CN100567233C - Contain the preparation and the application thereof of the all-fluoroalkyl compound of active end group - Google Patents
Contain the preparation and the application thereof of the all-fluoroalkyl compound of active end group Download PDFInfo
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- CN100567233C CN100567233C CNB2007100900289A CN200710090028A CN100567233C CN 100567233 C CN100567233 C CN 100567233C CN B2007100900289 A CNB2007100900289 A CN B2007100900289A CN 200710090028 A CN200710090028 A CN 200710090028A CN 100567233 C CN100567233 C CN 100567233C
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Abstract
The present invention relates to perfluoroalkyl monomer A and diisocyanate B synthetic a kind of all-fluoroalkyl compound that contains active end group in the presence of solvent and catalyzer by hydroxyl.And it is cooperated with the acrylic resin of hydroxyl, obtain the low surface energy coatings composition, be applied on the shell of boats and ships, submarine, play the antifouling effect of drag reduction, be applied on the aviation aircraft engine, play the anti-icing effect of waterproof, be applied on the skin, have automatically cleaning, anti-stain, anti-graffiti effect.
Description
Technical field
The present invention relates to fluorochemicals or composition, but it contains at least one fluorine-containing repeating unit and at least one fluorine-containing end group.The present invention relates to aspects such as coating simultaneously, and its fluoride composition can be used as coating composition and uses or use as other active additives.Add or use the goods of this fluoride composition can have lower surface energy.
Background technology
Coating or active additive mainly act on various body surfaces, rise and decorate or provide protection.Because long-term exposure is very easy to be subjected to the pollution of water, dust, greasy dirt etc. outside.Reduce dirt and retain or make body surface more easy to clean, just need coatingsurface to have lower surface tension, improve the self-cleaning of body surface at body surface.
On polymer and polymer base material, use some fluorochemical or fluorine-containing composition, make it have performances such as hydrophobic oleophobic, existing application widely.Mentioned in " organic fluorine chemistry product and industrial application thereof " as the Banks chief editor.Philips, R.W and Dettre, R.H. just disclose fluorochemical fragment (J.Col.and Interface Sci., 56 (2), 1976) in 1976, show any basically C that contains according to disclosed data
nF
2n+1Polymkeric substance, compound and the oligopolymer of (n 〉=6) all have the hydrophobic oleophobic performance.But when n 〉=8, some fluorochemical or fluorochemical monomer present solid wax shape character, separate than indissoluble, utilize difficulty.
Summary of the invention
One of purpose of the present invention provides a kind of mixture that contains the all-fluoroalkyl compound of active end group, and the preparation method.
Two of purpose of the present invention provides the low surface energy coatings composition of the mixture that comprises the described all-fluoroalkyl compound that contains active end group.
The mixture that contains the all-fluoroalkyl compound of active end group of the present invention is perfluoroalkyl monomer A and the diisocyanate B synthetic in the presence of solvent and catalyzer that contains hydroxyl.
Described A: be perfluoroalkyl monomer with hydroxyl of following structure:
C
nF
2n+1CH
2CH
2OH
N=6 in the formula, 8,10;
Described B: be vulcabond with following formula:
OCN-R-NCO
R is fat, alicyclic ring or aromatic divalent group in the formula, comprises the non-condensed nucleus aromatic group that the fat group, alicyclic group, monocyclic aromatic group, condensed nucleus aromatic group and other linking groups that are no less than two carbon connected.
Described A and B satisfy: hydroxyl is 1: 4 with the isocyano ratio; A and B account for 75～90% weight percents of total charging capacity.
Described vulcabond can be single, also the mixture that can be made up of two kinds or multiple vulcabond.
Described vulcabond comprises: hexamethylene diisocyanate, diformazan phenylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethyl cyclohexane support vulcabond, xylylene diisocyanate, toluene cyclohexalene vulcabond, 4,4 '-two (isocyanic ester cyclohexyl) methane, 2,4 '-tolylene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, 3,3 '-dimethyl diphenylmethane-4,4 '-vulcabond, 1,5-naphthalene diisocyanate, polymethine polyphenyl polyisocyanate.
Described solvent can be ester class or intensive polar solvent, for example ethyl acetate, butylacetate or N-Methyl pyrrolidone, N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE.Most preferably be to choose any one kind of them in ethyl acetate or the butylacetate or two kinds of solvents that mixing is formed.Consumption is the 10-25% weight percent of total charging capacity.
Described catalyzer is to choose any one kind of them in dibutyl tin laurate or the stannous octoate.Consumption is the 0.1-3% weight percent of total charging capacity.
The described mixture that contains the all-fluoroalkyl compound of active end group prepares as follows:
Under nitrogen or argon shield, vulcabond of the present invention under agitation is dissolved in the organic solvent system.After treating to dissolve fully, add catalyzer.Under 0～25 ℃, add the perfluoroalkyl monomer of hydroxyl in batches.Reacted 2-8 hour, Best Times is 2-6 hour; Under 60-80 ℃, reacted 2-10 hour, Best Times is 4-8 hour again.Be cooled to room temperature, obtain transparent low viscosity solution.
Described low surface energy coatings composition comprises: contain the mixture of the all-fluoroalkyl compound of active end group, the acrylic resin of at least a hydroxyl (commercially available prod), proper amount of diluting, color stuffing etc.
The ratio of the mixture of the described all-fluoroalkyl compound that contains active end group and the acrylic resin of hydroxyl is 1: 5 ~ 1: 15.
Described thinner comprises chooses any one kind of them in toluene, dimethylbenzene, acetone, the butanone or two kinds of solvents that mixing is formed.Consumption is the 10-50% weight percent of total charging capacity.
Described color stuffing is Rutile type Titanium Dioxide, talcum powder, mica, floats and choose any one kind of them in pearl, water-ground limestone, red iron oxide, the zinc oxide or two kinds, and two or more mixing is formed.
Described low surface energy coatings preparation method of composition: above-mentioned substance adopts technologies such as brushing or spraying according to routine system lacquer method mixed preparing, obtains smooth smooth low surface energy coat.
The resulting mixture that contains the all-fluoroalkyl compound of active end group has following over-all properties:
(1) good solubility property dissolves in common organic solvent and polar solvent.
(2) good reactivity worth, compound one end is the perfluoroalkyl structure, the other end is the isocyanic ester structure, can guarantee that compound has an active reaction end group.
(3) superior low surface energy, this compound one end group is the perfluor segment, and this product forms microcosmic " comb " shape structure with after resin cooperates, and the perfluor segment is " broach ", and the excellent hydrophobicity energy can be provided, and water contact angle is more than 100 °.
(4) superior persistence, behind this product and the resin solidification, the perfluor segment inserts resin with the chemical bond form, forms side chain, can be behind solvent wiping 600 times, water contact angle is constant substantially.
The mixture of the all-fluoroalkyl compound that contains active end group that the present invention obtains cooperates with the acrylic resin of hydroxyl, can obtain having performance coatings such as automatically cleaning, drag reduction.In national defence, industrial and agricultural production and daily life, have a wide range of applications.As aspects such as external wall, coating, drag reduction antifouling paint, antifog antiicing coatings important potential application is arranged.This technology is used for outdoor antenna, thereby can prevent that the accumulated snow deposition from guaranteeing communication quality; Be used on the shell of ship, submarine, not only reduce the resistance of water, improve route speed, can also reach antifouling effect; Be used in the interior wall energy of petroleum transportation pipeline and prevent to stick, stop up, reduce loss; Be used for the aviation aircraft engine, play the anti-icing effect of waterproof; Be used on the textiles, can also make waterproof, antifouling clothes etc.
Description of drawings
Fig. 1 is the surface energy water contact angle measurement effect figure of embodiment 3 low surface energy coats.
Fig. 2 is the surface energy water contact angle measurement effect figure of embodiment 4 low surface energy coats.
Fig. 3 is the surface energy water contact angle measurement effect figure of embodiment 5 low surface energy coats.
Fig. 4 is the surface energy water contact angle measurement effect figure of embodiment 6 low surface energy coats.
Embodiment
The present invention is further described for following listed examples, but the present invention is not only limited to these embodiment.
Embodiment 1: contain the preparation of mixture of the all-fluoroalkyl compound of active end group
60 parts of tolylene diisocyanates are dissolved in 140 parts the ethyl acetate, add 0.5 part of dibutyl tin laurate, add 800 parts of perfluoroalkyl ethanols then.Be reflected at 0-25 ℃ of following stirring reaction 4 hours, stirred 8 hours down at 60-80 ℃ again.After reactant is cooled to room temperature, obtain 1000 parts of homogeneous liquids.
Embodiment 2: contain the preparation of mixture of the all-fluoroalkyl compound of active end group
40 parts of '-diphenylmethane diisocyanates are dissolved in 200 parts the ethyl acetate, add 0.5 part of dibutyl tin laurate, add 700 parts of perfluoroalkyl ethanols then.Be reflected at 0-25 ℃ of following stirring reaction 2 hours, stirred 6 hours down at 60-80 ℃ again.After reactant is cooled to room temperature, obtain 1000 parts of homogeneous liquids.
Embodiment 3: the preparation of low surface energy coat
Embodiment 1 product is cooperated with acrylic resin (trade mark BS2150), prepares by following step:
A component: 100 parts of BS2150 acrylic resins, 60 parts of color stuffings (30 parts of red iron oxides, 20 parts of zinc oxide and 10 parts of water-ground limestones) and 60 parts of thinners (50 parts of dimethylbenzene and 10 parts of acetone mix) are joined in the container, high speed dispersion is 2 hours under the 2000rpm rotating speed, when fineness is 30～50 μ m, filter metering packing with 100 mesh filter screens;
The B component is the product of embodiment 1;
After A, B component be 5: 1 uniform mixing by weight, adopt the spraying coating process construction, self-vulcanizing, obtain smooth smooth low surface energy coat more than 10 hours set time.Can the water contact angle measurement reach 109 ° to coatingsurface.Effect is seen Fig. 1.This coating can be applicable to the antifouling needs of ship drag reduction, has good effect.
Embodiment 4: the preparation of low surface energy coat
Embodiment 1 product is cooperated with acrylic resin (trade mark BS9960), prepares by following step:
A component: 100 parts of BS9960 acrylic resins, 70 parts of color stuffings (10 parts of red iron oxides of Rutile type Titanium Dioxide, 50 parts float pearl and 10 parts of micas) and 60 parts of thinners (50 parts of toluene and 10 parts of butanone mix) are joined in the container, high speed dispersion is 3 hours under the 2000rpm rotating speed, when fineness is 30～50 μ m, filter metering packing with 100 mesh filter screens;
The B component is embodiment 1 product;
A, B component behind 8: 1 uniform mixing, are adopted the spraying coating process construction, self-vulcanizing, obtain smooth smooth low surface energy coat more than 10 hours set time, can the water contact angle measurement reach 107 ° to coatingsurface; Effect is seen Fig. 2.This coating can be applicable on the aviation aircraft, plays the anti-icing effect of waterproof.
Embodiment 5: the preparation of low surface energy coat
Embodiment 2 products are cooperated with acrylic resin (trade mark BS960), prepare by following step:
A component: 100 parts of BS960 acrylic resins, 70 parts of color stuffings (10 parts of Rutile type Titanium Dioxides, 25 parts of talcum powder, 25 parts of micas and 10 parts of water-ground limestones) and 60 parts of thinners (50 parts of dimethylbenzene and 10 parts of acetone mix) are joined in the container, high speed dispersion is 3 hours under the 2000rpm rotating speed, when fineness is 30～50 μ m, filter metering packing with 100 mesh filter screens;
The B component is the product of embodiment 2;
A, B component behind 11: 1 uniform mixing, are adopted and brush the technology construction, self-vulcanizing, obtain smooth smooth low surface energy coat more than 12 hours set time, can the water contact angle measurement reach 105 ° to coatingsurface.Effect is seen Fig. 3.This coating can be applicable on the outdoor antenna cover, can prevent the accumulated snow accumulation, thereby guarantees communication quality.
Embodiment 6: the preparation of low surface energy coat
The product of embodiment 2 is cooperated with acrylic resin (trade mark BS985), prepares by following step:
A component: 100 parts of BS985 acrylic resins, 75 parts of color stuffings (25 parts of talcum powder, 25 parts of micas and 25 parts of water-ground limestones) and 60 parts of thinners (50 parts of toluene and 10 parts of butanone mix) are joined in the container, high speed dispersion is 4 hours under the 2000rpm rotating speed, when fineness is 30～50 μ m, filter metering packing with 100 mesh filter screens;
B component: be the product of embodiment 2;
A, B component behind 10: 1 uniform mixing, are adopted and brush the technology construction, self-vulcanizing, obtain smooth smooth low surface energy coat more than 24 hours set time.Can the water contact angle measurement reach 100 ° to coatingsurface; Effect is seen Fig. 4.This coating can be applicable on the building external paint, anti-graffiti, as to keep building cleaning and attractive in appearance.
Embodiment 7:
Coating among the embodiment 4,5 is carried out anti-wiping experiment, and after 600 wipings of organic solvent, water contact angle is constant.
Claims (10)
1. a mixture that contains the all-fluoroalkyl compound of active end group is characterized in that, and is synthetic in the presence of solvent and catalyzer by perfluoroalkyl monomer A that contains hydroxyl and diisocyanate B;
Described A: be perfluoroalkyl monomer with hydroxyl of following structure:
C
nF
2n+1CH
2CH
2OH
N=6 in the formula, 8,10;
Described B: be vulcabond with following formula:
OCN-R-NCO
R is fat, alicyclic ring or aromatic divalent group in the formula;
Described A and B satisfy: hydroxyl is 1: 4 with the isocyano ratio; A and B account for 75～90% weight percents of total charging capacity.
2. according to the mixture of the all-fluoroalkyl compound that contains active end group of claim 1, it is characterized in that described R is fat group, alicyclic group, monocyclic aromatic group, condensed nucleus aromatic group and other link non-condensed nucleus aromatic group that group connected that is no less than two carbon.
3. according to the mixture of the all-fluoroalkyl compound that contains active end group of claim 1, it is characterized in that described vulcabond is an one or more combination.
4. according to the mixture of the all-fluoroalkyl compound that contains active end group of claim 2, it is characterized in that, described vulcabond comprises: hexamethylene diisocyanate, the diformazan phenylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethyl cyclohexane support vulcabond, xylylene diisocyanate, toluene cyclohexalene vulcabond, 4,4 '-two (isocyanic ester cyclohexyl) methane, 2,4 '-tolylene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, 3,3 '-dimethyl diphenylmethane-4,4 '-vulcabond, 1, the 5-naphthalene diisocyanate, the polymethine polyphenyl polyisocyanate.
5. according to the mixture of the all-fluoroalkyl compound that contains active end group of claim 1, it is characterized in that described solvent is ester class or intensive polar solvent.
6. according to the mixture of the all-fluoroalkyl compound that contains active end group of claim 5, it is characterized in that described solvent is ethyl acetate, butylacetate or N-Methyl pyrrolidone, N, N '-dimethyl formamide or N, N '-N,N-DIMETHYLACETAMIDE selects wherein one or both; Consumption is the 10-25% weight percent of total charging capacity.
7. according to the mixture of the all-fluoroalkyl compound that contains active end group of claim 1, it is characterized in that described catalyzer is to choose any one kind of them in dibutyl tin laurate or the stannous octoate, consumption is the 0.1-3% weight percent of total charging capacity.
8. according to the mixture of the all-fluoroalkyl compound that contains active end group of claim 1, it is characterized in that the preparation method is: under protection of inert gas; under agitation be dissolved in vulcabond in the organic solvent system; after the dissolving, add catalyzer, under 0～25 ℃ fully; the perfluoroalkyl monomer that in batches adds hydroxyl; reacted 2-8 hour, and under 60-80 ℃, reacted 2-1 0 hour again; be cooled to room temperature, obtain transparent low viscosity solution.
9. a low surface energy coatings composition is characterized in that, comprises acrylic resin, proper amount of diluting, the color stuffing that contains the mixture of the all-fluoroalkyl compound of active end group, at least a hydroxyl as claimed in claim 1.
10. according to the low surface energy coatings composition of claim 9, it is characterized in that the ratio of the mixture of the described all-fluoroalkyl compound that contains active end group and the acrylic resin of hydroxyl is 1: 5 ~ 1: 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100900289A CN100567233C (en) | 2007-03-26 | 2007-03-26 | Contain the preparation and the application thereof of the all-fluoroalkyl compound of active end group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100900289A CN100567233C (en) | 2007-03-26 | 2007-03-26 | Contain the preparation and the application thereof of the all-fluoroalkyl compound of active end group |
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|---|---|
| CN101024743A CN101024743A (en) | 2007-08-29 |
| CN100567233C true CN100567233C (en) | 2009-12-09 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TW200951292A (en) * | 2008-05-28 | 2009-12-16 | Twister Bv | Ice-phobic coating and use thereof |
| CN102352558B (en) * | 2011-06-10 | 2013-06-05 | 上海汇宇精细化工有限公司 | Stain-resistant leather treatment agent and preparation method |
| CN102876150A (en) * | 2011-07-14 | 2013-01-16 | 上海大通高科技材料有限责任公司 | High weather resistant anti-pasting and doodling-proof water-based paint and preparing method thereof |
| CN102676034B (en) * | 2012-04-24 | 2015-08-19 | 三元控股集团有限公司 | A kind of anti-graffiti coating being applicable to outdoor facilities and preparation method thereof |
| JP6188809B2 (en) * | 2012-10-04 | 2017-08-30 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ | Non-aqueous coating composition containing fluorine, coating method of the coating composition and use thereof |
| CN103483974A (en) * | 2013-10-10 | 2014-01-01 | 常熟市方塔涂料化工有限公司 | Environment-friendly grease proofing paint |
| MX2017007379A (en) | 2014-12-17 | 2017-11-06 | Dow Global Technologies Llc | Surfactants for polyurethane foams. |
| CN108976857A (en) * | 2017-06-01 | 2018-12-11 | 东莞前沿技术研究院 | Coating composition, covering and aerostatics |
| CN114058255B (en) * | 2020-07-30 | 2022-05-13 | 海洋化工研究院有限公司 | Low-surface-energy elastic three-proofing coating for nuclear equipment and preparation method thereof |
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Owner name: MARINE CHEMICAL RESEARCH INSTITUTE Free format text: FORMER NAME: RESEARCH INST OF OCEAN CHEMISTRY |
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Address after: 266071 Shandong Province, Qingdao city Jinhu Road No. 4 Patentee after: Marine Chemical Research Institute Address before: 266071 Shandong Province, Qingdao city Jinhu Road No. 4 Patentee before: Research Inst of Ocean Chemistry |
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