CN100338111C - Double-phobia polyurethane-polyacrylic ester microemulsion and preparation process thereof - Google Patents
Double-phobia polyurethane-polyacrylic ester microemulsion and preparation process thereof Download PDFInfo
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- CN100338111C CN100338111C CNB02113863XA CN02113863A CN100338111C CN 100338111 C CN100338111 C CN 100338111C CN B02113863X A CNB02113863X A CN B02113863XA CN 02113863 A CN02113863 A CN 02113863A CN 100338111 C CN100338111 C CN 100338111C
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Abstract
The present invention relates to an amphiphobic polyurethane-polyacrylic ester microemulsion and a preparation method thereof, which is characterized in that a polyurethane anion macromonomer whose end is provided with a perfluoro chain segment is copolymerized with an acrylate monomer by a conventional emulsion polymerization method, and a microemulsion with a core-shell structure with sparse molecular chains is formed. The amphiphobic polyurethane-polyacrylic ester microemulsion has both good physical properties of polyurethane and polyacrylic ester and the outstanding surface property of fluor-containing resin, and has wide application prospects in the field of paint.
Description
Affiliated technical field
The present invention relates to a kind of two thin property microemulsions and preparation method thereof, urethane (PU)-polyacrylic ester (PA) microemulsion of particularly a kind of not only hydrophobic but also oleophobic and preparation method thereof.
Background technology:
The polyurethane-polyacrylate compound aqueous dispersion has possessed urethane and polyacrylic ester advantage separately simultaneously, film performance good (Chinese patent, application number: 01108770.0).But, it still can not satisfy the requirement of some senior application or special coating at aspects such as pollution resistance, weathering resistance, organic solvent resistance, water tolerance, therefore consider to introduce the structure that fluoro-containing group changes the polyurethane-polyacrylate multipolymer, make the copolymerization glued membrane after the modification not only keep original characteristic, and improving weather resistance, the pollution resistance of filming effectively, application prospect is extensive.Usually, the method for introducing fluoro-containing group has three kinds: the one, fluorochemical monomer, as: the homopolymerization of trifluorochloroethylene, tetrafluoroethylene, fluorinated acrylate monomer or with the copolymerization (Japanese Patent JP63342022, international monopoly 9618665) of other vinyl monomers; The 2nd, when polymerization, add fluorochemical additive, as: Perfluorocaprylic Acid, (Japanese Patents 11293159) such as fluorocarbon surfactant FC-3, FN-3; The 3rd, the blend of fluoropolymer and other polymkeric substance (Japanese Patent JP11293281).The most popular at present external organic fluorine material that is used for coating is to introduce fluorin radical to carry out modification by copolymerization when preparation acrylate material and organosilicon material, (per) fluoropolymer, fluorine carbon teminal based polyalcohol is wherein arranged and fluoro-containing group is grafted on the fluoropolymer that constitutes on the main polymer chain etc.The research of domestic fluorine coating is the most representative to be quarternary copolymerized fluorine coating based on trifluorochloroethylene, and the research of fluorinated acrylate monomer and other fluorine resin is still belonged to blank.
The technical scheme of invention
The reason that fluoropolymer has characteristics such as excellent two thin property and automatically cleaning is that the perfluor side chain stretches in the polymkeric substance in air, occupied the interface of polymkeric substance and air, greatly reduces the surface energy of polymkeric substance, and it is difficult to by organic liquid and water infiltration.And C-F key bond energy is big, stable, and the structure that side chain coats main chain forms well " shielding protection " to the polymkeric substance interior molecules, makes its thermostability with height and outstanding unreactiveness.Therefore, as long as can make as much as possible the occupying on the polymer/air interface of perfluor side chain in the fluorinated component on the synthesis technique, just can make the fluoro-containing coating that performance is good, fluorine content is low, to reduce its cost.
The technical scheme that technical solution problem of the present invention is adopted is: based on patent applied for (application number: 01108770.0), make the double-phobia polyurethane-polyacrylic ester microemulsion with comb-type structure by special polymerization technique.The perfluor segment is positioned at chain end of comb copolymer, and during film forming, because hydrophobicity is with capillary different, the perfluor segment is easy to move to the surface of polymeric film, and the surface energy of system is reduced.According to the study, segmented copolymer, graft copolymer, hud typed latex can be no more than under the situation of 1Wt% at fluorine content, reach the non-infiltration effect identical with fluorine-containing homopolymer.In addition,, improved on the one hand the stability of fluorine-containing latex, can carry out crosslinkedly with aminoresin, Resins, epoxy, terpolycyantoamino-formaldehyde resin etc. again on the other hand, made the cross-linking type fluorocarbon coating owing to have-COOH in this polymer architecture.Innovation part of the present invention is: first the perfluor segment is introduced in the polyurethane-polyacrylate multipolymer, synthesize two thin property water-base resin, successfully realized high-performance, low cost and the Water-borne modification three's of fluoro-containing coating combination with pectination.
The invention has the beneficial effects as follows: the emulsion particle with present method preparation has nucleocapsid structure, it is to be shell with the double-phobia polyurethane, polyacrylic ester links by covalent linkage between the nucleocapsid and has micro phase separation structure for nuclear, can fully show the characteristics of each component of multipolymer self.The double-phobia polyurethane-polyacrylic ester microemulsion of preparation has low surface energy, low frictional properties, self-cleaning property, good weathering resistance, erosion resistance and gentle filming condition, has broad application prospects in paint field.
Synthetic method of the present invention:
The terminal perfluor segmental urethane negatively charged ion macromonomer water dispersion of being with of preparation earlier, the emulsion polymerisation process by routine makes this PU macromonomer and acrylic ester monomer copolymerization then, forms the composite micro-emulsion liquid with nucleocapsid structure.Wherein, the solid content of PU macromonomer water dispersion is 10-90%, and solid part weight ratio of urethane and polyacrylic ester is 9: 1-1: 9.
Two thin property PU macromonomer water dispersion among the present invention is earlier to make the performed polymer of end group for-NCO by polyisocyanates monomer and polyalcohols monomer by polyaddition reaction, uses the long-chain fluorine cpd partially end-blocked again, to introduce two thin groups.Use at last that excessive (methyl) acrylic acid hydroxy alkyl ester class monomer will be left-the NCO sealing, to introduce the reactable group.In order to give two certain wetting abilities of thin property PU molecular chain,, in this PU macromonomer, hydrophilic component such as carboxyl or tertiary amine groups have also been introduced to make stable water dispersion.
Polyisocyanates monomer used herein is selected inexpensive aromatic diisocyanate usually for use, as: tolylene diisocyanate, diphenylmethanediisocyanate, phenylene diisocyanate, biphenyl diisocyanate, naphthalene diisocyanate etc.If it is strict to the photostabilization of product, just need select the expensive aliphatic diisocyanate of price for use, as: isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dimethylene diisocyanate, methylcyclohexane diisocyanate etc.Usually select for use a kind of polyisocyanates to use separately, also can select for use two or more polyisocyanates to mix and use.
Polyvalent alcohol used herein can be a polyether glycol, as: polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, polyoxyethylene-propylene oxide glycol etc.Also can be polyester polyol, as: polyethylene glycol adipate, polypropylene adipate (PPA), poly adipate succinic acid ester, poly-epsilon-caprolactone, polybutene diacid glycol ester etc.Or the small molecules polyvalent alcohol, as: ethylene glycol, glycol ether, butyleneglycol etc.Usually select for use two or more to mix and use, to regulate its performance.Polyvalent alcohol and polyisocyanates are preparation polyurethane macromolecular monomeric main raw materials, and its amount ratio decide on soft, the hardness of required polymkeric substance, but all should guarantee-the NCO base is excessive, with the generation end group are-performed polymer of NCO base.Generally, in the starting material-NCO base and-molar ratio of OH base is between 1.05-2.
In order to make the double-phobia polyurethane macromonomer have certain wetting ability, also need introduce the polyvalent alcohol or the polyamine compound of hydrophilic radicals such as containing carboxyl or tertiary amine groups, as: dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, 2,3-dimethylolpropionic acid and methyldiethanolamine, ethyldiethanolamine etc.Usually select a kind of independent use for use, also can select for use two or more to mix and use.The consumption of this compounds should be so that the polyurethane macromolecular monomer water dispersion that makes be translucent is advisable to transparent.
As the end-capping reagent of introducing two thin groups, its consumption is the 20-50% (mol ratio) of remnants-NCO base with the long-chain fluorine cpd.The general formula of these long-chain fluorine cpd is Rf (CH
2) mR{ wherein Rf represent fluoro-containing group; M 〉=1; R is-OH ,-NH
2,-CONH
2,-SO
3NH
2, can be divided into four classes according to the composition difference of Rf: the perfluorochemical of all-fluoroalkyl compound, the perfluorochemical that contains heteroatomic all-fluoroalkyl compound, band amido or amide group and band sulphonamide key, listed the general structure of all kinds of fluorine cpd below.
All-fluoroalkyl compound: Rf=(CF
2) nCF
3(n=0-13)
Contain heteroatomic all-fluoroalkyl compound: Rf=R
1(CH
2) p (CF
2) nCF
3(R
1=O, S; P 〉=0; N=0-13)
The perfluorochemical of band amido or amide group: Rf=NR
2(CF
2) nCF
3(R
2=H, CO; N=0-13)
The perfluorochemical of band sulphonamide key: Rf=NR
2O
2S (CF
2) nCF
3(the same)
With the end-capping reagent of (methyl) acrylic acid hydroxy alkyl ester class monomer as the two keys of introducing, its amount ratio residue-NCO base excessive 5-20% (mol ratio).This compounds commonly used has: hydroxyethyl methylacrylate, Rocryl 410, Hydroxyethyl acrylate, Propylene glycol monoacrylate etc.
Double-phobia polyurethane-polyacrylic ester microemulsion among the present invention the ratio of each component is:
A acrylic ester monomer 5-45wt%
B double-phobia polyurethane macromonomer 5-45wt%
C functional monomer 1.0-15wt%
D tensio-active agent 0-2.5wt%
E chain-transfer agent 0.01-1.5wt%
F initiator 0.05-2.0wt%
H water 50-80wt%
Embodiment (1): with water, tensio-active agent, join in the reaction flask, stirring and dissolving under the room temperature, logical nitrogen 30 minutes, after adding initiator, be warming up to 75-85 ℃, begin to add monomer, chain-transfer agent, continue reaction 1-5 hour down at 80-85 ℃ then, be cooled to room temperature, last discharging.
A monomer used herein is selected for use and is contained a kind of C at least
1-C
12(methyl) alkyl acrylate, be preferably C
1-C
8(methyl) alkyl acrylate.The B monomer as previously mentioned.Two kinds of monomeric solid part weight ratios of A, B are 9: 1-1: 9.
The C monomer is selected functional vinyl monomers such as containing carboxyl class, cyano group class, amino class, hydroxy kind, epoxy base class and type siloxane for use.Preferred (methyl) vinylformic acid of carboxyl class function monomer and maleic anhydride etc.; The preferred propylene cyanogen of cyano group class function monomer etc.; The preferred acrylamide of amino class function monomer, N hydroxymethyl acrylamide etc.; Hydroxy kind function monomer preferable methyl Hydroxyethyl acrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate etc.; Preferred (methyl) glycidyl acrylate of epoxy base class function monomer etc.; The structure of type siloxane function monomer is:
Wherein: R
1Be H, CH
3-etc., R
2Can be C
1～C
4Alkyl and phenyl etc.; R
3Can be hydroxyl, carboxyl, amino, sulfonic acid (salt) base, C
1～C
4Alkoxyl group etc.; N is 10～80.
The D tensio-active agent can be an anion surfactant, can be nonionogenic tenside also, or both uses with.Wherein, the preferred Sodium dodecylbenzene sulfonate of anion surfactant, sodium lauryl sulphate, sodium laurylsulfonate etc.; The preferred paregal O of nonionogenic tenside, OS-10, OP-10, OP-7, OP-20 etc.
The E chain-transfer agent is selected alkyl sulfide alcohols, sulphur alkoxide, the mercaptan ethers of C2-C12 for use, preferred lauryl mercaptan.
The F initiator is selected the water-soluble peroxide class for use, preferred Potassium Persulphate, ammonium persulphate, hydrogen peroxide etc.
Embodiment (2): carry out the above-mentioned double-phobia polyurethane-polyacrylic ester microemulsion that makes and aminoresin, Resins, epoxy, terpolycyantoamino-formaldehyde resin etc. crosslinked, can make the cross-linking type fluorocarbon coating, the consumption of additional crosslink agent is 0.5-15% (Wt%).
The present invention is described further below in conjunction with embodiment.
Embodiment 1
The preparation of two thin property PU macromonomer water dispersions: add 111.15gIPDI (isophorone diisocyanate) in reaction flask, 11.27g butyleneglycol and 33.5g dimethylol propionic acid constantly stir and are warming up to 65 ℃, react 6 hours.Add 50mlN-methyl-2-pyrrolidone viscosity reduction, add 50g1 then, 1-dihydro perfluoro octanol reacted 3 hours.Add the 16.26g Jia Jibingxisuanβ-Qiang Yizhi at last, reacted 4 hours.Be cooled to room temperature, drip triethylamine 50g, and add deionized water 210ml under the stirring of fierceness, regulating pH value with triethylamine is 9.The thin property of this pair PU macromonomer water dispersion liquid that is translucent, solid content is 40.3%.
The preparation of double-phobia polyurethane-polyacrylic ester microemulsion: proportioning is as follows:
The A acrylic ester monomer:
Methyl methacrylate: 82.9g
Butyl methacrylate 63.1g
The two thin property PU macromonomer water dispersion 250g of B
The C functional monomer
Vinyl cyanide 6g
The D tensio-active agent
Sodium lauryl sulphate: 2.6g
OP-10 3.3g
E Dodecyl Mercaptan 1g
F Potassium Persulphate 1g
G water 350ml
Its preparation method is: water, tensio-active agent are joined reaction flask, stirring and dissolving under the room temperature, logical nitrogen 30 minutes, after adding initiator, be warming up to 80 ℃, begin to add monomer, chain-transfer agent, 80 ℃ of following insulation reaction 5 hours, be cooled to room temperature, discharging then.
Main performance index: solid content: 30.6% pH value: 7
Particle diameter :≤200nm hardness: 〉=H level
Sticking power (glass, tinplate): 100% (cross-hatching)
The contact angle of polymeric film and water: 〉=90 °
The contact angle of polymeric film and n-Hexadecane: 〉=50 °
This double-phobia polyurethane-polyacrylic ester microemulsion is suitable for use as top-grade furniture varnish.
Embodiment 2
The preparation of two thin property PU macromonomer water dispersions: add 111.15gIPDI (isophorone diisocyanate) in reaction flask, 18.8g Triethylene glycol and 33.5g dimethylol propionic acid constantly stir and are warming up to 65 ℃, react 6 hours.Add 50mlN-methyl-2-pyrrolidone viscosity reduction, add 50g1 then, 1-dihydro perfluoro octanol reacted 3 hours.Add the 16.26g Jia Jibingxisuanβ-Qiang Yizhi at last, reacted 4 hours.Be cooled to room temperature, drip triethylamine 50g, and add deionized water 210ml under the stirring of fierceness, regulating pH value with triethylamine is 9.The thin property of this pair PU macromonomer water dispersion is transparent liquid, and solid content is 41.0%.
The preparation of double-phobia polyurethane-polyacrylic ester microemulsion: proportioning is as follows:
The A acrylic ester monomer:
Methyl acrylate 82.3g
Butyl methacrylate 20.6g
Butyl acrylate: 34.4g
B PU macromonomer water dispersion 360g
The C functional monomer
Vinyl cyanide 7.1g
N hydroxymethyl acrylamide 4.3g
The D tensio-active agent
Sodium lauryl sulphate: 1.8g
OP-10 2.4g
E Dodecyl Mercaptan 0.5g
F Potassium Persulphate 1.7g
G water 340ml
Its preparation method is: water, tensio-active agent are joined reaction flask, and stirring and dissolving under the room temperature, logical nitrogen 30 minutes behind the adding initiator, is warming up to 80 ℃, begins to add monomer, chain-transfer agent, is incubated 5 hours down at 80 ℃ then, is cooled to room temperature, discharging.
Main performance index: solid content: 35% pH value: 7
Particle diameter :≤200nm hardness :≤B level
Sticking power (glass, tinplate): 100% (cross-hatching)
The contact angle of polymeric film and water: 〉=90 °
The contact angle of polymeric film and n-Hexadecane: 〉=50 °
This double-phobia polyurethane-polyacrylic ester microemulsion is suitable for use as fabric finishing agent.
Claims (10)
1, a kind of double-phobia polyurethane-polyacrylic ester microemulsion is characterized in that: solid part weight ratio of urethane and polyacrylic ester is 9: 1-1: 9, and wherein, polyurethane macromolecular monomer end has the long-chain fluorine cpd, and its general structure is as follows:
Rf (CH
2) mR, wherein, m 〉=1, R=-OH ,-NH
2,-CONH
2Or-SO
3NH
2Rf=fluorin radical, Rf are any of following compounds:
All-fluoroalkyl compound: (CF
2) nCF
3N=0-13;
Contain heteroatomic all-fluoroalkyl compound: R
1(CH
2) p (CF
2) nCF
3R
1=O or S; P 〉=0; N=0-13;
The perfluorochemical of band amido or amide group: NR
2(CF
2) nCF
3R
2=H or CO; N=0-13;
The perfluorochemical of band sulphonamide key: NR
2O
2S (CF
2) nCF
3R
2=H or CO; N=0-13.
2, double-phobia polyurethane-polyacrylic ester microemulsion according to claim 1 is characterized in that: it has the nucleocapsid structure of comb type molecular chain.
3, double-phobia polyurethane-polyacrylic ester microemulsion according to claim 1 and 2, it is characterized in that: the nucleocapsid structure of the comb type molecular chain of latex particle is to be shell with the double-phobia polyurethane, the long-chain fluorine cpd are broach, polyacrylic ester is nuclear, connect by covalent linkage between the nucleocapsid, and have micro phase separation structure.
4, the preparation method of claim 1 or 2 described double-phobia polyurethane-polyacrylic ester microemulsions, it is characterized in that: on the polyurethane macromolecular monomer, earlier make the performed polymer of end group by polyaddition reaction for-NCO by polyisocyanates monomer and polyalcohols monomer, use the long-chain fluorine cpd partially end-blocked again, to introduce two thin groups; Use at last that excessive (methyl) acrylic acid hydroxy alkyl ester class monomer will be left-the NCO sealing, to introduce the reactable group.
5, the preparation method of double-phobia polyurethane-polyacrylic ester microemulsion according to claim 4, it is characterized in that: during the preparation double-phobia polyurethane, the polyisocyanates monomer is aromatic diisocyanate, aliphatic diisocyanate or their mixture; Polyvalent alcohol is polyether glycol, polyester polyol or their mixture.
6, the preparation method of double-phobia polyurethane-polyacrylic ester microemulsion according to claim 4 is characterized in that: described long-chain fluorine cpd consumption is the 20-50% mole of remnants-NCO base.
7, the preparation method of double-phobia polyurethane-polyacrylic ester microemulsion according to claim 4, it is characterized in that: have certain wetting ability in order to make the double-phobia polyurethane molecule, to make stable water dispersion, in this double-phobia polyurethane macromonomer, also introduce hydrophilic radical.
8, the preparation method of double-phobia polyurethane-polyacrylic ester microemulsion according to claim 7 is characterized in that: the hydrophilic radical of introducing in the double-phobia polyurethane macromonomer is carboxyl or tertiary amine groups.
9, each described double-phobia polyurethane-polyacrylic ester microemulsion application in furniture lacquer of claim 1-3.
10, each described double-phobia polyurethane-polyacrylic ester microemulsion application in fabric finishing agent of claim 1-3.
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|---|---|---|---|
| CNB02113863XA CN100338111C (en) | 2002-06-12 | 2002-06-12 | Double-phobia polyurethane-polyacrylic ester microemulsion and preparation process thereof |
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|---|---|---|---|
| CNB02113863XA CN100338111C (en) | 2002-06-12 | 2002-06-12 | Double-phobia polyurethane-polyacrylic ester microemulsion and preparation process thereof |
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| CN100338111C true CN100338111C (en) | 2007-09-19 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318467C (en) * | 2004-08-04 | 2007-05-30 | 中国林业科学研究院林产化学工业研究所 | Fine emulsion polymerization method of polyurethane acrylic ester compound emulsion |
| CN100413901C (en) * | 2005-09-29 | 2008-08-27 | 上海申真企业发展有限公司 | Method for preparing inflaming retarding type copolymerization latex of urethane acrylate |
| CN101275054B (en) * | 2007-03-29 | 2012-06-20 | 比亚迪股份有限公司 | Ultraviolet cured paint composition and preparation thereof |
| CN101235195B (en) * | 2008-02-27 | 2010-06-02 | 烟台万华聚氨酯股份有限公司 | Cation water polyurethane/acrylic ester composite emulsion and preparation method thereof |
| CN101260179B (en) * | 2008-04-24 | 2011-03-23 | 东莞市宏达聚氨酯有限公司 | Method for preparing fluorine modifying water-base polyurethane emulsion, products and application thereof as industrial paint |
| CN104558505A (en) * | 2014-11-27 | 2015-04-29 | 南京夜视丽精细化工有限责任公司 | Preparation method of polyurethane modified fluorinated acrylic resin for reflecting material |
| CN104650314B (en) * | 2015-01-28 | 2017-04-12 | 中科院广州化学有限公司 | Dual-curing organic fluorine modified polyurethane pre-polymer and preparation method thereof as well as ultraviolet photo-cured membrane manufactured by polyurethane pre-polymer |
| CN104804496B (en) * | 2015-04-28 | 2017-10-03 | 中科院广州化学有限公司南雄材料生产基地 | A kind of low-surface-energy polyurethane photocureable coating and preparation method thereof |
| US10400136B2 (en) * | 2017-01-24 | 2019-09-03 | Hrl Laboratories, Llc | Multiphase waterborne coatings and methods for fabricating the same |
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| CN1089956A (en) * | 1993-01-19 | 1994-07-27 | 江苏石油化工学院 | A kind of novel method for preparing the polyurethane-acrylate copolymer emulsion |
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Assignee: Changfeng Chemicals International Ltd. Assignor: Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2008.12.2 to 2014.7.1 contract change Contract record no.: 2009510000105 Denomination of invention: Double-phobia polyurethane-polyacrylic ester microemulsion and preparation process thereof Granted publication date: 20070919 License type: Exclusive license Record date: 20091015 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.12.2 TO 2014.7.1; CHANGE OF CONTRACT Name of requester: SHANTOU CITY LONGHU CHANGFENG CHEMICAL INDUSTRY CO Effective date: 20091015 |
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| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070919 Termination date: 20110612 |