CN103172820A - Tung-oil-based waterborne polyurethane and preparation method thereof - Google Patents
Tung-oil-based waterborne polyurethane and preparation method thereof Download PDFInfo
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- CN103172820A CN103172820A CN2011104333378A CN201110433337A CN103172820A CN 103172820 A CN103172820 A CN 103172820A CN 2011104333378 A CN2011104333378 A CN 2011104333378A CN 201110433337 A CN201110433337 A CN 201110433337A CN 103172820 A CN103172820 A CN 103172820A
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Abstract
The invention relates to the technical field of biological materials and treatment and particularly relates to tung-oil-based waterborne polyurethane and a preparation method thereof. According to the tung oil-based waterborne polyurethane and the preparation method provided by the invention, water is taken as a dispersion medium, so that the tung-oil-based waterborne polyurethane has the advantages of being economical, non-toxic, free from pungent smell, non-combustible, environmentally-friendly, and the like; the water resistance of a waterborne polyurethane film is improved, the defect of poor water resistance of current waterborne polyurethane is overcome, a tung-oil-based waterborne polyurethane skeleton contains a tung oil ingredient to form a network structure so as to improve the water resistance of the waterborne polyurethane; the film formation performance of tung oil is good, so that the tung oil is introduced into the polyurethane skeleton to greatly improve the film formation performance of the waterborne polyurethane; and the tung oil ingredient contains a conjugated double bond, the curing process of the tung-oil-based waterborne polyurethane can be a thermal curing process, and more importantly, the curing process can be an oxidization curing process in the presence of oxygen, so that the tung-oil-based waterborne polyurethane can be stable for a long time under the conditions of air tightness and normal temperature.
Description
Technical field
The present invention relates to biomaterial and processing technology field, refer in particular to a kind of tung oil base water polyurethane and preparation method thereof.
Background technology
Tung oil is the local product resource of China, is renewable resources, and tung oil is the primary product in tung oil tree (Aleurites fordii) seeds, important industrial raw material and traditional exporting, the height of its value, purposes is wide, causes already the attention of many countries; Tung oil has special chemical structure and active chemical property.The exploitation of tung oil resource is combined with the modification of the large kind macromolecular material of industrialization, and to the high-performance development, be conducive to the industrial application of product.Coating take tung oil as main body can further enlarge purposes, and the high-grade product of tung oil can be used to smear aircraft and submarine shell, and strand and offshore petroleum drilling equipment etc.Waterborne polyurethane resin is filmed and is had excellent wear resistance, scuff resistance, adhesive property, snappiness and good low-temperature performance, high gloss, but there is poor water resistance, many defectives such as resistance to elevated temperatures is not good, and solvent resistance is bad, how to be incorporated in urethane tung oil and Water-borne modification, take full advantage of renewable resources, produce high-grade tung oil base water polyurethane, present or less problem that sets foot in.
Summary of the invention
The invention reside in for the problem that present tung oil is incorporated in urethane and Water-borne modification exists, and a kind of tung oil base water polyurethane that overcomes the above problems and preparation method thereof is provided.
For achieving the above object, the present invention adopts following technical scheme:
A kind of tung oil base water polyurethane: as shown in reaction formula 1 alcoholysis of tung oil and reaction formula 2 by modified tung oil through reaction preparation for oyster white or with the latex tung oil base water polyurethane of light brown:
Wherein: R is CH
3(CH
2)
3CH=CH-CH=CH-CH=CH-(CH
2)
7-
Reaction formula I
Reaction formula II
A kind of preparation method of the base water polyurethane of tung oil as mentioned above is characterized in that, preparation comprises the processing step of following order:
(1), preparation modified tung oil: tung oil is carried out modification to exchange by chain under the low first alcohol catalyst effect of molecule two (or three), produce modified tung oil, consist of the ester of the eleostearic acid of hydroxyl, comprise eleostearic acid glyceryl ester glycol, the viscous mixture of eleostearic acid glyceryl ester single methanol, low-molecular-weight diol list eleostearate, tung oil etc.;
(2), preparation contains the aqueous polyurethane dispersion of tung oil base, synthetic modified tung oil based mixtures, vulcabond, dimethylol propionic acid, polyester diol as main raw material, adopt the method for polycondensation in the step 1, and preparation contains the polyurethane prepolymer of hydrophilic radical carboxyl.
(3), with the polyurethane prepolymer cool to room temperature that contains the hydrophilic radical carboxyl (20-35 ℃) of preparation in step 2 and drip 15-30 part triethylamine and be neutralized between pH=7～8.5, then the deionized water that drips the 500-1500 weight part under shear action carries out aquation to be disperseed, 10-150 weight part quadrol chain extension then drips, Distillation recovery acetone, preparation contains the aqueous polyurethane dispersion of tung oil base.
The composition of each raw material following (by weight) in wherein said step 1: 432 parts of tung oil; The first pure 62-620 part of two (or three); Catalyzer 3-50 part; It is 10: 1～1: 1 that two (or three) unit alcohol is converted into mol ratio with tung oil.
Each material composition following (by weight) in wherein said step 2: 500 parts of modified tung oils; Vulcabond 100-1000 part; Dimethylol propionic acid 100-300 part; Polyester diol 100-1000 part; Dibutyl tin dilaurate 5-100 part; Acetone 100-700 part; Triethylamine 15-300 part; Deionized water 500-1500 part; Quadrol 10-150 part.
Wherein: isocyanate group and hydroxyl are converted into mole number, ratio=1.1 of its mole number～2.5.
In wherein said step 1 catalyzer be highly basic KOH, NaOH or strong acid p-methyl benzenesulfonic acid, to first hydroxy benzenesulfonic acid etc. or zinc acetate or manganese acetate or their supported catalyst, its consumption proportion is the 0.1%-8.0% scope with tung oil and the first pure total amount of lower molecular weight two (three) (by weight).
Wherein said step 1 temperature section and reaction times are: 50-80 ℃, reacted 2-7 hour; Or 90-110 ℃, reacted 2-7 hour; Or 120-140 ℃, reacted 1-4 hour.
In wherein said step 2, the mol ratio of isocyanate groups and hydroxyl is between 1.1-2.5.
In wherein said step 2, temperature section and reaction times are: 45 ℃, and reaction times 0.5-1 hour; 50-65 ℃, reaction times 3-7.5 hour; Its dimethylol propionic acid adds with the form of pressed powder.
Beneficial effect of the present invention is: tung oil base water polyurethane of preparation of the present invention and preparation method thereof: take water as dispersion medium, possess economy, nontoxic, have no irritating odor, do not fire, the advantage such as environmental protection; Utilize the distinctive tung oil resources advantage of China, take tung oil as main raw material, prepare aqueous polyurethane dispersion, widened deep processing and the range of application of tung oil, improve its using value, simultaneously, can reduce the dependency to petrochemicals; Help to improve the water repelling property that aqueous polyurethane is filmed, solve present aqueous polyurethane and have the poor defective of water repelling property, owing to containing the tung oil component in tung oil base water polyurethane skeleton, utilize the conjugated double bond system in tung oil, (as oxidation cross-linked) crosslinkable under proper condition, form network structure, thereby increase its water resisting property; Can appropriateness increase the content of wetting ability component in polyurethane skeleton, thereby solve or partly solve dispersing morphology, the adjustment solid content of latex particle in water, increase its wetting ability.Its expensive goods (isocyanic ester be non-benzene series example) is particularly useful for the antifogging coating as automobile windshield, is coated with simple to operately, does not need special curing apparatus; Be conducive to solve the relatively poor defective of polyurethane latex particle film forming properties, because the film forming properties of tung oil is good, by tung oil is incorporated in polyurethane skeleton, can improve to a great extent the film forming properties of aqueous polyurethane; Can prepare the single-component system, convenient operation and process stabilizing solve the inconvenience that two components or active function groups end-blocking bring.The tung oil component contains conjugated double bond, and its solidification process can be thermofixation, the oxidative cure that what is more important can be under aerobic exists, therefore, can be steady in a long-term under the condition of isolated air, normal temperature.
Embodiment:
Embodiment one
starting material: tung oil (industrial goods, carry out drying with anhydrous magnesium sulfate before using), ethylene glycol (chemical pure, before use, vacuum-drying 2 hours), tosic acid (chemical pure), pol-1256 (industrial goods, hydroxy radical content: 1.0mmo/g), Toluene-2,4-diisocyanate, 4-vulcabond (chemical pure), dibutyl tin dilaurate (analytical pure), acetone is (before use, use anhydrous magnesium sulfate drying, underpressure distillation), triethylamine (chemical pure), dimethylol propionic acid (industrial goods, use the initial vacuum drying), quadrol (chemical pure), deionized water.
1. the preparation of modified tung oil
Formula (by weight)
432 parts of tung oil
120 parts of ethylene glycol
6 parts of p-methyl benzenesulfonic acids
Concrete preparation method is:
Take 120 parts of ethylene glycol and join in band thermometer, reflux condensing tube (sharing with nitrogen ingress pipe), dropping funnel four-hole bottle, add 6 parts of p-methyl benzenesulfonic acids, stir, pass into nitrogen (eliminating oxygen), be warmed up to 65 ℃; Take 432 parts of tung oil in dropping funnel, and be added drop-wise in reaction mixture, after dripping, continue reaction 3 hours, be warmed up to 110 ℃, continue reaction 5 hours, be warmed up to subsequently 140 ℃, continue reaction 2 hours, shady and cool place is preserved in the product sealing.Resulting modified tung oil is light brown viscous liquid, and it is 6.6mmol/g that Tetra hydro Phthalic anhydride-pyridine method is measured its hydroxy radical content
2. the preparation of tung oil base water polyurethane dispersion
Concrete preparation method is:
After taking 200 parts of pol-1256,200 parts of modified tung oils and mixing, be transferred to 200 parts of acetone and be with in thermometer, reflux condensing tube, dropping funnel four-hole bottle, be warmed up to 45 ℃, stir; Take 275 parts of tolylene diisocyanates in dropping funnel, and be added drop-wise to gradually in reaction mixture, after dripping, continue reaction 0.5 hour, be warmed up to subsequently 65 ℃, and add 8.5 parts of dibutyl tin dilaurates, reacted 2 hours; Take 80 parts of dimethylol propionic acids and join in reaction mixture with the form of pressed powder, and adding appropriate acetone, continuing back flow reaction 3 hours (at this moment, viscosity increases, and can see that bubble obviously increases).Stopped reaction, cool to room temperature (between 25-35 ℃), take 66 parts of triethylamines and (be mixed with the acetone soln of 1: 1, by volume), under agitation be added drop-wise to gradually in reaction mixture, after being added dropwise to complete, continue to stir 15 minutes, then be transferred in dispersion machine, under the high speed shear effect, slowly drip 820 parts of water of water, after dripping, continue to stir 0.5 hour, add subsequently 15 parts of second diaminos to carry out chain extension, continue reaction 0.5 hour, Distillation recovery acetone obtains polyurethane aqueous dispersions.
Embodiment two
starting material: tung oil (industrial goods, carry out drying with anhydrous manganous sulfate before using), 1,4-butyleneglycol (chemical pure, before use, vacuum-drying 2 hours), potassium hydroxide (analytical pure), pol-1256 (industrial goods, hydroxy radical content: 1.0mmo/g), isophorone diisocyanate (chemical pure), dibutyl tin dilaurate (analytical pure), acetone is (before use, use anhydrous magnesium sulfate drying, underpressure distillation), triethylamine (chemical pure), dimethylol propionic acid (industrial goods, use the initial vacuum drying), isophorone diamine (chemical pure), deionized water.
1. the preparation of modified tung oil
Formula (by weight)
432 parts of tung oil
180 parts of BDOs
5 parts, potassium hydroxide
Concrete preparation method is:
Take 180 parts of BDOs and join in band thermometer, reflux condensing tube (sharing with nitrogen ingress pipe), dropping funnel four-hole bottle, add 5 parts of KOH, stir, pass into nitrogen (eliminating oxygen), be warmed up to 65 ℃; Take 432 parts of tung oil in dropping funnel, and be added drop-wise in reaction mixture, after dripping, continue reaction 3 hours, be warmed up to 110 ℃, continue reaction 5 hours, be warmed up to subsequently 140 ℃, continue reaction 1 hour.Cool to room temperature adds the boiling water of 1000 parts of 80 ℃ of left and right, fully vibration in microwave oscillator, then be placed in the thermostat container of 80 ℃, standing 24 hours, separatory was except anhydrating, this process 3 times repeatedly, then modified tung oil dry 24 hours (80, vacuum tightness is 0.001pa) in vacuum with gained be transferred in clear-glass bottle, add the anhydrous magnesium sulfate of 50 parts of left and right fully to shake up, standing, sealing is preserved, and gets supernatant liquid during use.Resulting modified tung oil is light brown viscous liquid, and it is 3.5mmol/g that Tetra hydro Phthalic anhydride-pyridine method is measured its hydroxy radical content
2. the preparation of tung oil base water polyurethane dispersion
Concrete preparation method is:
After taking 80 parts of pol-1256,100 parts of modified tung oils and mixing, be transferred to 100 parts of acetone and be with in thermometer, reflux condensing tube, dropping funnel four-hole bottle, be warmed up to 45 ℃, stir; Take 100 parts of tolylene diisocyanates in dropping funnel, and be added drop-wise to gradually in reaction mixture, after dripping, continue reaction 0.5 hour, be warmed up to subsequently 65 ℃, and add 6.5 parts of dibutyl tin dilaurates, reacted 2 hours; Take 25 parts of dimethylol propionic acids and join in reaction mixture with the form of pressed powder, and adding appropriate acetone, continuing back flow reaction 3 hours (at this moment, viscosity increases, and can see that bubble obviously increases).Stopped reaction, cool to room temperature (between 25-35 ℃), take 20 parts of triethylamines and (be mixed with the acetone fluid of 1: 1, by volume), under agitation be added drop-wise to gradually in reaction mixture, after being added dropwise to complete, continue to stir 15 minutes, then be transferred in fractal machine, under the high speed shear effect, slowly drip 650 parts of water of water, after dripping, continue to stir 0.5 hour, add subsequently 3 parts of second diaminos to carry out chain extension, continue reaction 0.5 hour, Distillation recovery acetone obtains polyurethane aqueous dispersions.
The above embodiment, it is preferred embodiments of the present invention, be not to limit the scope of the present invention, therefore all equivalences of doing according to the described structure of the present patent application the scope of the claims, feature and principle change or modify, all should be included in patent claim of the present invention.
Claims (8)
1. tung oil base water polyurethane: as shown in reaction formula 1 alcoholysis of tung oil and reaction formula 2 by modified tung oil through the reaction preparation for oyster white or with the latex tung oil base water polyurethane of light brown:
Wherein: R is CH
3(CH
2)
3CH=CH-CH=CH-CH=CH-(CH
2)
7-
Reaction formula I
Reaction formula II
2. the preparation method of tung oil base water polyurethane as claimed in claim 1, is characterized in that, preparation comprises the processing step of following order:
(1), preparation modified tung oil: tung oil is carried out modification to exchange by chain under the low first alcohol catalyst effect of molecule two (or three), produce modified tung oil, consist of the ester of the eleostearic acid of hydroxyl, comprise eleostearic acid glyceryl ester glycol, the viscous mixture of eleostearic acid glyceryl ester single methanol, low-molecular-weight diol list eleostearate, tung oil etc.;
(2), preparation contains the aqueous polyurethane dispersion of tung oil base, synthetic modified tung oil based mixtures, vulcabond, dimethylol propionic acid, polyester diol as main raw material, adopt the method for polycondensation in the step 1, and preparation contains the polyurethane prepolymer of hydrophilic radical carboxyl.
(3), with the polyurethane prepolymer cool to room temperature that contains the hydrophilic radical carboxyl (20-35 ℃) of preparation in step 2 and drip 15-30 part triethylamine and be neutralized between pH=7～8.5, then the deionized water that drips the 500-1500 weight part under shear action carries out aquation to be disperseed, 10-150 weight part quadrol chain extension then drips, Distillation recovery acetone, preparation contains the aqueous polyurethane dispersion of tung oil base.
3. the preparation method of a kind of tung oil base water polyurethane according to claim 2, is characterized in that, the composition of each raw material following (by weight) in described step 1: 432 parts of tung oil; The first pure 62-620 part of two (or three); Catalyzer 3-50 part; It is 10: 1～1: 1 that two (or three) unit alcohol is converted into mol ratio with tung oil.
4. the preparation method of a kind of tung oil base water polyurethane according to claim 2, is characterized in that, each material composition following (by weight) in described step 2: 500 parts of modified tung oils; Vulcabond 100-1000 part; Dimethylol propionic acid 100-300 part; Polyester diol 100-1000 part; Dibutyl tin dilaurate 5-100 part; Acetone 100-700 part; Triethylamine 15-300 part; Deionized water 500-1500 part; Quadrol 10-150 part.
Wherein: isocyanate group and hydroxyl are converted into mole number, ratio=1.1 of its mole number～2.5.
5. the preparation method of a kind of tung oil base water polyurethane according to claim 2, it is characterized in that, in described step 1 catalyzer be highly basic KOH, NaOH or strong acid p-methyl benzenesulfonic acid, to first hydroxy benzenesulfonic acid etc. or zinc acetate or manganese acetate or their supported catalyst, its consumption proportion is the 0.1%-8.0% scope with tung oil and the first pure total amount of lower molecular weight two (three) (by weight).
6. the preparation method of a kind of tung oil base water polyurethane according to claim 2, is characterized in that, described step 1 temperature section and reaction times are: 50-80 ℃, reacted 2-7 hour; Or 90-110 ℃, reacted 2-7 hour; Or 120-140 ℃, reacted 1-4 hour.
7. the preparation method of a kind of tung oil base water polyurethane according to claim 2, is characterized in that, in described step 2, the mol ratio of isocyanate groups and hydroxyl is between 1.1-2.5.
8. the preparation method of a kind of tung oil base water polyurethane according to claim 2, is characterized in that, in described step 2, temperature section and reaction times are: 45 ℃, and reaction times 0.5-1 hour; 50-65 ℃, reaction times 3-7.5 hour; Its dimethylol propionic acid adds with the form of pressed powder.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881049A (en) * | 2014-04-04 | 2014-06-25 | 中南林业科技大学 | Preparation method of eleostearic acid monoglyceride modified waterborne polyurethane emulsion |
| CN103881053A (en) * | 2014-04-04 | 2014-06-25 | 中南林业科技大学 | Method for preparing aqueous polyurethane emulsion modified by tung oil anhydride polyol |
| CN105693981A (en) * | 2015-03-09 | 2016-06-22 | 河南省科学院高新技术研究中心 | Tung oil polyol based anionic polyurethane with post-crosslinking capacity and preparation method of anionic polyurethane |
| CN105693988A (en) * | 2015-03-09 | 2016-06-22 | 河南省科学院高新技术研究中心 | Tung oil polyol based cationic polyurethane with post-crosslinking capacity and preparation method of cationic polyurethane |
| CN105713176A (en) * | 2015-03-09 | 2016-06-29 | 河南省科学院高新技术研究中心 | Tung oil polyhydric-alcohol-based nonionic polyurethane capable of being crosslinked later and preparation thereof |
| CN107022297A (en) * | 2017-04-15 | 2017-08-08 | 湖北铁神化工有限公司 | A kind of water-fast aqueous polyurethane coating with bi component and preparation method thereof |
| CN107189031A (en) * | 2017-06-02 | 2017-09-22 | 华南农业大学 | A kind of UV solidification polyurethane vegetable oil acid esters prepolymers and preparation method and application |
| CN107189032A (en) * | 2017-05-25 | 2017-09-22 | 华南农业大学 | A kind of multifunctional UV solidification polyurethane vegetable oil acid esters prepolymers and its preparation method and application |
| CN109942777A (en) * | 2019-03-28 | 2019-06-28 | 安徽名士达新材料有限公司 | A kind of development and application of aqueous wood oil |
| CN114318864A (en) * | 2022-01-07 | 2022-04-12 | 南通大学 | Finishing method of antibacterial cotton fabric |
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Cited By (16)
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|---|---|---|---|---|
| CN103881053A (en) * | 2014-04-04 | 2014-06-25 | 中南林业科技大学 | Method for preparing aqueous polyurethane emulsion modified by tung oil anhydride polyol |
| CN103881053B (en) * | 2014-04-04 | 2016-09-28 | 中南林业科技大学 | The preparation method of tung oil acid anhydride ester polyol modified aqueous polyurethane emulsion |
| CN103881049B (en) * | 2014-04-04 | 2016-09-28 | 中南林业科技大学 | The preparation method of eleostearic acid monoglyceride modified aqueous polyurethane emulsion |
| CN103881049A (en) * | 2014-04-04 | 2014-06-25 | 中南林业科技大学 | Preparation method of eleostearic acid monoglyceride modified waterborne polyurethane emulsion |
| CN105713176B (en) * | 2015-03-09 | 2018-04-20 | 河南省科学院高新技术研究中心 | The polynary alcohol radical of tung oil can post-crosslinking non-ionic polyurethane and preparation method thereof |
| CN105693981A (en) * | 2015-03-09 | 2016-06-22 | 河南省科学院高新技术研究中心 | Tung oil polyol based anionic polyurethane with post-crosslinking capacity and preparation method of anionic polyurethane |
| CN105693988A (en) * | 2015-03-09 | 2016-06-22 | 河南省科学院高新技术研究中心 | Tung oil polyol based cationic polyurethane with post-crosslinking capacity and preparation method of cationic polyurethane |
| CN105713176A (en) * | 2015-03-09 | 2016-06-29 | 河南省科学院高新技术研究中心 | Tung oil polyhydric-alcohol-based nonionic polyurethane capable of being crosslinked later and preparation thereof |
| CN107022297B (en) * | 2017-04-15 | 2019-08-02 | 湖北铁神新材料有限公司 | A kind of water-fast aqueous polyurethane coating with bi component and preparation method thereof |
| CN107022297A (en) * | 2017-04-15 | 2017-08-08 | 湖北铁神化工有限公司 | A kind of water-fast aqueous polyurethane coating with bi component and preparation method thereof |
| CN107189032A (en) * | 2017-05-25 | 2017-09-22 | 华南农业大学 | A kind of multifunctional UV solidification polyurethane vegetable oil acid esters prepolymers and its preparation method and application |
| CN107189032B (en) * | 2017-05-25 | 2020-10-23 | 华南农业大学 | Multifunctional UV (ultraviolet) curing polyurethane vegetable oleate prepolymer and preparation method and application thereof |
| CN107189031A (en) * | 2017-06-02 | 2017-09-22 | 华南农业大学 | A kind of UV solidification polyurethane vegetable oil acid esters prepolymers and preparation method and application |
| CN107189031B (en) * | 2017-06-02 | 2020-10-23 | 华南农业大学 | UV-cured polyurethane plant oleate prepolymer and preparation method and application thereof |
| CN109942777A (en) * | 2019-03-28 | 2019-06-28 | 安徽名士达新材料有限公司 | A kind of development and application of aqueous wood oil |
| CN114318864A (en) * | 2022-01-07 | 2022-04-12 | 南通大学 | Finishing method of antibacterial cotton fabric |
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Application publication date: 20130626 |