CN102093696B - Ketone-group-containing aqueous polyurethane resin capable of being cured at room temperature and preparation method thereof - Google Patents
Ketone-group-containing aqueous polyurethane resin capable of being cured at room temperature and preparation method thereof Download PDFInfo
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- CN102093696B CN102093696B CN2010105864825A CN201010586482A CN102093696B CN 102093696 B CN102093696 B CN 102093696B CN 2010105864825 A CN2010105864825 A CN 2010105864825A CN 201010586482 A CN201010586482 A CN 201010586482A CN 102093696 B CN102093696 B CN 102093696B
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Abstract
The invention discloses a ketone-group-containing aqueous polyurethane resin and a preparation method thereof. The ketone-group-containing aqueous polyurethane resin consists of the following components in part by weight: 55 to 80 parts of diisocyanate, 105 to 150 parts of polyester diol, 18 to 45 parts of hydroxyketone, 15 to 20 parts of dimethylolpropionic acid, 10 to 15 parts of triethylamine, 40 to 55 parts of acetone, 18 to 26 parts of adipic dihydrazide and 600 to 900 parts of deionized water. The preparation method comprises the steps of the preparation of a resin, the dispersion and emulsification of the resin in the deionized water, and the removal of the acetone in an aqueous resin. In the ketone-group-containing aqueous polyurethane resin, the crosslinking and curing of ketone groups (keto carbonyl groups) and the adipic dihydrazide can be performed when water is volatized and the resin forms film at room temperature; and a cured substance has good water resistance and alcohol resistance, and higher hardness. The water resistance and the alcohol resistance of the cured substance reach HG/T3828-2006 standard for 'Aqueous Coatings for Indoor Woodenware'. The hardness (scratch) reaches 2H.
Description
Technical field
The present invention relates to a kind of waterborne polyurethane resin and preparation method thereof, relate to a kind of waterborne polyurethane resin and preparation method thereof of ketone group containing of self-vulcanizing in particular.
Background technology
Waterborne polyurethane resin is because of using no or little the processing that desolventizes of organic solvent and necessity in preparation and use, organic volatile content is very low in the product, have fewer environmental impacts, thereby development very rapidly.But compare with solvent type polyurethane resin, conventional waterborne polyurethane resin also exists water-fast, anti-solvent and chemical resistance relatively poor; Shortcomings such as hardness is lower.This mainly is because waterborne polyurethane resin contains due to hydrophilic radical, the solvophilic property group.Though can pass through chain extension, propenoate, epoxy resin, organosilicon are compound etc., and method is carried out modification to aqueous polyurethane, often makes polyurethane structural complicated, and dispersiveness and stability in water are affected.And crosslinked be a kind of relatively effective means that improves the waterborne polyurethane resin performance, wherein room temperature (normal temperature) single component crosslinked aqueous polyurethane resin is praised highly because of easy to use obtaining.So-called normal temperature single component cross-linking system is that the material that forms crosslinking reaction is packaged among the individual system, and these materials that play crosslinking reaction do not react when the dispersion-s storage at normal temperature, and form crosslinked at normal temperature film forming afterreaction.The normal temperature single-component system is a kind of good cross-linking system, and it can realize single-component package, and is extremely easy to use, crosslinkedly can carry out at normal temperatures again, and it is little to consume energy.Yet, realize that this individual system is but very difficult technically, because often need through polystep reaction.Like the alkoxy silane cross linked system of steric hindrance type, the addition-crosslinked system of aldehyde-amine, carbonyl amine cross-linking system or the like, react that controlling factor is many at most, limitation is big, thereby effect is general.And the present invention provides a kind of through simple reaction can be connected to ketone group and obtains the ketone group containing waterborne polyurethane resin on the polyurethane chain once the step; And at room temperature carry out ketone group (ketone carbonyl) and the hydrazide group crosslinking curing that is contained in the AH in the resin in the water volatilization process, can obtain bigger ketone group content through formulating of recipe and realize bigger degree of crosslinking.
Summary of the invention
First technical problem to be solved by this invention provide a kind of through simple reaction with regard to getable ketone group containing waterborne polyurethane resin; This ketone group containing waterborne polyurethane resin contains the linking agent AH and forms the single component form; And at room temperature carry out the crosslinking curing of ketone group (ketone carbonyl) and AH in the water volatilization process, and cured article has good water tolerance, alcohol resistance and higher hardness.
Second technical problem to be solved by this invention provides the preparation method of the waterborne polyurethane resin of above-mentioned ketone group containing.
The technical scheme that the present invention adopted
A kind of ketone group containing waterborne polyurethane resin of ambient temperature curable, its raw material is formed and each proportion of raw materials is calculated as follows by weight:
55～80 parts of vulcabond
105～150 parts of polyester diol
18～45 parts of hydroxyketones
15～20 parts of dimethylol propionic acids
10～15 parts of triethylamines
40～55 parts in acetone
18～26 parts of AHs
600～900 parts of deionized waters
Said vulcabond is one or more the mixture in tolylene diisocyanate, diphenylmethanediisocyanate, the hexamethylene diisocyanate.
Said polyester diol is one or more the mixture in polycarbonate diol, polycaprolactone glycol, the polytetramethylene ether diol.
Described hydroxyketone is one or more the mixture in hydroxy acetophenone, hydroxypropiophenonepreparation, the oxobutanol.
The preparation method of the ketone group containing waterborne polyurethane resin of above-mentioned a kind of ambient temperature curable the steps include:
(1), with polyester diol at 110-120 ℃, stir dehydration 1-2 hour under the 700-750mmHg vacuum tightness; Logical then nitrogen adds dimethylol propionic acid down, mixes;
After be cooled to 30-50 ℃, add vulcabond, constant temperature 75-85 ℃ of reaction 2-3 hour;
Adding hydroxyketone mixing back again reacted 1-2 hour down for 75-85 ℃;
And then being cooled to 50 ℃ of adding triethylamines, 50-60 ℃ of following insulation added acetone after 40-60 minute, was cooled to below 10 ℃, got the base polyurethane prepolymer for use as of ketone group containing;
(2), the base polyurethane prepolymer for use as of step (1) gained ketone group containing was poured in the deionized water that has dissolved AH dispersion and emulsion 20-40 minute, the polyurethane resin water/acetone dispersion-s of ketone group containing;
(3), the polyurethane resin water/acetone dispersion-s underpressure distillation of step (2) gained ketone group containing is removed acetone, promptly got the waterborne polyurethane resin of ketone group containing.
Beneficial effect of the present invention
The present invention just can obtain the waterborne polyurethane resin of ketone group containing through simple reaction, and this resin contains the linking agent AH, when the water in the resin does not volatilize, does not produce the reaction of ketone group (ketone carbonyl) and AH, so this resin stable storing.At room temperature, then can carry out the crosslinking curing of ketone group (ketone carbonyl) and AH during the resin film forming, and cured article has good water tolerance, alcohol resistance and higher hardness when the water volatilization.Water-fast, alcohol resistance through detecting this resin cured matter reach HG/T3828-2006 " indoor water-borne wood coating " standard.Hardness (scratch) reaches 2H.This resin property is excellent, and is easy to use, need not during curing to add any catalyzer or heat.
Embodiment
Further specify the present invention below in conjunction with concrete embodiment and how to realize, but do not limit the present invention.
Embodiment 1
105 parts of polycaprolactone glycols at 110 ℃, are stirred dehydration 1 hour under the 750mmHg vacuum tightness; Logical then nitrogen adds 15 parts of dimethylol propionic acids down, mixes; Be cooled to 50 ℃, add 55 parts of tolylene diisocyanates, 75 ℃ of reactions of constant temperature 3 hours; Add 18 parts of oxobutanols and mix back 75 ℃ of following reactions 1 hour; Be cooled to 50 ℃ then and add 10 parts of triethylamines, 50 ℃ are incubated 60 minutes down; Add 40 parts of acetone, be cooled to below 10 ℃.Above system poured in 600 parts of deionized waters that dissolved 18 parts of AHs into dispersion and emulsion 20 minutes; It is 500mmHg that above system is decompressed to vacuum tightness, and the liquid temperature is 45 ℃, and acetone is removed in distillation, promptly gets the waterborne polyurethane resin of ketone group containing.
Embodiment 2
150 parts of polycarbonate diols at 120 ℃, are stirred dehydration 2 hours under the 700mmHg vacuum tightness; Logical then nitrogen adds 20 parts of dimethylol propionic acids down, mixes; Be cooled to 30 ℃, add 80 parts of hexamethylene diisocyanates, 85 ℃ of reactions of constant temperature 2 hours; Add 45 parts of hydroxy acetophenones and mix back 85 ℃ of following reactions 2 hours; Be cooled to 50 ℃ then and add 15 parts of triethylamines, 60 ℃ are incubated 40 minutes down; Add 55 parts of acetone, be cooled to below 10 ℃.Above system poured in 900 parts of deionized waters that dissolved 26 parts of AHs into dispersion and emulsion 40 minutes; It is 500mmHg that above system is decompressed to vacuum tightness, and the liquid temperature is 45 ℃, and acetone is removed in distillation, promptly gets the waterborne polyurethane resin of ketone group containing.
Embodiment 3
With 80 parts of polycarbonate diols, 45 parts of polytetramethylene ether diols stir dehydration 1.5 hours at 115 ℃ under the 740mmHg vacuum tightness; Logical then nitrogen adds 17 parts of dimethylol propionic acids down, mixes; Be cooled to 45 ℃, add 10 parts of diphenylmethanediisocyanates and 60 parts of tolylene diisocyanates, 80 ℃ of reactions of constant temperature 2.5 hours; Add 4 parts of hydroxypropiophenonepreparations and 20 parts of oxobutanols and mix back 82 ℃ of reactions 1.5 hours down; Be cooled to 50 ℃ then and add 12 parts of triethylamines, 56 ℃ are incubated 50 minutes down; Add 50 parts of acetone, be cooled to below 10 ℃.Above system poured in 800 parts of deionized waters that dissolved 22 parts of AHs into dispersion and emulsion 34 minutes; It is 500mmHg that above system is decompressed to vacuum tightness, and the liquid temperature is 45 ℃, and acetone is removed in distillation, promptly gets the waterborne polyurethane resin of ketone group containing.
The above content is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (6)
1. the ketone group containing waterborne polyurethane resin of an ambient temperature curable is characterized in that its raw material is formed and each raw materials in parts by weight is calculated as follows:
105～150 parts of polyester diol
15～20 parts of dimethylol propionic acids
55～80 parts of vulcabond
18～45 parts of hydroxyketones
10～15 parts of triethylamines
40～55 parts in acetone
18～26 parts of AHs
600～900 parts of deionized waters
Wherein said vulcabond is one or more the mixture in tolylene diisocyanate, diphenylmethanediisocyanate, the hexamethylene diisocyanate;
Said polyester diol is one or more the mixture in polycarbonate diol, polycaprolactone glycol, the polytetramethylene ether diol;
Described hydroxyketone is one or more the mixture in hydroxy acetophenone, hydroxypropiophenonepreparation, the oxobutanol.
2. the ketone group containing waterborne polyurethane resin of a kind of ambient temperature curable as claimed in claim 1 is characterized in that its raw material is formed and each raw materials in parts by weight is calculated as follows:
105 parts of polyester diol
15 parts of dimethylol propionic acids
55 parts of vulcabond
18 parts of hydroxyketones
10 parts of triethylamines
40 parts in acetone
18 parts of AHs
600 parts of deionized waters
Wherein said vulcabond is a tolylene diisocyanate;
Said polyester diol is a polycaprolactone glycol;
Described hydroxyketone is an oxobutanol.
3. the ketone group containing waterborne polyurethane resin of a kind of ambient temperature curable as claimed in claim 1 is characterized in that its raw material is formed and each raw materials in parts by weight is calculated as follows:
150 parts of polyester diol
20 parts of dimethylol propionic acids
80 parts of vulcabond
45 parts of hydroxyketones
15 parts of triethylamines
55 parts in acetone
26 parts of AHs
900 parts of deionized waters
Said vulcabond is a hexamethylene diisocyanate;
Said polyester diol is a polycarbonate diol;
Described hydroxyketone is a hydroxy acetophenone.
4. the ketone group containing waterborne polyurethane resin of a kind of ambient temperature curable as claimed in claim 1 is characterized in that its raw material is formed and each raw materials in parts by weight is calculated as follows:
125 parts of polyester diol
17 parts of dimethylol propionic acids
70 parts of vulcabond
24 parts of hydroxyketones
12 parts of triethylamines
50 parts in acetone
22 parts of AHs
800 parts of deionized waters
Wherein said vulcabond is the mixture of tolylene diisocyanate and diphenylmethanediisocyanate;
Said polyester diol is the mixture of polycarbonate diol and polytetramethylene ether diol;
Described hydroxyketone is the mixture of hydroxypropiophenonepreparation and oxobutanol.
5. according to the preparation method of the ketone group containing waterborne polyurethane resin of claim 1,2,3 or 4 arbitrary described a kind of ambient temperature curables, it is characterized in that comprising the steps:
(1), with polyester diol at 110-120 ℃, stir dehydration 1-2 hour under the 700-750mmHg vacuum tightness; Logical then nitrogen adds dimethylol propionic acid down, mixes;
After be cooled to 30-50 ℃, add vulcabond, constant temperature 75-85 ℃ of reaction 2-3 hour;
Adding hydroxyketone mixing back again reacted 1-2 hour down for 75-85 ℃;
And then being cooled to 50 ℃ of adding triethylamines, 50-60 ℃ of following insulation added acetone after 40-60 minute, was cooled to below 10 ℃, got the base polyurethane prepolymer for use as of ketone group containing;
(2), the base polyurethane prepolymer for use as of step (1) gained ketone group containing was poured in the deionized water that has dissolved AH dispersion and emulsion 20-40 minute, the polyurethane resin water/acetone dispersion-s of ketone group containing;
(3), the polyurethane resin water/acetone dispersion-s underpressure distillation of step (2) gained ketone group containing is removed acetone, promptly got the waterborne polyurethane resin of ketone group containing.
6. the preparation method of the ketone group containing waterborne polyurethane resin of a kind of ambient temperature curable as claimed in claim 5, it is 500mmHg that the underpressure distillation condition in the step (3) of it is characterized in that is promptly controlled vacuum tightness, the liquid temperature is 45 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2010105864825A CN102093696B (en) | 2010-12-14 | 2010-12-14 | Ketone-group-containing aqueous polyurethane resin capable of being cured at room temperature and preparation method thereof |
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| CN2010105864825A CN102093696B (en) | 2010-12-14 | 2010-12-14 | Ketone-group-containing aqueous polyurethane resin capable of being cured at room temperature and preparation method thereof |
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| CN102093696B true CN102093696B (en) | 2012-08-22 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336886A (en) * | 2011-07-05 | 2012-02-01 | 嵊州市科鼎聚氨酯制品厂 | Polyurethane for transmission friction wheels and preparation method thereof |
| CN102492281B (en) * | 2011-11-29 | 2013-06-19 | 上海应用技术学院 | Single-component water-based polyurethane/acrylate composite resin capable of being cured at room temperature and preparation method thereof |
| CN104829811B (en) * | 2015-04-30 | 2017-09-01 | 安吉县广泰化工纸业有限公司 | A kind of preparation technology of waterborne polyurethane resin |
| CN113817133A (en) * | 2021-09-18 | 2021-12-21 | 湖南松井新材料股份有限公司 | Room-temperature self-crosslinking water-based nonionic polyurethane dispersion and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1805990A (en) * | 2003-06-13 | 2006-07-19 | 氰特特种表面技术奥地利有限公司 | Self-crosslinking aqueous polyurethane dispersions |
| CN101265318A (en) * | 2008-05-15 | 2008-09-17 | 海聚高分子材料科技（广州）有限公司 | High-performance water-based polyurethane dispersoid and application thereof |
| CN101659809A (en) * | 2009-01-14 | 2010-03-03 | 佛山市顺德区德美油墨化工有限公司 | Water-based UV black ink with super-high solid content and preparation method thereof |
| CN101659785A (en) * | 2009-01-14 | 2010-03-03 | 佛山市顺德区德美油墨化工有限公司 | High-functionality water-based UV resin composition with 100% solid content and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1805990A (en) * | 2003-06-13 | 2006-07-19 | 氰特特种表面技术奥地利有限公司 | Self-crosslinking aqueous polyurethane dispersions |
| CN101265318A (en) * | 2008-05-15 | 2008-09-17 | 海聚高分子材料科技（广州）有限公司 | High-performance water-based polyurethane dispersoid and application thereof |
| CN101659809A (en) * | 2009-01-14 | 2010-03-03 | 佛山市顺德区德美油墨化工有限公司 | Water-based UV black ink with super-high solid content and preparation method thereof |
| CN101659785A (en) * | 2009-01-14 | 2010-03-03 | 佛山市顺德区德美油墨化工有限公司 | High-functionality water-based UV resin composition with 100% solid content and preparation method thereof |
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Owner name: JINJIANG DEFU RESIN CO., LTD. Free format text: FORMER OWNER: SHANGHAI INSTITUTE OF TECHNOLOGY Effective date: 20130428 |
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Effective date of registration: 20130428 Address after: 362200, No. 22 community, Hongshan Comprehensive Development Zone, Qingyang Town, Jinjiang, Fujian Patentee after: Jinjiang Defu Resin Co., Ltd. Address before: 200235 Xuhui District, Caobao Road, No. 120, Patentee before: Shanghai Institute of Technology |
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