CN1333029C - Acetacetic acid alkyl ester metal chelate coating drier and production thereof - Google Patents
Acetacetic acid alkyl ester metal chelate coating drier and production thereof Download PDFInfo
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- CN1333029C CN1333029C CNB2004100842881A CN200410084288A CN1333029C CN 1333029 C CN1333029 C CN 1333029C CN B2004100842881 A CNB2004100842881 A CN B2004100842881A CN 200410084288 A CN200410084288 A CN 200410084288A CN 1333029 C CN1333029 C CN 1333029C
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Abstract
The present invention relates to acetacetic acid alkyl ester metal chelate which is a new redox polymerization drier used for coating industry. The acetacetic acid alkyl ester metal chelate is suitable for a solvent based coating containing vegetable drying oil and a water based coating. The present invention is prepared by the following steps: alkyl alcohol and acetyl ketene react in the presence of a catalyst to obtain a corresponding acetacetic acid alkyl ester chelating agent; then the chelating agent and an inorganic metal salt are synthesized into an acetacetic acid alkyl ester metal chelate drier. The chelate drier has a drying property similar to that of a traditional metal soap drier on a solvent based coating and a water based coating, but the chelate drier is different from the deep color, high viscosity, strong odor and high toxicity of a traditional metal soap drier. The acetoacetic acid alkyl ester metal chelate drier can be preserved in a solid state, and the drier has the advantages of light color, low toxicity, wide sources of synthesis raw materials, simple preparation process and high yield and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of be used to the contain solvent based coating of dry vegetable oil and the terebine of water-borne coatings, specifically, relate to a kind of Acetacetic acid alkyl ester metal chelate coating drier.
Background technology
Organo-metallic soap siccative developing history is long, still is widely used so far.But along with the raising of people's environmental consciousness, for low toxicity, the continuous increase of non-toxic coatings demand, the limitation of traditional siccative more and more is obvious.
The tradition siccative, as cobalt naphthenate, tone dark, viscosity is big, and smell is heavy, and toxicity is big; Can cause simultaneously the mistake of coating to do phenomenon in use.Its reason mainly is some component such as the pigment in the coating, dispersion agent, and some compositions in the paint vehicle, or absorption, or exchanged the metal ion in the siccative, and urge working property thereby reduced, prolonged the time of drying of filming.The continuous development of water-borne coatings makes traditional siccative and coating lose the contradiction of doing between the phenomenon and becomes more outstanding.In the water-borne coatings except above-mentioned reason, the introducing of aqueous solvent has increased the possibility of urging dried metal ion to run off especially, usually the pH value of aqueous coating system is neutral alkalescence on the weak side, hydrolysis takes place in organo-metallic soap probably, it is adsorbed that the dissociative metal ion also can be neutralized agent, and the generation of these situations all can reduce the activity of siccative.So the siccative of seeking a kind of low toxicity and possessing continuous activity to be each big always one of siccative production firm research emphasis.
Add an amount of sequestrant to increase the siccative activity in traditional organo-metallic soap siccative, reducing the dried method of mistake is early, and a kind of comparatively effective means that still is widely studied so far.Sequestrant commonly used mostly is and contains the N sequestrant, and such as phenanthroline, dipyridyl (US2565897), such sequestrant are called as to urge in coating does promotor.Phenomenon is done in the mistake of urging the adding of doing promotor can effectively change in the coating, although people are very not definite to its effect in coating, find that but pass through some experiments the effective and a part of metal ion chelating in system of these sequestrants energy is urged the loss of doing effective constituent thereby reduced.
Though urge the adding of doing promotor to increase the activity of organo-metallic soap siccative, still do not change the siccative tone dark, viscosity is big, and smell is heavy, the shortcoming that toxicity is big.Having added the siccative that contains the N sequestrant also can make to a certain extent to film and produce the problem of variable color.Some nitrogenous sequestrant such as phenanthrolines, itself costs an arm and a leg dipyridyl, has also limited their extensive use.
Along with sequestrant is urged deepening continuously of dried area research at coating, abandon traditional organo-metallic soap, with sequestrant directly and some methods of urging dried metal ion-chelant to make the inner complex siccative occur thereupon.Such as oxine manganic drier (S.P.Potnis, Paintindia, 14 (9), 24,1964), Sasol Servo B.V company also releases dipyridyl manganic drier (Nuodex FS 530).Inner complex siccative of the present invention also belongs to such, but the present invention selects only to contain the sequestrant of O, i.e. β-diketone compounds.
Once be presented among the Ger975321 in the resin synthetic process and add acetylacetone cobalt, or behind the methyl aceto acetate cobalt, the dryness of resin has been enhanced.This method is not when joining lacquer inner complex to be added as siccative, but adds when synthetic resins, so can not be called siccative.
Point out among the EP1382648A1: chelating siccative principal feature is to improve environmental pollution, and to compare toxicity low with traditional siccative.The chelating siccative has the advantage of resistive connection skin.Employed basic structure is in this patent:
In the following formula: Z1, Z2 can be set at N, or O, works as Z1, when Z2 is all O, is β-diketone.R1, R2, R3 can be aliphatics alkane, also can be nitro-compound, halogen-containing alkane etc.But only lifted the example of one 2,4 diacetylmethane manganic chelates in this patent, the synthetic and application of other β-diketone metallo-chelate is not mentioned.
Among the Ger2634085 with methyl aceto acetate and morpholine altogether the chelating cobalt do siccative, except dryness is arranged preferably, also have the effect of crease-resistant skin.
Above these β-diketone compounds all is as sequestrant or with short chain β-diketone ester and contain the N compound jointly as sequestrant with β-diketone as the example of siccative, the present invention then uses the β-diketone ester of long-chain as sequestrant metal ion to be carried out chelating separately, and is different with them.And nearly all research about β-diketone class chelating siccative all only pays close attention to its performance in solvent based coating, and its research in water-borne coatings is not but carried out, and perhaps only mentions and do not do corresponding experiment.And we not only use in solvent based coating with siccative of the present invention, have more done related application in water-borne coatings, and in today that the water-borne coatings demand increases day by day, this has remedied the defective of this aspect to a certain extent.
Summary of the invention
The objective of the invention is to overcome that the siccative color and luster is dark in the above-mentioned background technology, viscosity is big, smell is heavy, toxicity is big and be only applicable to the dried defective of urging of oil-based solvent coating, provide a kind of urge the time of doing short, smell is light, toxicity is low, hold imitate active long, both be applicable to that urging of the solvent based coating that contains dry vegetable oil was dried, be applicable to also that water-borne coatings urged dried Acetacetic acid alkyl ester metal chelate coating drier.
The present invention is achieved in that this Acetacetic acid alkyl ester metal chelate coating drier has following chemical structure: [(M
N+) (A)
n] (H
2O)
pFormula (1)
Wherein: M is Co, Mn, and Ce, a kind of in Zr four metal ion species, A is the Acetacetic acid alkyl ester of following structure:
R is that the C atomicity is 4～18 aliphatic alkyl, comprises straight chained alkyl and branched-chain alkyl,
N represents an integer between 2～4
P represents an integer between 0～2
Metal ions M among the present invention is preferably metal ion Co
The preparation method's of the Acetacetic acid alkyl ester metal chelate coating drier among the present invention step comprises:
(1) under nitrogen atmosphere, alkyl alcohol and ketene dimer synthesis of acetyl alkyl acetate in the presence of catalyzer, the mol ratio of alkyl alcohol and ketene dimer is 1～1.20: 1, catalyzer is to choose any one kind of them in amines catalyst, acid catalyst, the Organometal compound catalyst, and catalyst levels is 0.15～0.85 (weight %) of reaction-ure mixture.
(2) Acetacetic acid alkyl ester makes corresponding Acetacetic acid alkyl ester metal chelate with the inorganic metal reactant salt that contains Co, Mn, Ce or Zr, and the mol ratio of Acetacetic acid alkyl ester and inorganic metal salt is 2～4: 1.
Described amines catalyst described in the step among the preparation method of the present invention (1) is to choose any one kind of them in triethylamine, Tributylamine or the pyridine, acid catalyst is to choose any one kind of them in the vitriol oil, the p-methyl benzenesulfonic acid, and the organo-metallic salt catalyst is a dibutyl tin dilaurate.
Inorganic metal salt described in the step among the preparation method of the present invention (2) is: choose any one kind of them in rose vitriol, Cobaltous diacetate, manganous sulfate, manganese acetate, cerous sulfate, ceric ammonium nitrate, zirconium oxychloride or the zirconium chloride.
The present invention has following advantage compared with the prior art:
(1) Acetacetic acid alkyl ester of the present invention and inner complex thereof are synthetic simple, and productive rate is higher, are fit to the needs of large-scale commercial production.
(2) Acetacetic acid alkyl ester cobalt chelates of the present invention can be dissolved among the resin that contains siccative oil, such as Synolac, also dissolves in some conventional solvents, has brought convenience for it is used for water-based system coating.
(3) Acetacetic acid alkyl ester cobalt chelates siccative of the present invention and traditional siccative such as cobalt iso-octoate have the similar dryness energy of urging.
(4) Acetacetic acid alkyl ester metal chelate siccative of the present invention can be preserved by solid, lighter color, and toxicity is low, the synthesis material wide material sources, preparation technology is simple, and productive rate is higher, is fit to large-scale commercial production.
Embodiment:
Now in conjunction with the embodiments content of the present invention is further described, but embodiment is not a limitation of the present invention.
Embodiment 1
A: the preparation of the positive butyl ester of etheric acid
1. reaction equation:
2. fill a prescription:
Reactant molar mass (g)
Propyl carbinol 1.05 77.7
Ketene dimer 1.0 84
98% vitriol oil (catalyzer) 0.5
3. operating process:
Four-hole boiling flask is loaded on the electronic constant speed stirrer, and left mouth is loaded onto the reflux water-dividing device, and right side mouth is loaded onto constant pressure funnel, and dropping funnel top mouth connects nitrogen ingress pipe, and four-hole is loaded onto thermometer, and reaction flask heats with flames of anger electric mantle.
Drop into propyl carbinol by prescription in reaction flask, the vitriol oil stirs down and heats up, logical nitrogen protection.Be heated to 90 ℃, treat slowly to drip behind the temperature-stable ketene dimer (this exothermic heat of reaction is violent, thus the control rate of addition so that temperature is controlled at about 90 ℃).After ketene dimer dropwises, at 90 ℃---100 ℃ were reacted 1 hour, were specifically decided by the ketene dimer degree of reacting completely, and reaction end is controlled with gas-chromatography.
Reaction finishes, and reactant is cooled to 50 ℃, is neutralized to neutrality with 10% aqueous sodium carbonate.Standing demix is removed water layer, and oil reservoir spends the night with anhydrous magnesium sulfate drying.Next day, the oil reservoir underpressure distillation is collected cut under 84 ℃ of-90 ℃/8mmHg, productive rate 80%--90%.
1. the positive butyl ester physical index of etheric acid:
Molecular formula:
Molecular weight: 158
Outward appearance: colourless transparent liquid
Boiling point: 84 ℃ of-90 ℃/8mmHg
n
D 28：1.4239
d
25：0.9622g/ml
B: the preparation of the positive butyl ester cobalt of etheric acid (+2) inner complex
1. fill a prescription:
Reactant molar mass (g)
The positive butyl ester 2.0 316 of etheric acid
Cobaltous diacetate tetrahydrate 1.0 249
The NaOH aqueous ethanolic solution
(1)In right amount
Aqueous ethanolic solution (95 weight %) is an amount of
Deionized water is an amount of
(1) herein and NaOH aqueous ethanolic solution hereinafter all be with the 30%NaOH aqueous solution and 95% aqueous ethanolic solution with weight ratio 1～2: 2～1 are mixed forms.
2. preparation process:
With the Cobaltous diacetate tetrahydrate with 400 gram aqueous ethanolic solution dissolvings fully, outward appearance is the red-purple clear solution.
Four-hole boiling flask is loaded on the electronic constant speed stirrer, and left side mouth is loaded onto reflux condensing tube, loads onto dropping funnel for right mouthful, and four-hole is loaded onto thermometer.In flask, add positive butyl ester of etheric acid and alcoholic acid mixed solution, under agitation drip the Cobaltous diacetate aqueous ethanolic solution,, have peach solid to separate out along with splashing into of Cobaltous diacetate.Drip and finish to drip NaOH aqueous ethanolic solution regulation system pH value again, make chelating complete to 7-8.The final reaction system is rose pink pasty state, stops to stir, and standing over night.
Reaction product is separated from system by suction filtration, gained incarnadine solid is the crude product of the positive butyl ester cobalt of etheric acid (+2) inner complex, with 60% methanol aqueous solution washing several times (inner complex also can contain some parts of crystal water under this condition), send vacuum-drying.
The positive butyl ester cobalt of etheric acid (+2) inner complex easily absorbs airborne oxygen, and cobalt is oxidized to+3 valencys by+divalent.Cobalt chelates also from rose pink to green transition, when reaching finite concentration, be blackish green.So, usually the positive butyl ester cobalt of etheric acid (+2) inner complex being stored in the positive butyl ester of etheric acid, the secluding air of trying one's best is to keep its stability.
3. product index:
(a). outward appearance: rose pink solid
(b) the positive butyl ester cobalt of etheric acid (+2) inner complex expressivity structure is as follows:
(c) cobalt contents (%):
Theoretical value: 15.82 (not containing crystal water) 14.43 (containing 2 parts of crystal water)
Measured value (calcination method): organism 76.14
Co
3O
4 23.86
Cobalt contents 17.52
(d) solvability: water insoluble and N-BUTYL ACETATE, dissolve in ethanol, acetone, dimethylbenzene, in No. 200 gasoline equal solvents, dissolving or dispersion in containing the vegetable oil acid resin.
4. the diffuse reflectance infrared spectroscopy peak of inner complex:
v(C＝O)1624cm
-1，v(C＝C)1528cm
-1，v(H
2O)3448cm
-1，v(Co-O)499-450cm
-1
C. application experiment
The dry vegetable oil resin that contains that adopts among the present invention is that output is big in the coatings industry, the Synolac that purposes is wide, and concrete model is the 389-9 Synolac, is provided by resin processing plant of Xinhua of Shanghai Paint Co., Ltd..This kind resin consists of soya-bean oil substantially, and phenylformic acid, tetramethylolmethane, glycerine and phthalic anhydride, solvent are No. 200 gasoline or dimethylbenzene, solid content about 60%.
Be made into varnish with the 389-9 Synolac, standard is as follows:
Color and luster: (iron cobalt colorimeter) is not more than 12
Outward appearance: transparent inorganic tool impurity
Viscosity: be coated with 4 glasss, second 40-80
Acid value: mgKOH/g is not more than 10
Solids content (%): 46
Varnish method of application, the drying property of coating and the performance test of filming all adopt every coating country of People's Republic of China (PRC) examination criteria.
Laboratory sample:
Blank sample: 389-9 alkyd varnish, siccative addition 0%
Contrast sample 1: in the 389-9 alkyd varnish, add traditional cobalt soap siccative, this experiment employing cobalt iso-octoate siccative, factory provides by Shanghai Paint Co., Ltd. head's weathering, addition be that metal quality accounts for resin solid part quality in the siccative 0.03%
Contrast sample 2: add the positive butyl ester cobalt of etheric acid of the present invention (+2) inner complex siccative in the 389-9 alkyd varnish, addition is identical with contrast sample 1.
Experimental result sees Table 1
Table 1
| Sample | 389-9 alkyd varnish consumption (g) | The siccative consumption (metal quality, g) | Surface drying (h) | Do solid work (h) | Hardness (1) |
| Blank sample | 150 | 0 | 22 | Do not do solid work after 7 days | B |
| Contrast sample 1 | 150 | 0.021 | 2.1 | 24 | F |
| Contrast sample 2 | 150 | 0.021 | 3.06 | 24 | F |
(1) pencil hardness is as the criterion to scratch.
Embodiment 2
A: the preparation of etheric acid n-pentyl ester
1. reaction equation:
2. fill a prescription:
Reactant molar mass (g)
Pentyl alcohol 1.0 88.2
Ketene dimer 1.0 84.0
Tosic acid (catalyzer) 0.5
3. operating process:
Press the reaction unit of example 1, drop into Pentyl alcohol in reaction flask, tosic acid stirs down and heats up, logical nitrogen protection.Be heated to 90 ℃, begin slowly to drip after stable ketene dimer (this exothermic heat of reaction is violent, thus the control rate of addition so that temperature is controlled at about 90 ℃).After ketene dimer dropwises, at 90 ℃---100 ℃ were reacted 2 hours.
Reaction finishes, and reactant is cooled to 50 ℃, with the 10% aqueous sodium carbonate neutrality that neutralizes.Standing demix is removed water layer, and oil reservoir spends the night with anhydrous magnesium sulfate drying.Underpressure distillation is collected 104 ℃--target product cut under-108 ℃/9mmHg, productive rate 80%.
4. physical index:
Molecular formula:
Molecular weight: 172
Outward appearance: colourless transparent liquid
Boiling point: 104 ℃---108 ℃/9mmHg
n
D 28：1.4275
d
25：0.9477g/ml
B: the preparation of etheric acid n-pentyl ester cobalt chelates
1. fill a prescription:
Reactant molar mass (g)
Etheric acid n-pentyl ester 2.0 344
Cobaltous diacetate tetrahydrate 1.0 249
The NaOH aqueous ethanolic solution is an amount of
Aqueous ethanolic solution (95 weight %) is an amount of
Deionized water is an amount of
2. preparation process:
With reference to example 1.Etheric acid n-pentyl ester cobalt (+2) inner complex also should be stored among the etheric acid n-pentyl ester, prevents that it is oxidized to green high price cobalt.
3. product index:
(a). outward appearance: rose pink solid
(b) etheric acid n-pentyl ester cobalt (+2) inner complex expressivity structure is as follows:
(c) cobalt contents (%):
Theoretical value: 14.71 (not containing crystal water) 13.50 (containing 2 parts of crystal water)
Measured value: (calcination method) organism 80.78
Co
3O
4 19.22
Cobalt contents 14.12
(the b solvability: water insoluble, acetone, No. 200 gasoline and N-BUTYL ACETATE dissolve in ethanol, dimethylbenzene, dissolving or disperse in containing the vegetable oil acid resin.
4. the diffuse reflectance infrared spectroscopy peak of inner complex:
v(C＝O)1621cm
-1，v(C＝C)1522cm
-1，v(H
2O)3368cm
-1 v(Co-O)491，446cm
-1
C. application experiment
Experiment material, method are with reference to example 1, and contrast sample 2 used siccative change and make etheric acid n-pentyl ester cobalt (+2) inner complex in the laboratory sample, and the siccative addition is constant, is 0.03%
Experimental result sees Table 2:
Table 2
| Sample | 389-9 alkyd varnish consumption (g) | The siccative consumption (metal quality, g) | Surface drying (h) | Do solid work (h) | Hardness (1) |
| Blank sample | 150 | 0 | 22 | Do not do solid work after 7 days | B |
| Contrast sample 1 | 150 | 0.021 | 2.1 | 24 | F |
| Contrast sample 2 | 150 | 0.021 | 3.27 | 24 | F |
(1) pencil hardness is as the criterion to scratch.
Embodiment 3
A: the preparation of the just own ester of etheric acid:
1. reaction equation:
2. fill a prescription:
Reactant molar mass (g)
N-hexyl alcohol 1.0 102
Ketene dimer 1.0 84.0
Triethylamine (catalyzer) 1.5ml
3. operating process:
Press the reaction unit of example 1, drop into n-hexyl alcohol in reaction flask, triethylamine stirs down and heats up, logical nitrogen protection.Be heated to 60 ℃, begin slowly to drip after stable ketene dimer (this exothermic heat of reaction is violent, thus the control rate of addition so that temperature is controlled at about 60 ℃).After ketene dimer dropwised, reaction was 1 hour about 60 ℃, specifically decides on the ketene dimer degree of reacting completely, and reaction end is controlled with gas-chromatography.
Reaction finishes, and reactant is cooled off.Underpressure distillation is collected 118 ℃--target product cut under-128 ℃/10mmHg.
3. the just own ester physical index of etheric acid:
Molecular formula:
Molecular weight: 186
Outward appearance: colourless transparent liquid
Boiling point: 118 ℃---128 ℃/10mmHg
n
D 28： 1.4302
d
25： 0.9364g/ml
B: the preparation of the just own ester cobalt of etheric acid (+2) inner complex
1. fill a prescription:
Reactant molar mass (g)
The just own ester 2.0 372 of etheric acid
Cobaltous diacetate tetrahydrate 1.0 249
Strong aqua (12.5 weight %) is an amount of
Aqueous ethanolic solution (95 weight %) is an amount of
Deionized water is an amount of
2. preparation process:
Will be complete with 400 gram aqueous ethanolic solution dissolvings by the Cobaltous diacetate tetrahydrate of formula ratio, outward appearance is the red-purple clear solution.
Get a four-hole boiling flask and be loaded on the electronic constant speed stirrer, left side mouth is loaded onto reflux condensing tube, loads onto dropping funnel for right mouthful, and four-hole is loaded onto thermometer.In flask, add just own ester of etheric acid and Cobaltous diacetate aqueous ethanolic solution, mix, stir a moment, promptly have a large amount of pink solid to separate out, complete for making chelating, drip 12.5% strong aqua, regulation system pH value dropwises to 7-8, and reaction system is rose pink pasty state, stop to stir, and standing over night.
Reaction product is separated from system by suction filtration, and crude product gets the just own ester cobalt of rose pink solid etheric acid (+2) inner complex (inner complex also can contain some parts of crystal water under this condition) with 60% methanol aqueous solution washing several times, send vacuum-drying.Preserve this inner complex in the just own ester of etheric acid.
3. product index:
(a). outward appearance: rose pink solid
(b) the just own ester cobalt of etheric acid (+2) inner complex expressivity structure is as follows:
(c) cobalt contents (%):
Theoretical value: 13.75 (not containing crystal water) 12.69 (containing 2 parts of crystal water)
Measured value: (calcination method) organism 83.84
Co
3O
4 16.16
Cobalt contents 11.87
(c) solvability: water insoluble, dissolve in ethanol, acetone, No. 200 gasoline, N-BUTYL ACETATE, dimethylbenzene, dissolving or dispersion in containing the vegetable oil acid resin.
4. the diffuse reflectance infrared spectroscopy peak of inner complex:
v(C＝O)1622cm
-1，v(C＝C)1525cm
-1，v(H
2O)3366cm
-1，v(Co-O)489，442cm
-1
C. application experiment
Experiment material, method are with reference to example 1, and contrast sample 2 used siccative change and make the just own ester cobalt of etheric acid (+2) inner complex in the laboratory sample, and the siccative addition is constant, is 0.03%.
Experimental result sees Table 3
Table 3
| Sample | 389-9 alkyd varnish consumption (g) | The siccative consumption (metal quality, g) | Surface drying (h) | Do solid work (h) | Hardness (1) |
| Blank sample | 150 | 0 | 22 | Do not do solid work after 7 days | B |
| Contrast sample 1 | 150 | 0.021 | 2.1 | 24 | F |
| Contrast sample 2 | 150 | 0.021 | 2.48 | 24 | F |
(1) pencil hardness is as the criterion to scratch.
Embodiment 4
A: the preparation of etheric acid n-octyl:
1. reaction equation:
2. fill a prescription:
Reactant molar mass (g)
N-Octanol 1.0 130
Ketene dimer 1.0 84.0
Triethylamine (catalyzer) 1.5ml
3. operating process:
Press the reaction unit of example 1, drop into n-Octanol in reaction flask, triethylamine stirs down and heats up, logical nitrogen protection.Be heated to 60 ℃, begin slowly to drip after stable ketene dimer (this exothermic heat of reaction is violent, thus the control rate of addition so that temperature is controlled at about 60 ℃).After ketene dimer dropwised, reaction was 3 hours about 60 ℃, specifically decides on the ketene dimer degree of reacting completely, and reaction end is controlled with gas-chromatography.
Reaction finishes, and reactant is cooled off.Target product cut under 150 155/10mmHg is collected in underpressure distillation.
4. etheric acid n-octyl physical index:
Molecular formula:
Molecular weight: 214
Outward appearance: colourless transparent liquid
Boiling point: 150-155/10mmHg
n
D 28：1.4353
d
25：0.9171g/ml
B: the preparation of etheric acid n-octyl cobalt (+2) inner complex
1. fill a prescription:
Reactant molar mass (g)
Etheric acid n-octyl 2.0 428
Cobaltous diacetate tetrahydrate 1.0 249
Strong aqua (12.5 weight %) is an amount of
Aqueous ethanolic solution (95 weight %) is an amount of
Deionized water is an amount of
2. preparation process:
With reference to example 3.Preserve this inner complex in the etheric acid n-octyl.
3. product index:
(a). outward appearance: rose pink solid
(b) etheric acid n-octyl cobalt (+2) inner complex expressivity structure is as follows:
(c) cobalt contents (%):
Theoretical value: 12.16 (not containing crystal water) 11.32 (containing 2 parts of crystal water)
Measured value: (calcination method): organism 88.06
Co
3O
4 11.94
Cobalt contents 8.77
(d) solvability: water insoluble, dissolve in ethanol, acetone, No. 200 gasoline, N-BUTYL ACETATE, dimethylbenzene.Dissolving or dispersion in containing the vegetable oil acid resin.
The diffuse reflectance infrared spectroscopy peak of 4 inner complexs:
v(C＝O)1622cm
-1，v(C＝C)1524cm
-1，v(Co-O)499--316cm
-1
C. application experiment:
Experiment material, method of application are with reference to example 1, and contrast sample 2 used siccative change and make etheric acid n-octyl cobalt (+2) inner complex in the laboratory sample, and the siccative addition is constant, is 0.03%
Experimental result sees Table 4:
Table 4
| Sample | 389-9 alkyd varnish consumption (g) | The siccative consumption (metal quality, g) | Surface drying (h) | Do solid work (h) | Hardness (1) |
| Blank sample | 150 | 0 | 22 | Do not do solid work after 7 days | B |
| Contrast sample 1 | 150 | 0.021 | 2.1 | 24 | F |
| Contrast sample 2 | 150 | 0.021 | 2.43 | 24 | F |
(1) pencil hardness is as the criterion to scratch.
Embodiment 5
A: the preparation of the different monooctyl ester of etheric acid
1. reaction equation:
2. fill a prescription:
Reactant molar mass (g)
Isooctyl alcohol 1.0 130
Ketene dimer 1.0 84.0
Triethylamine (catalyzer) 1.5ml
3. operating process:
Press the reaction unit of example 1, drop into isooctyl alcohol in reaction flask, triethylamine stirs down and heats up, logical nitrogen protection.Be heated to 60 ℃, begin slowly to drip after stable ketene dimer (this exothermic heat of reaction is violent, thus the control rate of addition so that temperature is controlled at about 60 ℃).After ketene dimer dropwised, reaction was 3 hours about 60 ℃, specifically decides on the ketene dimer degree of reacting completely, and reaction end is controlled with gas-chromatography.
Reaction finishes, and reactant is cooled off.Target product cut under 138 ℃ of-144 ℃/16mmHg is collected in underpressure distillation.
4. physical index:
Molecular formula:
Molecular weight: 214
Outward appearance: colourless transparent liquid
Boiling point: 138 ℃ of-144 ℃/16mmHg
n
D 28：1.4348
d
25：0.9248g/ml
B: the preparation of the different monooctyl ester cobalt of etheric acid (+2) inner complex:
1. fill a prescription:
Reactant molar mass (g)
The different monooctyl ester 2.0 428 of etheric acid
Cobaltous diacetate tetrahydrate 1.0 249
The NaOH aqueous ethanolic solution is an amount of
Aqueous ethanolic solution (95 weight %) is an amount of
Deionized water is an amount of
2. preparation process:
With reference to example 1.The different monooctyl ester cobalt of etheric acid (+2) inner complex is stored among the different monooctyl ester of etheric acid.
3. product index:
(a). outward appearance: rose pink solid
(b) the different monooctyl ester cobalt of etheric acid (+2) inner complex expressivity structure is as follows:
(c) cobalt contents (%):
Theoretical value: 12.16 (not containing crystal water) 11.32 (containing 2 parts of crystal water)
Measured value: (calcination method) organism 85.80
Co
3O
4 14.20
Cobalt contents 10.43
(d) solvability: water insoluble, dissolve in ethanol, acetone, No. 200 gasoline, N-BUTYL ACETATE, dimethylbenzene, dissolving or dispersion in containing the vegetable oil acid resin.
The diffuse reflectance infrared spectroscopy peak of 4 inner complexs:
v(C＝O)1623cm
-1，v(C＝C)1525cm
-，v(Co-O)424cm
-1
C. application experiment
Experiment material, method are with reference to example 1, and contrast sample 2 used siccative change and make the different monooctyl ester cobalt of etheric acid (+2) inner complex in the laboratory sample, and the siccative addition does not become 0.03%.
Experimental result sees Table 5
Table 5
| Sample | 389-9 alkyd varnish consumption (g) | The siccative consumption (metal quality, g) | Surface drying (h) | Do solid work (h) | Hardness (1) |
| Blank sample | 150 | 0 | 22 | Do not do solid work after 7 days | B |
| Contrast sample 1 | 150 | 0.021 | 2.1 | 24 | F |
| Contrast sample 2 | 150 | 0.021 | 2.68 | 24 | HB |
(1) pencil hardness is as the criterion to scratch.
Embodiment 6
A: the preparation of etheric acid ester in the last of the ten Heavenly stems
1. reaction equation:
2. fill a prescription:
Reactant molar mass (g)
Decyl alcohol 1.0 158
Ketene dimer 1.0 84
98% vitriol oil (catalyzer) 0.5
3. operating process:
Press the reaction unit of example 1, drop into decyl alcohol in reaction flask, 98% vitriol oil stirs down and heats up, logical nitrogen protection.Be heated to 90 ℃, begin slowly to drip after stable ketene dimer (this exothermic heat of reaction is violent, thus the control rate of addition so that temperature is controlled at about 90 ℃).After ketene dimer dropwised, reaction was 1 hour about 90---100 ℃, specifically decides on the ketene dimer degree of reacting completely, and reaction end is controlled with gas-chromatography.
Reaction finishes, and reactant is cooled to 50 ℃, with the 10% aqueous sodium carbonate neutrality that neutralizes.Standing demix is removed water layer, and oil reservoir spends the night with anhydrous magnesium sulfate drying.Target product cut under 164 ℃ of-168 ℃/8mmHg is collected in underpressure distillation.
4. physical index:
Molecular formula:
Molecule is heavy: 242
Outward appearance: colourless transparent liquid
Boiling point: 164 ℃ of-168 ℃/8mmHg
n
D 28：1.4397
d
25：0.9067g/ml
B: the preparation of etheric acid ester in last of the ten Heavenly stems cobalt (+2) inner complex
1. fill a prescription:
Reactant molar mass (g)
Etheric acid ester in the last of the ten Heavenly stems 2.0 484
Cobaltous diacetate tetrahydrate 1.0 249
Triethylamine is an amount of
Methyl alcohol is an amount of
Deionized water is an amount of
2. preparation process:
The Cobaltous diacetate tetrahydrate is complete with 210 gram methyl alcohol and 90 gram water dissolution, and outward appearance is the red-purple clear solution.
Four-hole boiling flask is loaded on the electronic constant speed stirrer, and left side mouth is loaded onto reflux condensing tube, loads onto dropping funnel for right mouthful, and four-hole is loaded onto thermometer.In flask, add the mixed solution of etheric acid ester in the positive last of the ten Heavenly stems and methyl alcohol, under agitation drip the Cobaltous diacetate methanol aqueous solution,, have peach solid to separate out along with splashing into of Cobaltous diacetate.Drip and finish, the triethylamine methyl alcohol mixed liquor regulation system pH value that drips weight ratio 50% again makes chelating complete to 7--8.The final reaction system is rose pink pasty state, stops to stir, and standing over night.
By suction filtration, gained incarnadine solid is the crude product of etheric acid ester cobalt in the positive last of the ten Heavenly stems (+2) inner complex with reaction product, with 60% methanol aqueous solution washing several times (inner complex also can contain some parts of crystal water under this condition), send vacuum-drying.Etheric acid ester in last of the ten Heavenly stems cobalt (+2) inner complex is stored among the etheric acid ester in the last of the ten Heavenly stems.
3. product index:
(a) outward appearance: rose pink solid
(b) etheric acid ester in last of the ten Heavenly stems cobalt (+2) inner complex expressivity structure is as follows:
(c) cobalt contents (%):
Theoretical value: 10.91 (not containing crystal water) 10.22 (containing 2 parts of crystal water)
Measured value: (calcination method) organism 89.78
Co
3O
4 10.22
Cobalt contents 7.51
(d) solvability: water insoluble, No. 200 gasoline dissolve in ethanol, acetone, and, N-BUTYL ACETATE, dimethylbenzene, dissolving or dispersion in containing the vegetable oil acid resin.
4. the diffuse reflectance infrared spectroscopy peak of inner complex:
v(C＝O)1622cm
-1，v(C＝C)1529cm
-1，v(Co-O)499-316cm
-1，v(H2O)3366cm
-1
C. application experiment
Experiment material, method are with reference to example 1, and contrast sample 2 used siccative change and make etheric acid ester in last of the ten Heavenly stems cobalt (+2) inner complex in the laboratory sample, and the siccative addition is constant, is 0.03%.
Experimental result sees Table 6:
Table 6
| Sample | 389-9 alkyd varnish consumption (g) | The siccative consumption (metal quality, g) | Surface drying (h) | Do solid work (h) | Hardness (1) |
| Blank sample | 150 | 0 | 22 | Do not do solid work after 7 days | B |
| Contrast sample 1 | 150 | 0.021 | 2.1 | 24 | F |
| Contrast sample 2 | 150 | 0.021 | 2.65 | 24 | F |
(1) pencil hardness is as the criterion to scratch.
Embodiment 7
A: the preparation of etheric acid ten diester:
1. reaction equation:
2. fill a prescription:
Reactant molar mass (g)
Lauryl alcohol 1.0 1%
Ketene dimer 1.0 84.0
98% vitriol oil (catalyzer) 0.5
3. operating process:
Press the reaction unit of example 1, drop into lauryl alcohol in reaction flask, 98% vitriol oil stirs down and heats up, logical nitrogen protection.Be heated to 90 ℃, begin slowly to drip after stable ketene dimer (this exothermic heat of reaction is violent, thus the control rate of addition so that temperature is controlled at about 90 ℃).After ketene dimer dropwised, reaction was 1 hour about 90-100 ℃, specifically decides on the ketene dimer degree of reacting completely, and reaction end is controlled with gas-chromatography.
Reaction finishes, and reactant is cooled to 50 ℃, with the 10% aqueous sodium carbonate neutrality that neutralizes.Standing demix is removed water layer, and oil reservoir spends the night with anhydrous magnesium sulfate drying.Target product cut under 182 ℃ of-186 ℃/8mmHg is collected in underpressure distillation.
4. physical index:
Molecular formula:
Molecular weight: 270
Outward appearance: colourless transparent liquid
Boiling point: 182 ℃ of-186 ℃/8mmHg
n
D 28：1.4433
d
25：0.8986g/ml
B: the preparation of etheric acid ten diester cobalt (+2) inner complexs
1. fill a prescription:
Reactant molar mass (g)
Etheric acid ten diester 2.0 540
Cobaltous diacetate tetrahydrate 1.0 249
The NaOH aqueous ethanolic solution is an amount of
Aqueous ethanolic solution (95 weight %) is an amount of
Deionized water is an amount of
2. preparation process:
With reference to example 1.Etheric acid ten diester cobalt (+2) inner complexs are stored among etheric acid ten diester.
3. product index:
(a). outward appearance: rose pink solid
(b) etheric acid ten diester cobalt (+2) inner complex expressivity structures are as follows:
(c) cobalt contents (%):
Theoretical value: 9.88 (not containing crystal water) 9.32 (containing 2 parts of crystal water)
Measured value: (calcination method) organism 89.74
Co
3O
4 10.26
Cobalt contents 7.53
(d) solvability: water insoluble, acetone dissolves in ethanol, dimethylbenzene, No. 200 gasoline and N-BUTYL ACETATE.Dissolving or dispersion in containing the vegetable oil acid resin.
The diffuse reflectance infrared spectroscopy peak of 4 inner complexs:
v(C＝O)1623cm
-1，v(C＝C)1526cm
-1，v(Co-O)491--316cm
-1
C. application experiment:
Experiment material, method are with reference to example 1, and contrast sample 2 used siccative change and make etheric acid ten diester cobalt (+2) inner complexs in the laboratory sample, and the siccative addition is constant, is 0.03%.
Experimental result sees Table 7:
Table 7
| Sample | 389-9 alkyd varnish consumption (g) | The siccative consumption (metal quality, g) | Surface drying (h) | Do solid work (h) | Hardness (1) |
| Blank sample | 150 | 0 | 22 | Do not do solid work after 7 days | B |
| Contrast sample 1 | 150 | 0.021 | 2.1 | 24 | F |
| Contrast sample 2 | 150 | 0.021 | 2.6 | 24 | F |
(1) pencil hardness is as the criterion to scratch.
Embodiment 1-7 brief summary:
(1) Acetacetic acid alkyl ester and inner complex thereof are synthetic simple, and productive rate is higher, are fit to the needs of large-scale commercial production.
(2) the Acetacetic acid alkyl ester cobalt chelates can be dissolved among the resin that contains siccative oil, such as Synolac, also dissolves in some conventional solvents, has brought convenience for it is used for water-based system coating.
(3) Acetacetic acid alkyl ester cobalt chelates siccative and traditional siccative such as cobalt iso-octoate have the similar dryness energy of urging.
Embodiment 8
The Acetacetic acid alkyl ester cobalt chelates is urged dried application experiment in water-base resin:
Used water-base resin is HD-E50 water-base epoxy ester (sharp heavy chemicals company limited, the solid content 40% used of Beijing Jin Hui).The siccative addition is 0.4% (urging dried metal quality to resin solid part quality).
Because there is no the judgement criteria that corresponding water-base resin is urged the dryness energy in the existing national standard, the present invention will adopt the method for following provisions:
1) surface drying of filming: after adding siccative in the water-base epoxy ester, varnish is diluted to solid content 20% with deionized water.With the spraying or standard blade coating device blade coating on 70*150mm detin layer tinplate, coating thickness is controlled between the 20--25 μ m, making sheet and the performance evaluation of filming are all finished in 23 ℃ ± 1 ℃ thermostatic chamber.Surface drying time is finished from making sheet and is begun to calculate, and concrete grammar touches dry method with reference to the finger among the GB1728-79.
2) film and do solid work: behind the surface drying of filming, oxygen gradually to the internal layer infiltration, impels the two key α of inner layer resin-H place formation superoxide from film coated surface, promptly is decomposed to form free radical and makes and film to the polymerization of depth curing cross-linked, reaches at last and does solid work.Along with doing solid work of filming, filming has also possessed certain rigidity and anti-solvent (as No. 200 gasoline) dissolved ability.For the evaluation of doing solid work with reference to the pressure filter paper method among the GB1728-79.
Experiment 1:
Table 8
| Sample | HD--E50( g) | Surface drying (min) | Do solid work (h) | Hardness (1) | The solvability of anti-No. 200 gasoline (2) |
| Blank sample | 40 | 6 | Do not do solid work after 7 days | ＜6B | 5 times |
| Cobalt iso-octoate | 40 | 8 | 96h is qualified | HB | ＞200 times are not broken |
| The positive butyl ester cobalt of etheric acid | 40 | 6 | 96h is qualified | B | ＞200 times are not broken |
| Etheric acid n-pentyl ester cobalt | 40 | 14 | 96h is qualified | B | 190 times |
| The just own ester cobalt of etheric acid | 40 | 14 | 96h is qualified | B | ＞200 times are not broken |
| Etheric acid n-octyl cobalt | 40 | 11 | 96h is qualified | B | 180 times |
| The different monooctyl ester cobalt of etheric acid | 40 | 9 | 96h is qualified | B | ＞200 times are not broken |
| Etheric acid ester in last of the ten Heavenly stems cobalt | 40 | 10 | 96h is qualified | 2B | 140 times |
| Etheric acid ten diester cobalts | 40 | 8 | 96h is qualified | B | 140 times |
(1) hardness is pencil hardness, is as the criterion to scratch
(2) solvability of anti-No. 200 gasoline is meant on model and drips an amount of No. 200 gasoline, and films with the rolled paper wiping of exerting oneself, and films with galling, exposes ground and is as the criterion.
Experiment 2:
By the above method sample preparation plate, and put into 60 ℃ baking oven immediately, refer to touch dry method at 60 ℃ of surface dryings that whether judge by GB1728-79.
The result is as follows:
Table 9
| Sample | (60 ℃) surface dryings (min) |
| Blank sample | 7 hours surface dryings not |
| Cobalt iso-octoate | 25 |
| The positive butyl ester cobalt of etheric acid | 24 |
| Etheric acid n-pentyl ester cobalt | 12 |
| The just own ester cobalt of etheric acid | 35 |
| Etheric acid n-octyl cobalt | 35 |
| The different monooctyl ester cobalt of etheric acid | 35 |
| Etheric acid ester in last of the ten Heavenly stems cobalt | 31 |
| Etheric acid ten diester cobalts | 28 |
Embodiment 8 brief summaries:
1. can find out from table 8 that Acetacetic acid alkyl ester cobalt chelates siccative is the same with traditional siccative to be had the water-base resin that contains dry vegetable oil and significantly urge the effect done.So blank sample does not contain the basic just crosslinking polymerization curing in a short time of siccative, does not therefore do solid work, and does not have hardness yet and can say, its anti-solvent solubility has great gap with the model that is added with siccative.
2. can learn also from table 8 that blank sample is similar to the model surface drying performance that has added siccative such as Acetacetic acid alkyl ester cobalt chelates.But in fact both have difference in essence.Do not add filming of siccative and crosslinking polymerization can't take place in a short time solidify, therefore if near or surpass under the softening temperature, blank sample is filmed and should be softened and can not surface drying.Added filming because for crosslinking polymerization solidifies surface drying of siccative, but near or above also surface drying under the softening temperature.We select 60 ℃ as probe temperature, and experimental result sees Table 9.As shown in Table 9, experimental result is consistent with anticipation, and this has illustrated that also Acetacetic acid alkyl ester cobalt chelates siccative of the present invention and traditional siccative have played same effect.
Claims (4)
1, a kind of Acetacetic acid alkyl ester metal chelate coating drier is characterized in that having following chemical expressivity structure: [(M
N+) (A) n] (H
2O) p formula (1)
Wherein: M is the Co metal ion, and A is the Acetacetic acid alkyl ester of following structure:
R is that the C atomicity is 4～18 aliphatic alkyl, comprises straight chained alkyl and branched-chain alkyl,
N represents 2,
P represents an integer between 0～2.
2, the preparation method of the described Acetacetic acid alkyl ester metal chelate coating drier of a kind of claim 1 is characterized in that step comprises:
(1) under nitrogen atmosphere, alkyl alcohol and ketene dimer synthesis of acetyl alkyl acetate in the presence of catalyzer, the mol ratio of alkyl alcohol and ketene dimer is 1～1.20: 1, catalyzer is to choose any one kind of them in amines catalyst, acid catalyst, the Organometal compound catalyst, catalyst levels is 0.15～0.85 weight % of reaction-ure mixture
(2) Acetacetic acid alkyl ester makes corresponding Acetacetic acid alkyl ester metal chelate with the inorganic metal reactant salt that contains Co, and the mol ratio of Acetacetic acid alkyl ester and inorganic metal salt is 2～4: 1.
3, preparation method according to claim 2, it is characterized in that in the described catalyzer, amines catalyst is to choose any one kind of them in triethylamine, Tributylamine or the pyridine, and acid catalyst is to choose any one kind of them in the vitriol oil, the p-methyl benzenesulfonic acid, and the organo-metallic salt catalyst is a dibutyl tin dilaurate.
4, preparation method according to claim 2 is characterized in that described inorganic metal salt is: choose any one kind of them in rose vitriol or the Cobaltous diacetate.
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| EP2607435A1 (en) * | 2011-12-20 | 2013-06-26 | Akzo Nobel Coatings International B.V. | Drier for autoxidisable coating composition |
| CN109266155A (en) * | 2018-09-20 | 2019-01-25 | 赵建平 | A kind of printing gloss oil and preparation method thereof |
| CN109321027A (en) * | 2018-09-21 | 2019-02-12 | 合肥市君科合成材料有限公司 | A kind of novel aqueous drier and preparation method thereof |
| CN111825553A (en) * | 2019-04-17 | 2020-10-27 | 青岛海湾精细化工有限公司 | Preparation method of methyl acetoacetate |
| CN110760213A (en) * | 2019-11-15 | 2020-02-07 | 沈阳澳宇化工有限公司 | Water-based composite drier and preparation method thereof |
| CN112175500B (en) * | 2020-09-18 | 2022-08-05 | 东来涂料技术（上海）股份有限公司 | Quick-drying elastic paint and use method thereof |
| CN114015358B (en) * | 2021-11-26 | 2023-07-21 | 上海华谊涂料有限公司 | Water-based oxidative crosslinking resin drier and preparation method thereof |
| CN115181479A (en) * | 2022-08-17 | 2022-10-14 | 安徽省巢湖市通用锚链有限公司 | Maintenance coating for navigation mark ship |
| CN117683458A (en) * | 2024-02-02 | 2024-03-12 | 北京超智控信科技有限公司 | Insulating coating material for self-closing line of electrified railway |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5846897A (en) * | 1997-03-19 | 1998-12-08 | King Industries, Inc. | Zirconium urethane catalysts |
| CN1280122A (en) * | 1999-07-08 | 2001-01-17 | 南通醋酸化工厂 | Method for producing acetylacetic ester |
| CN1524097A (en) * | 2001-05-29 | 2004-08-25 | Լ��ɭ����ɪ��������˾ | Organometallic compositons |
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2004
- 2004-11-17 CN CNB2004100842881A patent/CN1333029C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5846897A (en) * | 1997-03-19 | 1998-12-08 | King Industries, Inc. | Zirconium urethane catalysts |
| CN1280122A (en) * | 1999-07-08 | 2001-01-17 | 南通醋酸化工厂 | Method for producing acetylacetic ester |
| CN1524097A (en) * | 2001-05-29 | 2004-08-25 | Լ��ɭ����ɪ��������˾ | Organometallic compositons |
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