CN108586690A - A kind of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin and preparation method - Google Patents
A kind of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin and preparation method Download PDFInfo
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- 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
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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- C08G63/46—Polyesters chemically modified by esterification
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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Abstract
The invention discloses a kind of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin and preparation methods, and in terms of mass fraction, preparing raw material includes：4.0 parts of 24.4 parts of Fructus Zanthoxyli oil, 8.9 parts of trimethylolpropane, 0.0122 part of alcoholysis catalysts, 5.9 7.4 parts of phthalic anhydride, 11.1 13.32 parts of diisocyanate, 4.2 parts of 2,2 dihydromethyl propionic acid, 0.2 part of dibutyl tin dilaurate and triethylamine.The present invention is using Fructus Zanthoxyli oil as raw material, isophorone diisocyanate introduces urethano as modifying agent, 2,2 dihydromethyl propionic acids are aqueous monomers, it is simple for process, paint film has excellent rate of drying and good hardness, water resistance, acid resistance etc., and polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin makes non-edible Fructus Zanthoxyli oil further be developed and used in organic coating, there is good application prospect.
Description
Technical field
The invention belongs to painting technical fields, and in particular to a kind of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin
And preparation method.
Background technology
Phthalic resin coating has paint film adhesion good, bright, it is plentiful the features such as, and there is good application property, and
It can be widely used in the buildings such as bridge and machinery, vehicle with other resin modifieds at the dry or drying paint of a variety of different performances
, the application of ship, aircraft, instrument etc..In addition, alkyd resin raw material is easy to get, and it is simple for process, meet the society of sustainable development
It is required that.However, there is some shortcomings for alkyd resin：Paint film rate of drying is slow, hardness is low, water-fast, alkali resistance is bad.
Isocyanate-modified alkyd resin is also referred to as urethane alkyd resin, and part phthalic anhydride is replaced with diisocyanate, can
To improve the rate of drying of film, hardness and hydrolytic resistance, but the water for individually using Fructus Zanthoxyli oil to be synthesized with polyalcohol, polyacid
Alkyd resin rate of drying is slow, hardness is low, the disadvantage of water resistance and alkali resistance difference for property.
Invention content
The purpose of the present invention is to provide a kind of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin and preparation methods, overcome
The defects of aqueous alkide resin slow-drying that is prepared with cheap agricultural by-products Fructus Zanthoxyli oil, hardness is low and poor water resistance,
The polyurethane-modified aqueous alkide resin that the present invention is synthesized using cheap Fructus Zanthoxyli oil is with excellent from dry rate and good
Hardness and water resistance, it is at low cost, environmentally protective, have good application prospect.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, in terms of mass fraction, the polyurethane-modified Chinese prickly ash
The raw material for preparing of seed oil aqueous alkide resin includes：
Further, the alcoholysis catalysts are lithium hydroxide.
Further, the diisocyanate is different Buddhist diisocyanates.
A kind of preparation method of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, includes the following steps：
(1) alcoholysis：Under the protection of nitrogen, first Fructus Zanthoxyli oil and trimethylolpropane are added in reactor and are warming up to
120 DEG C, alcoholysis catalysts are added, is continuously heating to 230 DEG C and is reacted, when alcoholysate and volumetric concentration 95% ethyl alcohol according to
1:When being in clear shape after the volume ratio mixing of (3~4), it is cooled to 180 DEG C；
(2) it is esterified：Phthalic anhydride and reflux solvent is added, is continuously heating to 220 DEG C, insulation reaction measures reaction
Object acid value is cooled to 180 DEG C immediately when acid value reaches 10mgKOH/g or less, obtains alkyd resin prepolymer, and vacuum filtration removes
The water that remaining reflux solvent and reaction generate in dereaction object, is cooled to 70 DEG C；
(3) polyurethane-modified：In the case where nitrogen continues protection, 2, the 2- dihydroxy first that is dissolved in n,N-Dimethylformamide
Base propionic acid and dibutyl tin dilaurate are added in reactor, then diisocyanate is instilled polymerization system, are warming up to 80 DEG C of guarantors
Temperature reaction；
(4) it is neutralized into salt：Step (3) after reaction, is cooled to 70~60 DEG C, is added after triethylamine neutralizes and continues to cool down
To 40 DEG C hereinafter, deionized water dilution is added, and vigorous dispersion, obtain polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin.
Further, 0.5~1h is reacted after being continuously heating to 230 DEG C in step (1)；Step (2) is continuously heating to 220
DEG C, 2~3h of insulation reaction.
Further, the addition of reflux solvent is that reactant gross mass after phthalic anhydride is added in step (2)
5%.
Further, diisocyanate is instilled into polymerization system in step (3), 1~1.5h of time for adding is warming up to 80 DEG C
Insulation reaction 2h.
Further, it is added in step (4) in triethylamine and 30min, vigorous dispersion time is 30min.
Further, the reflux solvent is dimethylbenzene.
Further, the solid content of prepared polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin is 40%~44%.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention replaces other plant oil with cheap Fructus Zanthoxyli oil, rationally can efficiently utilize Fructus Zanthoxyli oil, and can be with
Reduce alkyd cost of material.With 2,2- dihydromethyl propionic acids for aqueous monomers, diisocyanate is modifying agent, preparation process letter
Single, obtained aqueous alkide resin has excellent certainly dry speed, flexibility and adhesive force and good hardness, water resistance
And acid resistance, overcome the aqueous alkide resin rate of drying individually synthesized with polyalcohol, polyacid with Fructus Zanthoxyli oil slowly, hardness
The disadvantage of low, water resistance and alkali resistance difference, it is environmentally protective, good application prospect is made it have, timber, gold are can be widely applied to
Protection decoration function is made on the surface of the products such as category, plastics.
Specific implementation mode
Embodiments of the present invention are described in further detail below：
A kind of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, is prepared by the raw material of following mass fraction：
Wherein, alcoholysis catalysts are lithium hydroxide, and diisocyanate is different Buddhist diisocyanates, 2,2- dihydroxymethyls
Propionic acid is aqueous monomers.
A kind of preparation method of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, includes the following steps：
(1) alcoholysis：Under the protection of nitrogen, first Fructus Zanthoxyli oil and trimethylolpropane are added in reactor, are warming up to
120 DEG C, alcoholysis catalysts lithium hydroxide is added, is continuously heating to 230 DEG C, 0.5~1h is reacted, when alcoholysate and volumetric concentration
95% ethyl alcohol presses 1 at 25 DEG C:When after (3~4) volume mixture being in clear shape, it is cooled to 180 DEG C；
(2) it is esterified：Reactor is added in phthalic anhydride and the refluxing xylene solvent of reactant gross mass 5%, after
It is continuous to be warming up to 220 DEG C, 2~3h of insulation reaction, it measures reactant acid value and cools down immediately when acid value is reduced to 10mgKOH/g or less
To 180 DEG C, alkyd resin prepolymer is obtained, after the water that remaining dimethylbenzene and reaction generate in reactant is removed by suction filtration under vacuum, drop
Temperature is to 70 DEG C；
(3) polyurethane-modified：Nitrogen continue protection under, 2 be dissolved in suitable n,N-Dimethylformamide,
After 2- dihydromethyl propionic acids and dibutyl tin dilaurate are added in reactor, then different Buddhist diisocyanates are slowly dropped into
Polymerization system, 1~1.5h are dripped off, and heat up 80 DEG C of insulation reaction 2h.
(4) it is neutralized into salt：Be added when being cooled to 70~60 DEG C in triethylamine and 30min, continue to be cooled to 40 DEG C hereinafter, plus
Enter appropriate amount of deionized water dilution, and vigorous dispersion 30min, obtains polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin.
The present invention is described in further detail with reference to embodiment：
Comparative example
(1) alcoholysis：Under the protection of nitrogen, reactor first is added in 24.4g Fructus Zanthoxyli oils and 10.0g trimethylolpropanes
In, 120 DEG C are warming up to, 0.0122g lithium hydroxides are added, are continuously heating to 230 DEG C, when alcoholysate obtained by the reaction and volume point
The ethyl alcohol that number is 95% is according to 1:3 volume ratio is in clear shape after being mixed at 25 DEG C, is cooled to 180 DEG C immediately；
(2) it is esterified：After being cooled to 180 DEG C, 7.0g phthalic anhydrides, 4.9g benzoic acid and 2.3g dimethylbenzene are added anti-
Device is answered, 220 DEG C of progress insulation reactions is continuously heating to, measures reactant acid value and dropped immediately when acid value is reduced to 12mgKOH/g
Temperature is to 180 DEG C to get alkyd resin prepolymer；
(3) Water-borne modification：After being cooled to 180 DEG C, by 6.2g trimellitic anhydrides addition reactor, the insulation reaction at 180 DEG C,
When reactant acid value is down to 46mgKOH/g, it is cooled to 120 DEG C immediately；
(4) dilution is neutralized：After being cooled to 120 DEG C, 12.0g ethylene glycol monobutyl ethers are added, continue to be added when being cooled to 65 DEG C
In 3.9g triethylamines and 30min, continue to be cooled to 30 DEG C, the dilution of 50g deionized waters is added, and be dispersed with stirring 30min, consolidate
The aqueous alkide resin that content is 44%.
Embodiment 1
1) alcoholysis：Under the protection of nitrogen, reactor first is added in 24.4g Fructus Zanthoxyli oils and 8.9g trimethylolpropanes
In, 120 DEG C are warming up to, 0.0122g lithium hydroxides are added, is continuously heating to 230 DEG C, 0.5h is reacted, when alcoholysate and 95% second
Alcohol is 1 at 25 DEG C:It is in clear shape after 3 volume mixtures, is cooled to 180 DEG C；
(2) it is esterified：Reactor is added in 5.9g phthalic anhydrides and 1.96g dimethylbenzene, is continuously heating to 220 DEG C, is protected
Temperature reaction 2h, measures reactant acid value and is cooled to 180 DEG C immediately when acid value is reduced to 11.0mgKOH/g or less, obtain alkyd tree
Fat prepolymer is cooled to 70 DEG C after just remaining solvent xylene and water is removed by suction filtration under vacuum in reactant；
(3) polyurethane-modified：Nitrogen continue protection under, by 4.2g 2,2- dihydromethyl propionic acids are dissolved in 6.0g's
After being added in reactor in n,N-Dimethylformamide, proper catalyst dibutyl tin dilaurate is added, then 13.32g is different
Isophorone diisocyanate is slowly dropped into polymerization system, and 1.5h is dripped off, and heat up 80 DEG C of insulation reaction 2h.
(4) it is neutralized into salt：Be added when being cooled to 70 DEG C in 4.0g triethylamines and 30min, continue to be cooled to 40 DEG C hereinafter, plus
Enter the dilution of 80g deionized waters, and vigorous dispersion 30min, it is 40% polyurethane-modified aqueous alkide resin to obtain solid content.
Embodiment 2
1) alcoholysis：Under the protection of nitrogen, reactor first is added in 24.4g Fructus Zanthoxyli oils and 8.9g trimethylolpropanes
In, 120 DEG C are warming up to, 0.0122g lithium hydroxides are added, is continuously heating to 230 DEG C, 1h is reacted, when alcoholysate and volumetric concentration
95% ethyl alcohol presses 1 at 25 DEG C:It is in clear shape after 4 volume mixtures, is cooled to 180 DEG C；
(2) it is esterified：Reactor is added in 6.6g phthalic anhydrides and 2.0g dimethylbenzene, is continuously heating to 220 DEG C, heat preservation
2.5h is reacted, reactant acid value is measured and is cooled to 180 DEG C immediately when acid value is reduced to 9.7mgKOH/g or less, obtains alkyd resin
Prepolymer is cooled to 70 DEG C after the water that remaining solvent xylene and reaction generate in reactant is removed by suction filtration under vacuum；
(3) polyurethane-modified：Nitrogen continue protection under, by 4.2g 2,2- dihydromethyl propionic acids are dissolved in 6.0g N,
After being added in reactor in dinethylformamide, proper catalyst dibutyl tin dilaurate is added, then by the different Fo Er of 12.3g
Ketone diisocyanate is slowly dropped into polymerization system, and 1.5h is dripped off, and heat up 80 DEG C of insulation reaction 2h.
(4) it is neutralized into salt：Be added when being cooled to 60 DEG C in 3.4g triethylamines and 30min, continue to be cooled to 40 DEG C hereinafter, plus
Enter the dilution of 80g deionized waters, and vigorous dispersion 30min, it is 40% polyurethane-modified aqueous alkide resin to obtain solid content.
Embodiment 3
1) alcoholysis：Under the protection of nitrogen, reactor first is added in 24.4g Fructus Zanthoxyli oils and 8.9g trimethylolpropanes
In, 120 DEG C are warming up to, 0.0122g lithium hydroxides are added, is continuously heating to 230 DEG C, 0.8h is reacted, when alcoholysate is dense with volume
The ethyl alcohol of degree 95% presses 1 at 25 DEG C:It is in clear shape after 3.5 volume mixtures, is cooled to 180 DEG C；
(2) it is esterified：Reactor is added in 7.4g phthalic anhydrides and 2.04g dimethylbenzene, is continuously heating to 220 DEG C, is protected
Temperature reaction 3h, measures reactant acid value and is cooled to 180 DEG C immediately when acid value is reduced to 10.2mgKOH/g or less, obtain alkyd tree
Fat prepolymer is cooled to 70 DEG C after the water that remaining solvent xylene and reaction generate in reactant is removed by suction filtration under vacuum；
(3) polyurethane-modified：Nitrogen continue protection under, by 4.2g 2,2- dihydromethyl propionic acids are dissolved in 6.0gN,
After being added in reactor in dinethylformamide, proper catalyst dibutyl tin dilaurate is added, then by the different Fo Er of 11.1g
Ketone diisocyanate is slowly dropped into polymerization system, and 1h is dripped off, and heat up 80 DEG C of insulation reaction 2h.
(4) it is neutralized into salt：Be added when being cooled to 65 DEG C in 4.0g triethylamines and 30min, continue to be cooled to 40 DEG C hereinafter, plus
Enter the dilution of 80g deionized waters, and vigorous dispersion 30min, it is 40% polyurethane-modified aqueous alkide resin to obtain solid content.
By the lotion and paint film property of comparative example and Examples 1 to 3, test result is as follows：
The paint film property result of 1 embodiment and comparative example of table
By table 1 it is found that the present invention uses the aqueous alkide resin that Fructus Zanthoxyli oil synthesis of polyurethane is modified, with isophorone
As modifying agent, 2,2- dihydromethyl propionic acids are polymerize diisocyanate as aqueous monomers, simple for process.With unmodified tree
Fat comparative example is compared, and polyurethane-modified resin paint film shows excellent rate of drying in the case where being not added with drier,
His performance also increases, and is mainly shown as hardness, water resistance, acid resistance and alkali resistance.Although flexibility and adhesive force
It can be declined, but be changed little.
Claims (10)
1. a kind of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, which is characterized in that in terms of mass fraction, the polyurethane
The raw material for preparing of modified Fructus Zanthoxyli oil aqueous alkide resin includes：
2. a kind of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin according to claim 1, which is characterized in that the alcohol
Solution catalyst is lithium hydroxide.
3. a kind of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin according to claim 1, which is characterized in that described two
Isocyanates is different Buddhist diisocyanates.
4. a kind of preparation method of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin described in claim 1, which is characterized in that
Include the following steps：
(1) alcoholysis：Under the protections of nitrogen, first Fructus Zanthoxyli oil and trimethylolpropane are added in reactor and are warming up to 120 DEG C,
Alcoholysis catalysts are added, is continuously heating to 230 DEG C and is reacted, when the ethyl alcohol of alcoholysate and volumetric concentration 95% is according to 1:(3~
4) when being in clear shape after volume ratio mixing, 180 DEG C are cooled to；
(2) it is esterified：Phthalic anhydride and reflux solvent is added, is continuously heating to 220 DEG C, insulation reaction measures reactant acid
Value, when acid value reaches 10mgKOH/g or less, is cooled to 180 DEG C, obtains alkyd resin prepolymer immediately, is removed by suction filtration under vacuum anti-
The water that remaining reflux solvent and reaction generate in object is answered, is cooled to 70 DEG C；
(3) polyurethane-modified：In the case where nitrogen continues protection, 2, the 2- dihydroxymethyls third that are dissolved in n,N-Dimethylformamide
Acid and dibutyl tin dilaurate are added in reactor, then diisocyanate is instilled polymerization system, and it is anti-to be warming up to 80 DEG C of heat preservations
It answers；
(4) it is neutralized into salt：Step (3) after reaction, is cooled to 70~60 DEG C, is added after triethylamine neutralizes and continues to be cooled to 40
DEG C hereinafter, deionized water dilution is added, and vigorous dispersion obtains polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin.
5. a kind of preparation method of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, feature exist according to claim 4
In 0.5~1h of reaction after being continuously heating to 230 DEG C in step (1)；Step (2) is continuously heating to 220 DEG C, and insulation reaction 2~
3h。
6. a kind of preparation method of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, feature exist according to claim 4
In the addition of reflux solvent is 5% of reactant gross mass after phthalic anhydride is added in step (2).
7. a kind of preparation method of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, feature exist according to claim 4
In diisocyanate being instilled polymerization system in step (3), 1~1.5h of time for adding is warming up to 80 DEG C of insulation reaction 2h.
8. a kind of preparation method of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, feature exist according to claim 4
In in the middle addition triethylamine of step (4) and 30min, vigorous dispersion time are 30min.
9. a kind of preparation method of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, feature exist according to claim 4
In the reflux solvent is dimethylbenzene.
10. a kind of preparation method of polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin, feature exist according to claim 4
In the solid content of prepared polyurethane-modified Fructus Zanthoxyli oil aqueous alkide resin is 40%~44%.
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Application publication date: 20180928 |