CN107090066A - Self-emulsification aqueous urea isobutylaldehyde formaldehyde resin and preparation method thereof - Google Patents
Self-emulsification aqueous urea isobutylaldehyde formaldehyde resin and preparation method thereof Download PDFInfo
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- CN107090066A CN107090066A CN201710389547.9A CN201710389547A CN107090066A CN 107090066 A CN107090066 A CN 107090066A CN 201710389547 A CN201710389547 A CN 201710389547A CN 107090066 A CN107090066 A CN 107090066A
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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 application provides a kind of self-emulsification aqueous urea isobutylaldehyde formaldehyde resin and preparation method thereof, by the way that isobutylaldehyde, 37% formaldehyde, urea and 50% sulfuric acid are mixed, is reacted 180 minutes at 90 DEG C, dimethylbenzene is added to be sufficiently stirred for, stratification, takes organic phase to remove after dimethylbenzene, obtains resin prepolymer；Under nitrogen protection; Water-borne modification monomer is added in above-mentioned resin prepolymer; it is warming up to after certain temperature, isothermal reaction is cooled to 90 DEG C to certain acid number; it is 300 ~ 3000cps to add diluent regulation reactant viscosity; 70 DEG C are cooled to, it is 6 ~ 8 to add triethylamine and be neutralized to pH value, is stirred 30 minutes; add deionized water high-speed stirred to emulsify 60 minutes, obtain self-emulsification aqueous urea isobutylaldehyde formaldehyde resin.The self-emulsification aqueous urea isobutylaldehyde formaldehyde resin excellent storage stability, has good compatibility with other water-base resin systems.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to self-emulsification aqueous urea-isobutyl aldehyde-formolite resin and
Its preparation method.
Background technology
Urea-isobutyl aldehyde-formolite resin is a kind of colourless or yellowish aldehyde condensation resin, and in coating/ink formulations
Raw material have good compatibility, with excellent yellowing resistance energy, can effectively improve adhesive force, hardness, the gloss of coating
The richness of degree, solids content and film, is a kind of multifunctional coating/ink addition agent.However, traditional urea-isobutyl aldehyde-formolite
Resin is oily molten type hard resin, is only used in solvent based coating and ink system.With the enhancing of people's environmental consciousness, respectively
State is to volatile organic matter in coating/ink（VOC）Limitation it is more and more stricter, for example, Waterborne wood in China's national standard
VOC content≤250g/L of device coating, VOC content≤120g/L of aqueous architectural coating；Unite States Standard is VOC content≤50g/
L；German blue sky makes standard be VOC content≤1.05g/L.Low VOC even coating/ink product of Diamond Search are increasingly by people
Attention, the Water-borne modification trend of coating/ink is increasingly apparent, the main development direction as current coating/ink.It is used as one
Important coating/ink used additives resin is planted, the Water-borne modification of urea-isobutyl aldehyde-formolite resin is not only able to widen this resin
Application, and have positive meaning to the Water-borne modification for promoting coating/ink, the focus studied as people.
The content of the invention
Based on this, it is necessary to which for problem present in background technology, there is provided a kind of self-emulsification aqueous urea-isobutylaldehyde-first
Urea formaldehyde.
In addition, the present invention also provides a kind of preparation method of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin.
A kind of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin, structural formula is as follows：
,
Wherein, R isOr, R1 is selected from inclined
At least one of benzenetricarboxylic anhydride, maleic anhydride and phthalic anhydride, R2 are dihydromethyl propionic acid.
A kind of preparation method of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin, comprises the following steps：
Isobutylaldehyde, 37% formaldehyde, urea and 50% sulfuric acid are mixed, reacted 180 minutes at 90 DEG C, dimethylbenzene is added and is sufficiently stirred for,
Stratification, takes organic phase to remove after dimethylbenzene, obtains resin prepolymer；
Under nitrogen protection, Water-borne modification monomer is added in the resin prepolymer, is warming up to after certain temperature, isothermal reaction is extremely
Certain acid number, is cooled to 90 DEG C, and it is 300 ~ 3000cps to add diluent regulation reactant viscosity, is cooled to 70 DEG C, adds three second
Amine is neutralized to pH value for 6 ~ 8, stirs 30 minutes, adds deionized water high-speed stirred and emulsifies 60 minutes, obtain self-emulsification aqueous urea-
Isobutylaldehyde-formaldehyde resin；
The Water-borne modification monomer in trimellitic anhydride, maleic anhydride, phthalic anhydride and dihydromethyl propionic acid at least
It is a kind of；
The structural formula of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is as follows：
,
Wherein, R isOr, R1 is selected from inclined
At least one of benzenetricarboxylic anhydride, maleic anhydride and phthalic anhydride, R2 are dihydromethyl propionic acid.
In one of the embodiments, the mass ratio relation between each raw material is：
37% 100 parts of formaldehyde；
30 ~ 90 parts of isobutylaldehyde；
20 ~ 30 parts of urea；
50% 1 ~ 5 part of sulfuric acid；
4 ~ 10 parts of Water-borne modification monomer；
50 ~ 80 parts of dimethylbenzene；
15 ~ 40 parts of diluent；
70 ~ 160 parts of deionized water.
In one of the embodiments, the diluent in propylene glycol monobutyl ether, sec-butyl alcohol and n-butanol at least
It is a kind of.
In one of the embodiments, certain acid number is 45 mgKOH/g ~ 80mgKOH/g.
In one of the embodiments, the solids content of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin be 30% ~
50%。
In one of the embodiments, the method for taking organic phase to remove dimethylbenzene is specially：Organic phase is taken in vacuum
Degree -0.095MPa, 130 DEG C of vacuum distillations 60 minutes, removes dimethylbenzene.
Above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin excellent storage stability, has well with other water-base resin systems
Compatibility.
Embodiment
In order to facilitate the understanding of the purposes, features and advantages of the present invention, specific reality below to the present invention
The mode of applying is described in detail.Many details are elaborated in the following description to fully understand the present invention.But
The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case of bright intension, therefore the present invention is not limited to the specific embodiments disclosed below.
A kind of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin, structural formula is as follows：
,
Wherein, R isOr, R1 is selected from inclined
At least one of benzenetricarboxylic anhydride, maleic anhydride and phthalic anhydride, R2 are dihydromethyl propionic acid.
Above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin, R bases be the carboxylic acid structure with ionization, make it have compared with
Good hydrophily, forms additionally by grafting Water-borne modification monomer internal emulsification, preferable oil-in-water micelle volume can be formed, with good
Good bin stability.
Above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is prepared by following methods：
S110, by isobutylaldehyde, 37% formaldehyde（Mass concentration is 37% formalin）, urea and 50% sulfuric acid（Mass concentration is
50% aqueous sulfuric acid）Mixing, reacts 180 minutes at 90 DEG C, adds dimethylbenzene and is sufficiently stirred for, and stratification takes organic phase to take off
After dimethylbenzene, resin prepolymer is obtained.
Wherein, take organic phase remove dimethylbenzene method be specially：Take organic phase in vacuum -0.095MPa, 130 DEG C subtract
Pressure distillation 60 minutes, removes dimethylbenzene.
S120, under nitrogen protection, Water-borne modification monomer is added in above-mentioned resin prepolymer, is warming up to after certain temperature,
Isothermal reaction is cooled to 90 DEG C to certain acid number, and it is 300 ~ 3000cps to add diluent regulation reactant viscosity, is cooled to 70
DEG C, it is 6 ~ 8 that addition triethylamine, which is neutralized to pH value, is stirred 30 minutes, adds deionized water high-speed stirred and emulsifies 60 minutes, obtains certainly
Emulsify aqueous urea-isobutyl aldehyde-formolite resin.
Wherein, the mass ratio relation between each raw material is as follows：
37% 100 parts of formaldehyde；
30 ~ 90 parts of isobutylaldehyde；
20 ~ 30 parts of urea；
50% 1 ~ 5 part of sulfuric acid；
4 ~ 10 parts of Water-borne modification monomer；
50 ~ 80 parts of dimethylbenzene；
15 ~ 40 parts of diluent；
70 ~ 160 parts of deionized water.
Wherein, Water-borne modification monomer is in trimellitic anhydride, maleic anhydride, phthalic anhydride and dihydromethyl propionic acid
It is at least one.
It is appreciated that the above-mentioned certain temperature that is warming up in certain temperature be according to the solution temperature of Water-borne modification monomer come
Fixed.
Diluent is selected from least one of propylene glycol monobutyl ether, sec-butyl alcohol and n-butanol.
Because this elementary reaction is solvent-free reaction, when system reaction temperature is reduced to 90 DEG C, system viscosity is very big very
To the scene that glass transition occurs, it is unfavorable for the progress of next step neutralization reaction, accordingly, it would be desirable to be carried out using diluent molten
The viscosity of simultaneously final regulation system is solved in the scope that can preferably disperse.
Wherein, certain acid number of the isothermal reaction into certain acid number is：45 mgKOH/g ~80mgKOH/g.
The solids content of above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is 30% ~ 50%.
The preparation method of above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is simple, and the self-emulsification aqueous urea prepared-
Isobutylaldehyde-formaldehyde resin excellent storage stability, has good compatibility with other water-base resin systems.
It is specific embodiment below.
Embodiment 1
216kg isobutylaldehydes, the formaldehyde of 243kg 37%, 60kg urea and the sulfuric acid of 5.2kg 50% are mixed, 180 points are reacted at 90 DEG C
Clock, adds 150kg dimethylbenzene and is sufficiently stirred for, stratification, takes organic phase to subtract under the conditions of vacuum is -0.095MPa, 130 DEG C
After pressure distillation 60 minutes, removing dimethylbenzene, resin prepolymer is obtained.
Under nitrogen protection, 17kg trimellitic anhydrides are added in the above-mentioned resin prepolymers of 100kg, 170 DEG C, perseverance are warming up to
Temperature reaction to acid number is 80mgKOH/g, is cooled to 90 DEG C, and it is 600cps, cooling to add 40kg n-butanols regulation reactant viscosity
To 70 DEG C, it is 6 ~ 8 to add 17kg triethylamines and be neutralized to pH value, stirs 30 minutes, adds the emulsification of 213kg deionized waters high-speed stirred
60 minutes, obtain self-emulsification aqueous urea-isobutyl aldehyde-formolite resin.
After testing, the solids content of above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is 45%, and viscosity is 300cps,
Average grain diameter is 105nm, and storage at normal temperature stability was up to 1 year or so, and the compatibility of water-base resin system is as shown in table 1（Test and
Assessment method refers to 7.2 stability of emulsion in GB11543-2008）：
The compatibility of the water-base resin system of table 1
| Resin types | Dewatering ability |
| Waterborne polyurethane resin | 6 |
| Aqueous epoxy resins | 5 |
| Water-based acrylic resin | 6 |
| Water-based epoxy acrylic resin | 5 |
| Aqueous melamine resin | 6 |
Embodiment 2
108kg isobutylaldehydes, the formaldehyde of 243kg 37%, 60kg urea and 3.75kg50% sulfuric acid are mixed, 180 points are reacted at 90 DEG C
Clock, adds 125kg dimethylbenzene and is sufficiently stirred for, stratification, takes organic phase to subtract under the conditions of vacuum is -0.095MPa, 130 DEG C
After pressure distillation 60 minutes, removing dimethylbenzene, resin prepolymer is obtained.
Under nitrogen protection, 11kg maleic anhydrides are added in the above-mentioned resin prepolymers of 100kg, 90 DEG C, constant temperature are warming up to
Reaction to acid number is 60mgKOH/g, and it is 600cps to add 40kg propylene glycol monobutyl ethers regulation reactant viscosity, is cooled to 70 DEG C,
It is 6 ~ 8 to add 12kg triethylamines and be neutralized to pH value, stirs 30 minutes, adds 300kg deionized waters high-speed stirred and emulsify 60 minutes,
Obtain self-emulsification aqueous urea-isobutyl aldehyde-formolite resin.
After testing, the solids content of above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is 45%, and viscosity is 300cps,
Average grain diameter is 100nm, and storage at normal temperature stability was up to 1 year or so, and the compatibility of water-base resin system is as shown in table 2（Test and
Assessment method refers to 7.2 stability of emulsion in GB11543-2008）：
The compatibility of the water-base resin system of table 2
| Resin types | Dewatering ability |
| Waterborne polyurethane resin | 5 |
| Aqueous epoxy resins | 5 |
| Water-based acrylic resin | 6 |
| Water-based epoxy acrylic resin | 5 |
| Aqueous melamine resin | 6 |
Embodiment 3
216kg isobutylaldehydes, the formaldehyde of 243kg 37%, 60kg urea and the sulfuric acid of 11kg 50% are mixed, reacted 180 minutes at 90 DEG C,
Add 150kg dimethylbenzene to be sufficiently stirred for, stratification, take organic phase to be depressurized under the conditions of vacuum is -0.095MPa, 130 DEG C
After distillation 60 minutes, removing dimethylbenzene, resin prepolymer is obtained.
Under nitrogen protection, 11kg phthalic anhydrides are added in the above-mentioned resin prepolymers of 100kg, 130 DEG C are warming up to,
Isothermal reaction to acid number is 50mgKOH/g, is cooled to 90 DEG C, and it is 600cps, drop to add 40kg sec-butyl alcohols regulation reactant viscosity
Temperature is to 70 DEG C, and it is 6 ~ 8 to add 10kg triethylamines and be neutralized to pH value, stirs 30 minutes, adds 300kg deionized waters high-speed stirred breast
Change 60 minutes, obtain self-emulsification aqueous urea-isobutyl aldehyde-formolite resin.
After testing, the solids content of above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is 35%, and viscosity is 280cps,
Average grain diameter is 96nm, and storage at normal temperature stability was up to 1 year or so, and the compatibility of water-base resin system is as shown in table 3（Test and comment
Method is determined with reference to 7.2 stability of emulsion in GB11543-2008）：
The compatibility of the water-base resin system of table 3
| Resin types | Dewatering ability |
| Waterborne polyurethane resin | 6 |
| Aqueous epoxy resins | 5 |
| Water-based acrylic resin | 5 |
| Water-based epoxy acrylic resin | 5 |
| Aqueous melamine resin | 6 |
Embodiment 4
144kg isobutylaldehydes, the formaldehyde of 243kg 37%, 60kg urea and the sulfuric acid of 5.2kg 50% are mixed, 180 points are reacted at 90 DEG C
Clock, adds 150kg dimethylbenzene and is sufficiently stirred for, stratification, takes organic phase to subtract under the conditions of vacuum is -0.095MPa, 130 DEG C
After pressure distillation 60 minutes, removing dimethylbenzene, resin prepolymer is obtained.
Under nitrogen protection, 12kg dihydromethyl propionic acids are added in the above-mentioned resin prepolymers of 100kg, 190 DEG C are warming up to,
Isothermal reaction to acid number is 45mgKOH/g, is cooled to 90 DEG C, and it is 600cps, drop to add 40kg n-butanols regulation reactant viscosity
Temperature is to 70 DEG C, and it is 6 ~ 8 to add 9.1kg triethylamines and be neutralized to pH value, stirs 30 minutes, adds 200kg deionized water high-speed stirreds
Emulsification 60 minutes, obtains self-emulsification aqueous urea-isobutyl aldehyde-formolite resin.
After testing, the solids content of above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is 45%, and viscosity is 300cps,
Average grain diameter is 104nm, and storage at normal temperature stability was up to 1 year or so, and the compatibility of water-base resin system is as shown in table 4（Test and
Assessment method refers to 7.2 stability of emulsion in GB11543-2008）：
The compatibility of the water-base resin system of table 4
| Resin types | Dewatering ability |
| Waterborne polyurethane resin | 6 |
| Aqueous epoxy resins | 5 |
| Water-based acrylic resin | 6 |
| Water-based epoxy acrylic resin | 6 |
| Aqueous melamine resin | 6 |
Embodiment 5
216kg isobutylaldehydes, the formaldehyde of 243kg 37%, 60kg urea and the sulfuric acid of 5.2kg 50% are mixed, 180 points are reacted at 90 DEG C
Clock, adds 150kg dimethylbenzene and is sufficiently stirred for, stratification, takes organic phase to subtract under the conditions of vacuum is -0.095MPa, 130 DEG C
After pressure distillation 60 minutes, removing dimethylbenzene, resin prepolymer is obtained.
Under nitrogen protection, 10.3kg trimellitic anhydrides are added in the above-mentioned resin prepolymers of 100kg, 170 DEG C are warming up to,
Isothermal reaction to acid number is 54mgKOH/g, is cooled to 90 DEG C, and it is 600cps, drop to add 40kg n-butanols regulation reactant viscosity
Temperature is to 70 DEG C, and it is 6 ~ 8 to add 10.8kg triethylamines and be neutralized to pH value, stirs 30 minutes, adds 242kg deionized water high-speed stirreds
Emulsification 60 minutes, obtains self-emulsification aqueous urea-isobutyl aldehyde-formolite resin.
After testing, the solids content of above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is 40%, and viscosity is 300cps,
Average grain diameter is 100nm, and storage at normal temperature stability was up to 1 year or so, and the compatibility of water-base resin system is as shown in table 5（Test and
Assessment method refers to 7.2 stability of emulsion in GB11543-2008）：
The compatibility of the water-base resin system of table 5
| Resin types | Dewatering ability |
| Waterborne polyurethane resin | 6 |
| Aqueous epoxy resins | 5 |
| Water-based acrylic resin | 6 |
| Water-based epoxy acrylic resin | 5 |
| Aqueous melamine resin | 6 |
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but can not
Therefore it is interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection model of the present invention
Enclose.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (7)
1. a kind of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin, it is characterised in that structural formula is as follows：
,
Wherein, R isOr, R1 is selected from inclined
At least one of benzenetricarboxylic anhydride, maleic anhydride and phthalic anhydride, R2 are dihydromethyl propionic acid.
2. a kind of preparation method of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin, it is characterised in that comprise the following steps：
Isobutylaldehyde, 37% formaldehyde, urea and 50% sulfuric acid are mixed, reacted 180 minutes at 90 DEG C, dimethylbenzene is added and is sufficiently stirred for,
Stratification, takes organic phase to remove after dimethylbenzene, obtains resin prepolymer；
Under nitrogen protection, Water-borne modification monomer is added in the resin prepolymer, is warming up to after certain temperature, isothermal reaction is extremely
Certain acid number, is cooled to 90 DEG C, and it is 300 ~ 3000cps to add diluent regulation reactant viscosity, is cooled to 70 DEG C, adds three second
Amine is neutralized to pH value for 6 ~ 8, stirs 30 minutes, adds deionized water high-speed stirred and emulsifies 60 minutes, obtain self-emulsification aqueous urea-
Isobutylaldehyde-formaldehyde resin；
The Water-borne modification monomer in trimellitic anhydride, maleic anhydride, phthalic anhydride and dihydromethyl propionic acid at least
It is a kind of；
The structural formula of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is as follows：
,
Wherein, R isOr, R1 is selected from inclined
At least one of benzenetricarboxylic anhydride, maleic anhydride and phthalic anhydride, R2 are dihydromethyl propionic acid.
3. the preparation method of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin according to claim 2, it is characterised in that each
Mass ratio relation between raw material is：
37% 100 parts of formaldehyde；
30 ~ 90 parts of isobutylaldehyde；
20 ~ 30 parts of urea；
50% 1 ~ 5 part of sulfuric acid；
4 ~ 10 parts of Water-borne modification monomer；
50 ~ 80 parts of dimethylbenzene；
15 ~ 40 parts of diluent；
70 ~ 160 parts of deionized water.
4. the preparation method of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin according to Claims 2 or 3, its feature exists
In the diluent is selected from least one of propylene glycol monobutyl ether, sec-butyl alcohol and n-butanol.
5. the preparation method of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin according to claim 2, it is characterised in that institute
Certain acid number is stated for 45 mgKOH/g ~ 80mgKOH/g.
6. the preparation method of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin according to claim 2, it is characterised in that institute
The solids content for stating self-emulsification aqueous urea-isobutyl aldehyde-formolite resin is 30% ~ 50%.
7. the preparation method of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin according to claim 2, it is characterised in that institute
Stating the method for taking organic phase to remove dimethylbenzene is specially：Organic phase is taken in vacuum -0.095MPa, 130 DEG C of 60 points of vacuum distillations
Clock, removes dimethylbenzene.
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| CN110016112A (en) * | 2019-05-06 | 2019-07-16 | 岳阳市英泰合成材料有限公司 | Water-soluble urea-isobutyl aldehyde-formolite resin and preparation method thereof |
| CN110358043A (en) * | 2019-05-06 | 2019-10-22 | 岳阳市英泰合成材料有限公司 | Non-ionic self-emulsifying aqueous urea-isobutyl aldehyde-formolite resin and preparation method thereof |
| CN110358034A (en) * | 2019-05-06 | 2019-10-22 | 岳阳市英泰合成材料有限公司 | Self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic and preparation method thereof |
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| CN108440732B (en) * | 2018-03-13 | 2020-05-08 | 广东工业大学 | Light-curable aqueous urea-isobutyraldehyde-formaldehyde resin and preparation method thereof |
| CN110016112A (en) * | 2019-05-06 | 2019-07-16 | 岳阳市英泰合成材料有限公司 | Water-soluble urea-isobutyl aldehyde-formolite resin and preparation method thereof |
| CN110358043A (en) * | 2019-05-06 | 2019-10-22 | 岳阳市英泰合成材料有限公司 | Non-ionic self-emulsifying aqueous urea-isobutyl aldehyde-formolite resin and preparation method thereof |
| CN110358034A (en) * | 2019-05-06 | 2019-10-22 | 岳阳市英泰合成材料有限公司 | Self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic and preparation method thereof |
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