CN108484854A - A kind of uV curable urea-isobutyl aldehyde-formolite resin and preparation method thereof - Google Patents
A kind of uV curable urea-isobutyl aldehyde-formolite resin and preparation method thereof Download PDFInfo
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- CN108484854A CN108484854A CN201810206288.6A CN201810206288A CN108484854A CN 108484854 A CN108484854 A CN 108484854A CN 201810206288 A CN201810206288 A CN 201810206288A CN 108484854 A CN108484854 A CN 108484854A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
- C08G12/12—Ureas; Thioureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/44—Chemically modified polycondensates by esterifying
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Abstract
The invention belongs to paint fields more particularly to a kind of uV curable urea isobutylaldehyde formaldehyde resin and preparation method thereof.The present invention provides a kind of uV curable urea isobutylaldehyde formaldehyde resins, it can be cured under ultraviolet light with unsaturated double-bond, the experimental results showed that, have preferable hardness, adhesive force high after uV curable urea isobutylaldehyde formaldehyde resin solidification.In addition, uV curable urea isobutylaldehyde formaldehyde resin hardening time of the present invention is short, gloss is high after solidification, and weather resistance is good, without using reactive diluent when solidification, reduces the influence to environmental and human health impacts.The present invention also provides a kind of preparation methods of uV curable urea isobutylaldehyde formaldehyde resin, the terminal aldehyde group of urea isobutylaldehyde formaldehyde resin is oxidized to carboxyl, the epoxy addition with glycidyl acrylate one end connects unsaturated double-bond again, uV curable urea isobutylaldehyde formaldehyde resin is obtained, step is few, simple for process.
Description
Technical field
The invention belongs to paint field more particularly to a kind of uV curable urea-isobutyl aldehyde-formolite resin and its preparations
Method.
Background technology
Urea-isobutyl aldehyde-formolite resin is a kind of important multifunctional coating auxiliary agent, has yellowing resistance good, solubility property
It is excellent, the adhesive force of film, and the performances such as glossiness and hardness that can improve film can not only be improved.The application of coating additive
It is horizontal, it has also become to weigh one of the mark of coating material production technical merit.Ultraviolet light solidification (UV-curing) is to utilize ultraviolet light
In, shortwave, under uv radiation, photoinitiator in liquid UV materials is irradiated to be changed into free radical or cation, to cause
Resin polymerization containing active function groups is cross-linked into the process of insoluble insoluble solid paint film, and UV-curing technology is because with height
Effect, economical, energy saving, applicability extensively, advantages of environment protection and be widely used in the fields such as coating, ink, adhesive.It can be ultraviolet
Photocureable coating auxiliary agent is usually sticky liquid at room temperature, and photoinitiator is added after mixing, passes through ultraviolet light irradiation
The painting membrane product with good adhesion and peel strength is formed afterwards.But after existing uV curable coating additive solidification
Hardness and adhesive force up for improve.
Invention content
The present invention provides a kind of uV curable urea-isobutyl aldehyde-formolite resin, for solve it is existing can UV light
Change the problem of hardness after coating additive solidification and adhesive force are up for improving.
The specific technical solution of the present invention is：
A kind of uV curable urea-isobutyl aldehyde-formolite resin has knot shown in structure and/or formula (II) shown in formula (I)
Structure；
The present invention also provides a kind of preparation methods of uV curable urea-isobutyl aldehyde-formolite resin, including：
A) urea-isobutyl aldehyde-formolite resin is dissolved in organic solvent, the hydrogen peroxide of 3wt%~10wt% is added, carried out
Oxidation reaction obtains the compound of formula (III) structure；
B) by the compound of formula (III) structure and glycidyl acrylate and/or (methyl) glycidyl acrylate
It is dissolved in organic solvent, under antioxidant protection, carries out catalysis reaction, obtain with structure and/or formula shown in formula (I)
(II) the uV curable urea-isobutyl aldehyde-formolite resin of structure shown in.
Preferably, the temperature of the oxidation reaction is 60~80 DEG C；
The time of the oxidation reaction is 3~5h.
Preferably, the temperature of the catalysis reaction is 85~120 DEG C；
The time of the catalysis reaction is 6~10h.
Preferably, the molecular weight of the urea-isobutyl aldehyde-formolite resin is 800~5000；
The hydroxyl value of the urea-isobutyl aldehyde-formolite resin is 50~200mgKOH/g.
Preferably, the catalyst of the catalysis reaction is one kind in triphenylphosphine, triethylamine or N-N- dimethyl benzylamines
Or it is a variety of.
Preferably, the antioxidant is 2,6- DI-tert-butylphenol compounds, hydroquinone, phosphite ester triphenylmethyl methacrylate or 1,3,6
It is one or more in [bis- -2 (the 3H)-benzofuranones of (1,1- dimethyl ethyls) -3- (2,3- 3,5-dimethylphenyls) of 5,7-].
Preferably, the mass ratio of the urea-isobutyl aldehyde-formolite resin and the hydrogen peroxide is 18~21：10~12.
Preferably, the urea-isobutyl aldehyde-formolite resin, the glycidyl acrylate and/or the contracting of (methyl) acrylic acid
The mass ratio of water glyceride, the catalyst and the antioxidant is 18~21：5~8：0.6~1.4：0.3~0.8.
Preferably, urea-isobutyl aldehyde-formolite resin is dissolved in organic solvent by step a), is added 3wt%~10wt%'s
Hydrogen peroxide, carries out oxidation reaction, and the compound for obtaining formula (III) structure is specially：
By urea-isobutyl aldehyde-formolite resin, stirring and dissolving is in organic solvent at 40~50 DEG C, 300~500rpm stirrings
The lower hydrogen peroxide that 3wt%~10wt% is added, carries out oxidation reaction, obtains the compound of formula (III) structure.
In conclusion the present invention provides a kind of uV curable urea-isobutyl aldehyde-formolite resin, have shown in formula (I)
Structure.UV curable urea-isobutyl aldehyde-formolite resin of the present invention has unsaturated double-bond, can occur under ultraviolet light solid
Change, the experimental results showed that, there is preferable hardness, attachment after uV curable urea-isobutyl aldehyde-formolite resin solidification of the present invention
Power is high.In addition, uV curable urea-isobutyl aldehyde-formolite resin curing time of the present invention is short, gloss is high after solidification, weatherability
Can be good, without using reactive diluent when solidification, reduce the influence to environmental and human health impacts.The present invention also provides one kind
The preparation method of uV curable urea-isobutyl aldehyde-formolite resin, in the preparation method, the end of urea-isobutyl aldehyde-formolite resin
Aldehyde radical is oxidized to carboxyl, then connects unsaturated double-bond with the epoxy addition of glycidyl acrylate one end, and obtaining can be ultraviolet
Photocuring urea-isobutyl aldehyde-formolite resin, step are few, simple for process.
Specific implementation mode
The present invention provides a kind of uV curable urea-isobutyl aldehyde-formolite resin, for solve it is existing can UV light
Change the problem of hardness after coating additive solidification and adhesive force are up for improving.
Those skilled in the art can use for reference present disclosure, be suitably modified technological parameter realization.In particular, it should be pointed out that
All similar substitutions and modifications are apparent to those skilled in the art, they are considered as being included in this hair
It is bright.The product and preparation method of the present invention is described by preferred embodiment, and related personnel can obviously not depart from
Method described herein is modified or is suitably changed and is combined in the content of present invention, spirit and scope, to realize and apply
The technology of the present invention.
A kind of uV curable urea-isobutyl aldehyde-formolite resin has knot shown in structure and/or formula (II) shown in formula (I)
Structure；
UV curable urea-isobutyl aldehyde-formolite resin of the present invention has unsaturated double-bond, can occur under ultraviolet light
Solidification, and there is preferable hardness after curing, and adhesive force is high.In addition, uV curable urea-isobutylaldehyde-of the present invention
Formaldehyde resin hardening time is short, and gloss is high after solidification, and weather resistance is good, without using reactive diluent when solidification, reduces pair
The influence of environmental and human health impacts.
The present invention also provides a kind of preparation methods of uV curable urea-isobutyl aldehyde-formolite resin, including：
A) urea-isobutyl aldehyde-formolite resin is dissolved in organic solvent, the hydrogen peroxide of 3wt%~10wt% is added, carried out
Oxidation reaction obtains the compound of formula (III) structure；
B) by the compound of formula (III) structure and glycidyl acrylate and/or (methyl) glycidyl acrylate
It is dissolved in organic solvent, under antioxidant protection, carries out catalysis reaction, obtain with structure and/or formula shown in formula (I)
(II) the uV curable urea-isobutyl aldehyde-formolite resin of structure shown in.
In the present invention, the structural formula of urea-isobutyl aldehyde-formolite resin is：
In the present invention, chemically reacted one of in the preparation method of uV curable urea-isobutyl aldehyde-formolite resin
Formula is：
In the present invention, the temperature of oxidation reaction is 60~80 DEG C；
The time of oxidation reaction is 3~5h.
In the present invention, the hydrogen peroxide of 3wt%~10wt% dilutes to obtain by the hydrogen peroxide of 30wt% using deionized water.
Oxidation reaction is insulation reaction, and in the oxidation reaction, the terminal aldehyde group of urea-isobutyl aldehyde-formolite resin is oxidized to carboxyl.
After carrying out oxidation reaction, before obtaining the compound of formula (III) structure, further include：Change to formula (III) structure
It closes object to be purified, sodium sulfite is added and/or potassium sulfite restores remaining hydrogen peroxide, ethyl acetate extracts formula
(III) after the compound of structure, rotary evaporation goes out ethyl acetate.
In the present invention, the temperature for being catalyzed reaction is 85~120 DEG C；
The time of catalysis reaction is 6~10h.
In the present invention, pass through titrated acid value and/or the extent of reaction of infrared spectrum control catalysis reaction.
In catalysis is reacted, the compound and the epoxy addition of glycidyl acrylate one end of formula (III) structure connect
Unsaturated double-bond obtains uV curable urea-isobutyl aldehyde-formolite resin.Also, in catalysis is reacted, in order to protect formula
(III) compound of structure is not oxidized, and catalysis reaction carries out in nitrogen atmosphere, and by primary antioxidant, secondary antioxidant, from
By the multiple anti-oxidation protection of base agent for capturing, to obtain the uV curable urea-isobutyl aldehyde-formolite tree of faint yellow clear
Fat.
The molecular weight of urea-isobutyl aldehyde-formolite resin is 800~5000；
The hydroxyl value of urea-isobutyl aldehyde-formolite resin is 50~200mgKOH/g.
In the present invention, the catalyst that is catalyzed reaction be triphenylphosphine, triethylamine or one kind in N-N- dimethyl benzylamines or
It is a variety of.
Antioxidant is 2,6 di t butyl phenol, hydroquinone, phosphite ester triphenylmethyl methacrylate or the 1,3,6 [bis- (1,1- of 5,7-
Dimethyl ethyl) -2 (3H)-benzofuranones of -3- (2,3- 3,5-dimethylphenyls)] in it is one or more.
The mass ratio of urea-isobutyl aldehyde-formolite resin and hydrogen peroxide is 18~21：10~12.
Urea-isobutyl aldehyde-formolite resin, glycidyl acrylate and/or (methyl) glycidyl acrylate, catalyst
Mass ratio with antioxidant is 18~21：5~8：0.6~1.4：0.3~0.8.
Methyl methacrylate contains methyl compared with methyl acrylate on side chain, the methyl contained on side chain can make
Photo-curing rate is slack-off, and viscosity is different.Glycidyl acrylate and/or (methyl) glycidyl acrylate arbitrary proportion
Combination, obtains the uV curable urea-isobutyl aldehyde-formolite resin of different performance.
In the present invention, organic solvent is acetone and/or butanone in step a)；In step b) organic solvent be toluene and/or
Dimethylbenzene.
More specifically, organic solvent is acetone in step a)；Organic solvent is toluene in step b)；Urea-isobutyl aldehyde-formolite
The quality of resin, acetone, hydrogen peroxide, deionized water, toluene, (methyl) glycidyl acrylate, catalyst and antioxidant
Than being 18~21：15~17：10~12：38~41：4~6：5~8：0.6~1.4：0.3~0.8.
In the present invention, urea-isobutyl aldehyde-formolite resin is dissolved in organic solvent by step a), and 3wt%~10wt% is added
Hydrogen peroxide, carry out oxidation reaction, the compound for obtaining formula (III) structure is specially：
By urea-isobutyl aldehyde-formolite resin, stirring and dissolving is in organic solvent at 40~50 DEG C, 300~500rpm stirrings
The lower hydrogen peroxide that 3wt%~10wt% is added, carries out oxidation reaction, obtains the compound of formula (III) structure.
It in the present invention, is added after the hydrogen peroxide of 3wt%~10wt%, before carrying out oxidation reaction, further includes：Slowly rise
Temperature is to 60~80 DEG C.
The present invention provides a kind of uV curable urea-isobutyl aldehyde-formolite resins, have structure shown in formula (I).This hair
Bright uV curable urea-isobutyl aldehyde-formolite resin has unsaturated double-bond, can be cured under ultraviolet light, and real
Test the result shows that, have preferable hardness, adhesive force high after uV curable urea-isobutyl aldehyde-formolite resin solidification of the present invention.
In addition, uV curable urea-isobutyl aldehyde-formolite resin curing time of the present invention is short, gloss is high after solidification, and weather resistance is good,
Without using reactive diluent when solidification, reduce the influence to environmental and human health impacts.The present invention also provides one kind can be purple
The preparation method of outer photocuring urea-isobutyl aldehyde-formolite resin, in the preparation method, the terminal aldehyde group of urea-isobutyl aldehyde-formolite resin
It is oxidized to carboxyl, then unsaturated double-bond is connected with the epoxy addition of glycidyl acrylate one end, obtaining can UV light
Change urea-isobutyl aldehyde-formolite resin, step is few, simple for process.
For a further understanding of the present invention, below in conjunction with the embodiment of the present invention, to the technical side in the embodiment of the present invention
Case is clearly and completely described, it is clear that and described embodiments are only a part of the embodiments of the present invention, rather than all
Embodiment.Based on the embodiments of the present invention, those of ordinary skill in the art institute without making creative work
The every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
In the present embodiment, uV curable urea-isobutyl aldehyde-formolite resin is prepared according to following steps：
Step 1)：In clean and dry reaction kettle, 120g urea-isobutyl aldehyde-formolites resin and 100g third are put into successively
Ketone is warming up to 40 DEG C, and stirring to urea-isobutyl aldehyde-formolite resin is dissolved in acetone；
Step 2)：The hydrogen peroxide of 68g 30wt% is diluted to 5wt% with deionized water, is then put into reaction kettle and high
Speed stirring so that hydrogen peroxide and acetone can then be to slowly warm up to 65 DEG C in a kettle by mechanical dispersion to uniform；
Step 3)：Keep the temperature 3h, carry out oxidation reaction, the terminal aldehyde group of urea-isobutyl aldehyde-formolite resin be diluted after hydrogen peroxide
Complete oxidation, discharging；
Step 4)：Urea-isobutyl aldehyde-formolite resin after the oxidation of acquisition is purified, was incited somebody to action using 21g sodium sulfites
The hydrogen peroxide of amount restores, then is extracted with ethyl acetate, is repeatedly washed using saturated nacl aqueous solution, removes other and be dissolved in water
Impurity, rotary evaporation goes out solvent to get the compound of formula (III) structure；
Step 5)：By the compound of formula (III) structure, 30g toluene, 42.65g glycidyl methacrylate, 7.21g
N, N- dimethyl benzylamine, 3.00g 2,6- DI-tert-butylphenol compounds, 3.00g phosphite ester triphenylmethyl methacrylates, 3.00g antioxidant 1,3,6 [5,
Bis- -2 (the 3H)-benzofuranones of (1,1- dimethyl ethyl) -3- (2,3- 3,5-dimethylphenyl) of 7-] it puts into reaction kettle successively, lead to
Enter drying nitrogen and be warming up to 110 DEG C, keeps the temperature 7h, carry out catalysis reaction, the compound and glycidyl of formula (III) structure
The epoxy addition of ester one end connects unsaturated double-bond, and cooling discharging is obtained with shown in structure shown in formula (I) and/or formula (II)
The uV curable urea-isobutyl aldehyde-formolite resin of structure.
Embodiment 2
In the present embodiment, uV curable urea-isobutyl aldehyde-formolite resin is prepared according to following steps：
Step 1)：In clean and dry reaction kettle, 120g urea-isobutyl aldehyde-formolites resin and 100g third are put into successively
Ketone is warming up to 40 DEG C, stirring to dissolving；
Step 2)：The hydrogen peroxide of 68g 30wt% concentration is diluted to 5wt% using deionized water, then puts into reaction kettle
In and high-speed stirred so that hydrogen peroxide and acetone can then be to slowly warm up to 65 in a kettle by mechanical dispersion to uniform
℃；
Step 3)：Keep the temperature 3h, carry out oxidation reaction, the terminal aldehyde group of urea-isobutyl aldehyde-formolite resin be diluted after hydrogen peroxide
Complete oxidation, discharging；
Step 4)：Urea-isobutyl aldehyde-formolite resin after the oxidation of acquisition is purified, was incited somebody to action using 21g sodium sulfites
The hydrogen peroxide of amount restores, then is extracted with ethyl acetate, is repeatedly washed using saturated nacl aqueous solution, removes other and be dissolved in water
Impurity, rotary evaporation goes out solvent to get the compound of formula (III) structure；
Step 5)：By the compound of formula (III) structure, 30g toluene, 38.44g glycidyl methacrylate, 7.16g
N, N- dimethyl benzylamine, 2.98g 2,6- DI-tert-butylphenol compounds, 2.98g phosphite ester triphenylmethyl methacrylates, 2.98g antioxidant 1,3,6 [5,
Bis- -2 (the 3H)-benzofuranones of (1,1- dimethyl ethyl) -3- (2,3- 3,5-dimethylphenyl) of 7-] it puts into reaction kettle successively, lead to
Enter drying nitrogen and be warming up to 110 DEG C, keeps the temperature 6h, carry out catalysis reaction, the compound and glycidyl of formula (III) structure
The epoxy addition of ester one end connects unsaturated double-bond, and cooling discharging is obtained with shown in structure shown in formula (I) and/or formula (II)
The uV curable urea-isobutyl aldehyde-formolite resin of structure.
Embodiment 3
In the present embodiment, uV curable urea-isobutyl aldehyde-formolite resin is prepared according to following steps：
Step 1)：In clean and dry reaction kettle, 120g urea-isobutyl aldehyde-formolites resin and 100g third are put into successively
Ketone is warming up to 40 DEG C, and stirring to urea-isobutyl aldehyde-formolite resin is dissolved in acetone；
Step 2)：The hydrogen peroxide of 68g 30wt% concentration is diluted to 5wt% using deionized water, then puts into reaction kettle
In and high-speed stirred so that hydrogen peroxide and acetone can then be to slowly warm up to 65 in a kettle by mechanical dispersion to uniform
℃；
Step 3)：3h is kept the temperature, oxidation reaction, the dioxygen after making the terminal aldehyde group of urea-isobutyl aldehyde-formolite resin be diluted are carried out
Water complete oxidation, discharging；
Step 4)：Urea-isobutyl aldehyde-formolite resin after the oxidation of acquisition is purified, was incited somebody to action using 21g sodium sulfites
The hydrogen peroxide of amount restores, then is extracted with ethyl acetate, is repeatedly washed using saturated nacl aqueous solution, removes other and be dissolved in water
Impurity, rotary evaporation goes out solvent to get the compound of formula (III) structure；
Step 5)：By the compound of formula (III) structure, 30g toluene, 14.22g glycidyl methacrylate,
25.63g glycidyl methacrylate, 7.17g N, N- dimethyl benzylamine, 2.99g 2,6 di t butyl phenols, 2.99g
Phosphite ester triphenylmethyl methacrylate, [5,7- bis- (1,1- the dimethyl ethyl) -3- (2,3- 3,5-dimethylphenyl) -2 of 2.99g antioxidant 1,3,6
(3H)-benzofuranone] it puts into reaction kettle successively, it is passed through drying nitrogen and is warming up to 110 DEG C, keep the temperature 6.5h, be catalyzed anti-
It answers, the compound of formula (III) structure connects unsaturated double-bond with the epoxy addition of glycidyl acrylate one end, and cooling goes out
Material, obtains the uV curable urea-isobutyl aldehyde-formolite resin with structure shown in structure and/or formula (II) shown in formula (I).
Embodiment 4
In the present embodiment, uV curable urea-isobutyl aldehyde-formolite resin is prepared according to following steps：
Step 1)：In clean and dry reaction kettle, 120g urea-isobutyl aldehyde-formolites resin and 100g third are put into successively
Ketone is warming up to 40 DEG C, and stirring to urea-isobutyl aldehyde-formolite resin is dissolved in acetone；
Step 2)：The hydrogen peroxide of 68g 30wt% concentration is diluted to 5wt% using deionized water, then puts into reaction kettle
In and high-speed stirred so that hydrogen peroxide and acetone can then be to slowly warm up to 65 in a kettle by mechanical dispersion to uniform
℃；
Step 3)：Keep the temperature 3h, carry out oxidation reaction, the terminal aldehyde group of urea-isobutyl aldehyde-formolite resin be diluted after hydrogen peroxide
Complete oxidation, discharging；
Step 4)：Urea-isobutyl aldehyde-formolite resin after the oxidation of acquisition is purified, was incited somebody to action using 21g sodium sulfites
The hydrogen peroxide of amount restores, then is extracted with ethyl acetate, is repeatedly washed using saturated nacl aqueous solution, removes other and be dissolved in water
Impurity, rotary evaporation goes out solvent to get the compound of formula (III) structure；
Step 5)：By the compound of formula (III) structure, 30g toluene, 28.43g glycidyl methacrylate,
12.81g glycidyl methacrylate, 7.19g N, N- dimethyl benzylamine, 3.00g 2,6 di t butyl phenols, 3.00g
Phosphite ester triphenylmethyl methacrylate, [5,7- bis- (1,1- the dimethyl ethyl) -3- (2,3- 3,5-dimethylphenyl) -2 of 3.00g antioxidant 1,3,6
(3H)-benzofuranone] it puts into reaction kettle successively, it is passed through drying nitrogen and is warming up to 110 DEG C, keep the temperature 6.5h, be catalyzed anti-
It answers, the compound of formula (III) structure connects unsaturated double-bond with the epoxy addition of glycidyl acrylate one end, and cooling goes out
Material, obtains the uV curable urea-isobutyl aldehyde-formolite resin with structure shown in structure and/or formula (II) shown in formula (I).
Embodiment 5
In the present embodiment, uV curable urea-isobutyl aldehyde-formolite resin is prepared according to following steps：
Step 1)：In clean and dry reaction kettle, 120g urea-isobutyl aldehyde-formolites resin and 100g third are put into successively
Ketone is warming up to 40 DEG C, and stirring to urea-isobutyl aldehyde-formolite resin is dissolved in acetone；
Step 2)：The hydrogen peroxide of 68g 30wt% concentration is diluted to 5wt% using deionized water, then puts into reaction kettle
In and high-speed stirred so that hydrogen peroxide and acetone can then be to slowly warm up to 65 in a kettle by mechanical dispersion to uniform
℃；
Step 3)：3h is kept the temperature, oxidation reaction, the dioxygen after making the terminal aldehyde group of urea-isobutyl aldehyde-formolite resin be diluted are carried out
Water complete oxidation, discharging；
Step 4)：Urea-isobutyl aldehyde-formolite resin after the oxidation of acquisition is purified, was incited somebody to action using 21g sodium sulfites
The hydrogen peroxide of amount restores, then is extracted with ethyl acetate, is repeatedly washed using saturated nacl aqueous solution, removes other and be dissolved in water
Impurity, rotary evaporation goes out solvent to get the compound of formula (III) structure；
Step 5)：By the compound of formula (III) structure, 30g toluene, 21.32g glycidyl methacrylate,
19.22g glycidyl methacrylate, 7.18g N, N- dimethyl benzylamine, 2.99g 2,6 di t butyl phenols, 2.99g
Phosphite ester triphenylmethyl methacrylate, [5,7- bis- (1,1- the dimethyl ethyl) -3- (2,3- 3,5-dimethylphenyl) -2 of 2.99g antioxidant 1,3,6
(3H)-benzofuranone] it puts into reaction kettle successively, it is passed through drying nitrogen and is warming up to 110 DEG C, keep the temperature 6.5h, be catalyzed anti-
It answers, the compound of formula (III) structure connects unsaturated double-bond with the epoxy addition of glycidyl acrylate one end, and cooling goes out
Material, obtains the uV curable urea-isobutyl aldehyde-formolite resin with structure shown in structure and/or formula (II) shown in formula (I).
Embodiment 6
The preparation of uV curable urea-isobutyl aldehyde-formolite paint film
UV curable urea-isobutyl aldehyde-formolite resin (solid content 85%, the organic solvent third that embodiment 1 is obtained
Ketone) 0.1wt% photoinitiators TPO (2,4,6- trimethylbenzoyls diphenyl phosphine oxide) and 0.4wt% photoinitiators 184 is added
(1- hydroxycyclohexyl phenyl ketones), after stirring evenly at room temperature, is spread evenly across in tinplate sheet, 60 DEG C of baking oven bakings
0.5h is placed on ultraviolet radiation-curable on UV curing crawler belts.About 22 μm of coating layer thickness, light source is 20cm with coating distance, purple
The power of outer curing is 2000W, light intensity 20mW/cm2。
The measurement of hardness of film is measured according to GB/T1730-1993 national standards, and adhesive force is surveyed according to GB/T1720-1979
It is fixed.Test result is that the hardness of cured film is 2H, and adhesive force is 0 grade, cure times 12s.
Embodiment 7
The preparation of uV curable urea-isobutyl aldehyde-formolite paint film
UV curable urea-isobutyl aldehyde-formolite resin (solid content 85%, the organic solvent third that embodiment 1 is obtained
Ketone) 0.5wt% photoinitiators 184 (1- hydroxycyclohexyl phenyl ketones) are added, after stirring evenly at room temperature, it is spread evenly across horse
On mouth iron plate, 60 DEG C of baking ovens toast 0.5h, are placed on ultraviolet radiation-curable on UV curing crawler belts.About 22 μm of coating layer thickness, light
Source is 20cm with coating distance, and the power of uv curing machine is 2000W, light intensity 20mW/cm2。
The measurement of hardness of film is measured according to GB/T1730-1993 national standards, and adhesive force is surveyed according to GB/T1720-1979
It is fixed.Test result is that the hardness of cured film is H~2H, and adhesive force is 0 grade, cure times 10s.
Embodiment 8
Basic performance progress to the uV curable urea-isobutyl aldehyde-formolite resin that embodiment 1 to embodiment 5 obtains
Test, the results are shown in Table 1.
The basic performance of 1 uV curable urea-isobutyl aldehyde-formolite resin of the present invention of table
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of uV curable urea-isobutyl aldehyde-formolite resin, which is characterized in that have structure and/or formula shown in formula (I)
(II) structure shown in；
2. a kind of preparation method of uV curable urea-isobutyl aldehyde-formolite resin, which is characterized in that including：
A) urea-isobutyl aldehyde-formolite resin is dissolved in organic solvent, the hydrogen peroxide of 3wt%~10wt% is added, is aoxidized
Reaction, obtains the compound of formula (III) structure；
B) compound of formula (III) structure and glycidyl acrylate and/or (methyl) glycidyl acrylate are dissolved
In organic solvent, under antioxidant protection, catalysis reaction is carried out, is obtained with structure shown in formula (I) and/or formula (II) institute
Show the uV curable urea-isobutyl aldehyde-formolite resin of structure.
3. preparation method according to claim 2, which is characterized in that the temperature of the oxidation reaction is 60~80 DEG C；
The time of the oxidation reaction is 3~5h.
4. preparation method according to claim 2, which is characterized in that the temperature of the catalysis reaction is 85~120 DEG C；
The time of the catalysis reaction is 6~10h.
5. preparation method according to claim 2, which is characterized in that the molecular weight of the urea-isobutyl aldehyde-formolite resin is
800~5000；
The hydroxyl value of the urea-isobutyl aldehyde-formolite resin is 50~200mgKOH/g.
6. preparation method according to claim 2, which is characterized in that it is described catalysis reaction catalyst be triphenylphosphine,
It is one or more in triethylamine or N-N- dimethyl benzylamines.
7. preparation method according to claim 6, which is characterized in that the antioxidant be 2,6- DI-tert-butylphenol compounds,
Hydroquinone, phosphite ester triphenylmethyl methacrylate or 1,3,6 [bis- (1,1- the dimethyl ethyls) -3- (2,3- 3,5-dimethylphenyls) of 5,7- -2
(3H)-benzofuranone] in it is one or more.
8. preparation method according to claim 2, which is characterized in that the urea-isobutyl aldehyde-formolite resin and the dioxygen
The mass ratio of water is 18~21：10~12.
9. preparation method according to claim 7, which is characterized in that the urea-isobutyl aldehyde-formolite resin, the propylene
The mass ratio of acid glycidyl ester and/or (methyl) glycidyl acrylate, the catalyst and the antioxidant is 18
~21：5~8：0.6~1.4：0.3~0.8.
10. preparation method according to claim 2, which is characterized in that step a) dissolves urea-isobutyl aldehyde-formolite resin
In organic solvent, the hydrogen peroxide of 3wt%~10wt% is added, carries out oxidation reaction, obtains the compound tool of formula (III) structure
Body is：
By urea-isobutyl aldehyde-formolite resin, in organic solvent, 300~500rpm stirrings are lower to be added stirring and dissolving at 40~50 DEG C
Enter the hydrogen peroxide of 3wt%~10wt%, carries out oxidation reaction, obtain the compound of formula (III) structure.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452387A (en) * | 2019-03-14 | 2019-11-15 | 广东工业大学 | A kind of polysiloxanes of uV curable and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050043501A1 (en) * | 2003-08-22 | 2005-02-24 | Degussa Ag | Radiation-curable resins based on ketone-aldehyde and/or urea-aldehyde resins and a process for preparing them |
| CN1856556A (en) * | 2004-02-03 | 2006-11-01 | 德古萨公司 | Utilization of radiohardenable resins based on ketone and/or urea aldehyde resins |
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2018
- 2018-03-13 CN CN201810206288.6A patent/CN108484854B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050043501A1 (en) * | 2003-08-22 | 2005-02-24 | Degussa Ag | Radiation-curable resins based on ketone-aldehyde and/or urea-aldehyde resins and a process for preparing them |
| CN1856556A (en) * | 2004-02-03 | 2006-11-01 | 德古萨公司 | Utilization of radiohardenable resins based on ketone and/or urea aldehyde resins |
Non-Patent Citations (1)
| Title |
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| 汪昭玮等: "可UV固化脲-异丁醛-甲醛树脂的合成与表征", 《化工新型材料》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452387A (en) * | 2019-03-14 | 2019-11-15 | 广东工业大学 | A kind of polysiloxanes of uV curable and its preparation method and application |
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