CN110358034A - Self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic and preparation method thereof - Google Patents

Self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic and preparation method thereof Download PDF

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CN110358034A
CN110358034A CN201910369457.2A CN201910369457A CN110358034A CN 110358034 A CN110358034 A CN 110358034A CN 201910369457 A CN201910369457 A CN 201910369457A CN 110358034 A CN110358034 A CN 110358034A
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self
isobutyl aldehyde
resin
added
ionic
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张一甫
杨健
欧德培
易新亮
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YUEYANG INTECH SYNTHETIC MATERIALS CO Ltd
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YUEYANG INTECH SYNTHETIC MATERIALS CO Ltd
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    • C08G12/00Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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    • C08G18/752Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
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Abstract

The present invention provides a kind of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic and preparation method thereof, urea-isobutyl aldehyde-formolite resin is added in reaction kettle, appropriate diluent, which is added, dissolves solid part sufficiently, then heats to 65 ~ 75 DEG C;It is passed through nitrogen, suitable dibutyl tin dilaurate and polyisocyanates is added, after reaction is down to 50% or less to NCO content, dihydromethyl propionic acid is added, reaction to NCO content is down to 0.1% hereinafter, be cooled to 55 ~ 65 DEG C, and 25 ~ 35min of triethylamine neutralization reaction is added, deionized water high-speed stirred is added to emulsify 50 ~ 70 minutes, the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic is obtained by filtration.The self-emulsification aqueous urea-isobutyl aldehyde-formolite resin excellent storage stability of the ionic has good compatibility with other water-base resin systems.

Description

Self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, more particularly to the self-emulsification aqueous urea-isobutyl aldehyde-formolite of ionic Resin and preparation method thereof.
Background technique
Urea-isobutyl aldehyde-formolite resin is a kind of colourless or yellowish aldehyde condensation resin, in coating/ink formulations Raw material have good compatibility, have excellent yellowing resistance energy, can effectively improve adhesive force, hardness, the gloss of coating The richness of degree, solid content and film, is a kind of multifunctional coating/ink addition agent.However, traditional urea-isobutyl aldehyde-formolite Resin is the molten type hard resin of oil, is only used in solvent based coating and ink system.
It is polluted the environment using solvent based coating/ink, water paint/ink environment is friendly, coating/ink Water-borne modification Trend is increasingly apparent, becomes the main direction of development of current coating/ink.As a kind of important coating/ink used additives tree Rouge, the Water-borne modification of urea-isobutyl aldehyde-formolite resin are not only able to widen the application range of this resin, and to promotion coating/oil The Water-borne modification of ink has positive meaning, becomes the focus of people's research.
Summary of the invention
Based on this, it is necessary to which the problem of being directed to background technique provides a kind of self-emulsification aqueous urea-isobutyl of ionic Aldehyde-formaldehyde resin.
In addition, the present invention also provides a kind of preparation methods of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic.
A kind of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic, structural formula are as follows:
,
Wherein, R is, R1Selected from isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI), 4-4 '-two Methylenebis phenyl isocyanate, hexamethylene diisocyanate, benzene dimethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydrides At least one of diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, tetramethylxylylene diisocyanate;
A kind of preparation method of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic, comprising the following steps:
Urea-isobutyl aldehyde-formolite resin is added in reaction kettle, appropriate diluent, which is added, dissolves solid part sufficiently, then heats up To 65 ~ 75 DEG C;It is passed through nitrogen, suitable dibutyl tin dilaurate and polyisocyanates is added, reaction to NCO content is down to After 50% or less, it is added dihydromethyl propionic acid, reaction to NCO content is down to 0.1% hereinafter, be cooled to 55 ~ 65 DEG C, and triethylamine is added 25 ~ 35min of neutralization reaction is added deionized water high-speed stirred and emulsifies 50 ~ 70 minutes, it is self-emulsification aqueous that ionic is obtained by filtration Urea-isobutyl aldehyde-formolite resin.
The polyisocyanates is selected from isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI), 4-4 '-diphenyl methane two Isocyanates, hexamethylene diisocyanate, benzene dimethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates, At least one of cyclohexanedimethyleterephthalate diisocyanate, tetramethylxylylene diisocyanate;
The structural formula of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic is as follows:
,
Wherein, R is, (there are two branches for R group, how to connect on resin, please consider) R1Selected from different Your ketone of fluorine diisocyanate, toluene di-isocyanate(TDI), 4-4 '-methyl diphenylene diisocyanate, hexamethylene diisocyanate, Benzene dimethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates, cyclohexanedimethyleterephthalate diisocyanate, four At least one of xylene diisocyanate;
Solid urea-isobutylaldehyde-formaldehyde resin hydroxyl value is 40mgKOH/g ~ 80mgKOH/g in one of the embodiments,;
The diluent is selected from least one of acetone, propylene glycol monobutyl ether and n-butanol in one of the embodiments,;
The additive amount (mass parts) of the dibutyl tin dilaurate is polyisocyanates additive amount in one of the embodiments, The 0.02% ~ 0.20% of (mass parts);
In one of the embodiments, the mass parts ratio of the polyisocyanates and urea-isobutyl aldehyde-formolite resin be 8% ~ 30%;
The mass ratio of the material of the dihydromethyl propionic acid and polyisocyanates is 1:1 in one of the embodiments,;
In one of the embodiments, the solid content of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of the ionic be 30% ~ 60%。
Polyisocyanates, dihydromethyl propionic acid and triethylamine are linked into urea-isobutyl aldehyde-formolite tree by reaction by the present invention In fat chain, the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic is formd.
The above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin excellent storage stability of ionic, can be obtained the storage of high solids content The good lotion of stability is deposited, storage at normal temperature stability was more than 18 months;There is good compatibility with other water-base resin systems.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below to specific reality of the invention The mode of applying is described in detail.In the following description, numerous specific details are set forth in order to facilitate a full understanding of 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 where 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 of ionic, structural formula are as follows:
,
Wherein, R is, R1Selected from isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI), 4-4 '-two Methylenebis phenyl isocyanate, hexamethylene diisocyanate, benzene dimethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydrides At least one of diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, tetramethylxylylene diisocyanate;
The above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic, R base be with ionic hydrophilic group group (carboxylate), it Be by urea-isobutyl aldehyde-formolite resin hydroxyl in polyisocyanates-NCO group reacts, then again with dihydroxymethyl third Primary hydroxyl in acid reacts to obtain;It, can shape after high speed emulsifies to introduce hydrophilic radical in oligomer macromolecular chain At stable oil-in-water micelle volume, to reach the requirement of Water-borne modification, and excellent storage stability.
The above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic is prepared by following methods:
Urea-isobutyl aldehyde-formolite resin is added in reaction kettle, appropriate diluent, which is added, dissolves solid part sufficiently, then heats up To 65 ~ 75 DEG C;It is passed through nitrogen, suitable dibutyl tin dilaurate and polyisocyanates is added, reaction to NCO content is down to After 50% or less, it is added dihydromethyl propionic acid, reaction to NCO content is down to 0.1% hereinafter, be cooled to 55 ~ 65 DEG C, and triethylamine is added 25 ~ 35min of neutralization reaction is added deionized water high-speed stirred and emulsifies 50 ~ 70 minutes, it is self-emulsification aqueous that ionic is obtained by filtration Urea-isobutyl aldehyde-formolite resin.
Wherein, polyisocyanates is selected from isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI), 4-4 '-diphenyl methane Diisocyanate, hexamethylene diisocyanate, benzene dimethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates At least one of ester, cyclohexanedimethyleterephthalate diisocyanate, tetramethylxylylene diisocyanate;
Diluent is selected from least one of acetone, propylene glycol monobutyl ether and n-butanol;
Wherein, Solid urea-isobutylaldehyde-formaldehyde resin hydroxyl value is 40mgKOH/g ~ 80mgKOH/g;
The additive amount (mass parts) of dibutyl tin dilaurate is the 0.02% ~ 0.20% of polyisocyanates additive amount (mass parts);
The mass parts ratio of polyisocyanates and urea-isobutyl aldehyde-formolite resin is 8% ~ 30%;
The mass ratio of the material of dihydromethyl propionic acid and polyisocyanates is 1:1;
The solid content of the upper self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic is 30% ~ 60%;
The preparation method of the above-mentioned self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic is simple, the ionic self-emulsifying prepared Aqueous urea-isobutyl aldehyde-formolite resin excellent storage stability has good compatibility with other water-base resin systems.
The following are specific embodiments.
Embodiment 1
100kg urea-isobutyl aldehyde-formolite resin is added in reaction kettle, appropriate diluent, which is added, dissolves solid part sufficiently, then It is warming up to 70 DEG C;It is passed through nitrogen, 0.02kg dibutyl tin dilaurate and 12kg hexamethylene diisocyanate is added, reaction is extremely After NCO content is down to 50% or less, 9.5kg dihydromethyl propionic acid is added, the reaction was continued when being down to 0.1% or less to NCO content, drop 7.17kg triethylamine neutralization reaction 30min is added to 60 DEG C in temperature, and 193kg deionized water high-speed stirred is added and emulsifies 60 minutes, mistake Filter obtains the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic.
The performance of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic: through detecting, solid content 40%;Average grain Diameter is 125nm;Storage at normal temperature stability was more than 18 months;The compatibility of water-base resin system is as shown in table 1.
The compatibility of 1 water-base resin system of table
Resin types Centrifugal stability
Waterborne polyurethane resin 7
Aqueous epoxy resins 7
Water-based acrylic resin 6
Water-based epoxy acrylic resin 6
Aqueous melamine resin 7
* test and assessment method are with reference to 7.2 stability of emulsion in GB11543-2008
Embodiment 2
100kg urea-isobutyl aldehyde-formolite resin is added in reaction kettle, appropriate diluent, which is added, dissolves solid part sufficiently, then It is warming up to 70 DEG C;It is passed through nitrogen, 0.2kg dibutyl tin dilaurate and 15.76kg isoflurane chalcone diisocyanate, reaction is added After NCO content is down to 50% or less, 9.51kg dihydromethyl propionic acid is added, continues that the reaction was continued is down to 0.1% or less to NCO content When, 60 DEG C are cooled to, 7.17kg triethylamine neutralization reaction 30min is added, 310kg deionized water high-speed stirred is added and emulsifies 60 points The self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic is obtained by filtration in clock.
The performance of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic: through detecting, solid content 30%;Average grain Diameter is 110nm;Storage at normal temperature stability was more than 18 months;The compatibility of water-base resin system is as shown in table 2.
The compatibility of 2 water-base resin system of table
Resin types Centrifugal stability
Waterborne polyurethane resin 7
Aqueous epoxy resins 6
Water-based acrylic resin 6
Water-based epoxy acrylic resin 6
Aqueous melamine resin 6
* test and assessment method are with reference to 7.2 stability of emulsion in GB11543-2008
Embodiment 3
100kg urea-isobutyl aldehyde-formolite resin is added in reaction kettle, appropriate diluent, which is added, dissolves solid part sufficiently, then It is warming up to 70 DEG C;It is passed through nitrogen, 0.05kg dibutyl tin dilaurate and 9kg toluene di-isocyanate(TDI) is added, reaction to NCO contains After amount is down to 50% or less, drop 7kg dihydromethyl propionic acid is added, the reaction was continued when being reduced to 0.1% or less to NCO content, cooling 5.05kg triethylamine neutralization reaction 30min is added to 60 DEG C in temperature, and 148kg deionized water high-speed stirred is added and emulsifies 60 minutes, mistake Filter obtains the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic.
The performance of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic: through detecting, solid content 45%;Average grain Diameter is 86nm;Storage at normal temperature stability was more than 18 months;The compatibility of water-base resin system is as shown in table 3.
The compatibility of 3 water-base resin system of table
Resin types Centrifugal stability
Waterborne polyurethane resin 7
Aqueous epoxy resins 6
Water-based acrylic resin 7
Water-based epoxy acrylic resin 7
Aqueous melamine resin 7
* test and assessment method are with reference to 7.2 stability of emulsion in GB11543-2008
Embodiment 4
100kg urea-isobutyl aldehyde-formolite resin is added in reaction kettle, 20kg propylene glycol monobutyl ether, which is added, keeps solid part sufficiently molten Solution, then heats to 70 DEG C;It is passed through nitrogen, 0.04kg dibutyl tin dilaurate and 8kg 4-4 '-diphenyl methane two is added After reaction is down to 50% or less to NCO content, 12.8kg dihydromethyl propionic acid is added, the reaction was continued to NCO content in isocyanates When being reduced to 0.1% or less, 60 DEG C are cooled to, 9.6kg triethylamine neutralization reaction 30min is added, it is high that 242kg deionized water is added The self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic is obtained by filtration in fast stirring and emulsifying 60 minutes.
The performance of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic: through detecting, solid content 35%;Average grain Diameter is 104nm;Storage at normal temperature stability was more than 18 months;The compatibility of water-base resin system is as shown in table 4.
The compatibility of 4 water-base resin system of table
Resin types Centrifugal stability
Waterborne polyurethane resin 6
Aqueous epoxy resins 6
Water-based acrylic resin 7
Water-based epoxy acrylic resin 7
Aqueous melamine resin 7
* test and assessment method are with reference to 7.2 stability of emulsion in GB11543-2008
Embodiment 5
100kg urea-isobutyl aldehyde-formolite resin is added in reaction kettle, 25kg n-butanol, which is added, dissolves solid part sufficiently, then It is warming up to 70 DEG C;It is passed through nitrogen, 0.17kg dibutyl tin dilaurate and 9kg tetramethylxylene diisocyanate is added After reaction is down to 50% or less to NCO content, 27kg dihydromethyl propionic acid is added in ester, continues that the reaction was continued is down to NCO content When 0.1% or less, 60 DEG C are cooled to, 20.35kg triethylamine neutralization reaction 30min is added, 156kg deionized water high-speed stirring is added Emulsification 60 minutes is mixed, the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic is obtained by filtration.
The performance of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic: through detecting, solid content 50%;Average grain Diameter is 100nm;Storage at normal temperature stability was more than 18 months;The compatibility of water-base resin system is as shown in table 5.
The compatibility of 5 water-base resin system of table
Resin types Centrifugal stability
Waterborne polyurethane resin 7
Aqueous epoxy resins 6
Water-based acrylic resin 6
Water-based epoxy acrylic resin 6
Aqueous melamine resin 7
* test and assessment method are with reference to 7.2 stability of emulsion in GB11543-2008
Embodiment 6
100kg urea-isobutyl aldehyde-formolite resin is added in reaction kettle, 25kg n-butanol, which is added, dissolves solid part sufficiently, then It is warming up to 70 DEG C;It is passed through nitrogen, 0.17kg dibutyl tin dilaurate and 9kg tetramethylxylene diisocyanate is added After reaction is down to 50% or less to NCO content, 27kg dihydromethyl propionic acid is added in ester, continues that the reaction was continued is down to NCO content When 0.1% or less, 60 DEG C are cooled to, 20.35kg triethylamine neutralization reaction 30min is added, 156kg deionized water high-speed stirring is added Emulsification 60 minutes is mixed, the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic is obtained by filtration.
The performance of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic: through detecting, solid content 50%;Average grain Diameter is 100nm;Storage at normal temperature stability was more than 18 months;The compatibility of water-base resin system is as shown in table 5.
The compatibility of 5 water-base resin system of table
Resin types Centrifugal stability
Waterborne polyurethane resin 7
Aqueous epoxy resins 6
Water-based acrylic resin 6
Water-based epoxy acrylic resin 6
Aqueous melamine resin 7
* test and assessment method are with reference to 7.2 stability of emulsion in GB11543-2008
(embodiment of one solid content 60% of supplement).
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (6)

1. a kind of self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic, structural formula are as follows:
,
Wherein, R is, R1Selected from isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI), 4-4 '-two Methylenebis phenyl isocyanate, hexamethylene diisocyanate, benzene dimethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydrides At least one of diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, tetramethylxylylene diisocyanate.
2. the preparation method of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic described in claim 1, including following step It is rapid:
Urea-isobutyl aldehyde-formolite resin is added in reaction kettle, appropriate diluent, which is added, dissolves solid part sufficiently, then heats up To 65 ~ 75 DEG C;It is passed through nitrogen, suitable dibutyl tin dilaurate and polyisocyanates is added, reaction to NCO content is down to After 50% or less, it is added dihydromethyl propionic acid, reaction to NCO content is down to 0.1% hereinafter, be cooled to 55 ~ 65 DEG C, and triethylamine is added 25 ~ 35min of neutralization reaction is added deionized water high-speed stirred and emulsifies 50 ~ 70 minutes, it is self-emulsification aqueous that ionic is obtained by filtration Urea-isobutyl aldehyde-formolite resin;
The polyisocyanates is selected from isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI), two isocyanide of 4-4 '-diphenyl methane Acid esters, hexamethylene diisocyanate, benzene dimethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates, hexamethylene At least one of alkane dimethylene diisocyanate, tetramethylxylylene diisocyanate.
3. the preparation method of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic according to claim 2, feature The hydroxyl value for being the urea-isobutyl aldehyde-formolite resin is 40mgKOH/g ~ 80mgKOH/g.
4. the preparation method of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic according to claim 2 or 3, special Sign is that the diluent is selected from least one of acetone, propylene glycol monobutyl ether and n-butanol.
5. the preparation method of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic according to claim 2, feature Be the dibutyl tin dilaurate additive amount (mass parts) be polyisocyanates additive amount (mass parts) 0.02% ~ 0.20%。
6. the preparation method of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic according to claim 2, feature The mass parts ratio for being the polyisocyanates and urea-isobutyl aldehyde-formolite resin is 8% ~ 30%;
The preparation method of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic according to claim 2, feature exist In the mass ratio of the material of the dihydromethyl propionic acid and polyisocyanates is 1:1;
The preparation method of the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic according to claim 2, feature exist In the self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of the ionic solid content be 30% ~ 60%.
CN201910369457.2A 2019-05-06 2019-05-06 Self-emulsification aqueous urea-isobutyl aldehyde-formolite resin of ionic and preparation method thereof Pending CN110358034A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107090066A (en) * 2017-05-27 2017-08-25 岳阳市英泰材料科技有限公司 Self-emulsification aqueous urea isobutylaldehyde formaldehyde resin and preparation method thereof
CN108440732A (en) * 2018-03-13 2018-08-24 广东工业大学 Photo curable aqueous urea-isobutyl aldehyde-formolite resin of one kind and preparation method thereof
CN108440741A (en) * 2018-03-13 2018-08-24 广东工业大学 A kind of cationic photocurable urea-isobutyl aldehyde-formolite resin and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107090066A (en) * 2017-05-27 2017-08-25 岳阳市英泰材料科技有限公司 Self-emulsification aqueous urea isobutylaldehyde formaldehyde resin and preparation method thereof
CN108440732A (en) * 2018-03-13 2018-08-24 广东工业大学 Photo curable aqueous urea-isobutyl aldehyde-formolite resin of one kind and preparation method thereof
CN108440741A (en) * 2018-03-13 2018-08-24 广东工业大学 A kind of cationic photocurable urea-isobutyl aldehyde-formolite resin and preparation method thereof

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Application publication date: 20191022