) * | 2018-07-26 | 2020-02-07 | 浙江华峰热塑性聚氨酯有限公司 | Waterproof moisture-permeable thermoplastic polyurethane polymer and preparation method thereof |
| CN110760180B (en) * | 2018-07-26 | 2021-10-12 | 浙江华峰热塑性聚氨酯有限公司 | Waterproof moisture-permeable thermoplastic polyurethane polymer and preparation method thereof |
| CN112574383A (en) * | 2020-12-14 | 2021-03-30 | 上海华峰超纤科技股份有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN112574383B (en) * | 2020-12-14 | 2022-01-21 | 上海华峰超纤科技股份有限公司 | Waterborne polyurethane emulsion and preparation method and application thereof |
| CN113416338A (en) * | 2021-07-05 | 2021-09-21 | 海南赛诺实业有限公司 | Antifogging easy-to-tear coating film and preparation method thereof |
| CN113416338B (en) * | 2021-07-05 | 2022-07-26 | 海南赛诺实业有限公司 | Anti-fog easy-uncovering coating film and preparation method thereof |
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