CN109206591A - A kind of watersoluble closed type polyisocyanate crosslinking agent and preparation method thereof of high deblocking temperature - Google Patents
A kind of watersoluble closed type polyisocyanate crosslinking agent and preparation method thereof of high deblocking temperature Download PDFInfo
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- CN109206591A CN109206591A CN201710535295.6A CN201710535295A CN109206591A CN 109206591 A CN109206591 A CN 109206591A CN 201710535295 A CN201710535295 A CN 201710535295A CN 109206591 A CN109206591 A CN 109206591A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8041—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3271
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of watersoluble closed type polyisocyanate crosslinking agents and preparation method thereof of high deblocking temperature shown in following formula.Isocyanate trimer react with hydroxyethyl ethylenediamine under condition of ice bath and prepares branching type polymer backbone, then it is reacted to obtain the performed polymer of isocyanate groups sealing end with polymer backbone with aromatic diisocyanate, reactive isocyanate groups finally remaining with the closing of trimethyl hydroxyethylammonium ethylenediamine, and it is neutralized with organic acid, a kind of watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature is obtained, has higher application prospect in the fields such as cathode electrophoresis dope and baking vanish.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of poly- isocyanide of watersoluble closed type of high deblocking temperature
Acid esters crosslinking agent and preparation method thereof.
Background technique
Report is turned into the sealing end of isocyanates (NCO) base for the first time early in Petersen in 1949, then Wicks
(Blocked isocynate [J] .progress in organic coatings, 1975,3:73-99) is to isocyanates
The problems such as closing and its application method, has made detailed commentary.Compared with non-close type polyisocyanate crosslinking agent, enclosed type is poly-
The reactivity that isocyanate crosslinking solves isocyanate groups is big, very sensitive to moisture and mixed with resin
The problems such as validity period is short.Nowadays, as the laws and regulations for reducing coating VOC content etc. are increasingly sound, the Water-borne modification of coating
Development has become main trend, but compares solvent based coating, and there is water resistance, solvent resistance and resistance to height for water paint
The poor problem of temperature, so in order to improve its physical mechanical property, watersoluble closed type polyisocyanate crosslinking agent has become people
The emphasis of concern.
Under normal circumstances, the preparation method of watersoluble closed type polyisocyanate crosslinking agent is in high molecular main chain or branch
Ion or non-ionic hydrophilic radical, such as the Lv Yisheng (preparation of enclosed type aqueous polyisocyanate curing agent are introduced in structure
And its performance study [J] coatings industry, 2007,37 (12): 17-19) utilize isophorone diisocyanate (IPDI) tripolymer
It reacts to obtain isocyanate-terminated performed polymer with non-ionic hydrophilic chain extender glycol monoethyl ether, then with methyl ethyl ketoxime
Enclosed type aqueous polyisocyanate curing agent is prepared for for sealer, hence it is evident that improves the resistance to of aqueous polyurethane film after solidifying
Water, solvent resistant and mechanical property；T.Wang etc. with IPDI and triethanolamine (TEOA) for Material synthesis performed polymer, then respectively with
Butanol (BAO) and 3,5- dimethyl pyrazole (DMP) are that sealer obtains cation blocked type polyisocyanate crosslinking agent, work as use
The curing performance of resin can be better met when DMP is as sealer.But entire crosslinking is improved with the hydrophily of end group at present
The hydrophilic correlative study report of agent molecule is very few.
Summary of the invention
The present invention is from Molecular Design, first with the reactivity of isocyanate trimer and different active hydrogens
Difference prepares branching type polymer backbone, is then reacted, is obtained with polymer backbone with the aromatic diisocyanate of high activity
The performed polymer of isocyanate groups sealing end, while aromatic ring structure being introduced into crosslinking agent structure, it is conducive to improve cured later painting
The mechanical performance of layer, is eventually adding hydrophilic capping reagent, and neutralize with organic acid, realizes crosslinking agent using the high-hydrophilic of end group
Water dispersible, prepare it is a kind of it is high deblocking temperature watersoluble closed type polyisocyanate crosslinking agent, cathode electrophoresis dope with
And baking vanish etc. has higher application study to be worth.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature, has the following structure formula:
In formula:
R1=HCOO, CH3COO、HCOOCOO
A kind of watersoluble closed type polyisocyanate crosslinking agent and preparation method thereof of above-mentioned high deblocking temperature, it is characterised in that
Under nitrogen protection, stirring carries out whole process, and each component weighs addition reaction system according to the mass fraction, step 1, in ice bath item
Under part, 18.0~21.0 parts of organic solvents and 9.7~13.3 parts of isocyanate trimers are added in four-hole boiling flask；Step 2,
In 1.8~3.2 parts of organic solvents and 1.0~1.1 parts of hydroxyethyl ethylenediamine are added drop-wise in system in 0.1~0.5h, react
0.5~1.0h reaches theoretical value to NCO content；Step 3,2.0~4.0 parts of organic solvent and the two of 3.5~5.0 parts different is added
Cyanate, is warming up to 40~50 DEG C, and 1.0~1.5h of insulation reaction makes NCO content reach theoretical value；Step 4, in 0.2~0.5h
7.7~8.0 parts of trimethyl hydroxyethylammonium ethylenediamine is added, 2.0~3.0h of insulation reaction is cooled to room temperature；Step 5,4.4 are added
~9.0 parts of organic acid stirs 0.2~0.5h.
It is that organic solvent is a kind of in butanone, cyclohexanone or Isosorbide-5-Nitrae-dioxane in experimentation as improved.
It is that isocyanate trimer is hexamethylene diisocyanate trimer or different Fo Er in step 1 as improved
It is a kind of in ketone diisocyanate trimer.
It is that diisocyanate is toluene di-isocyanate(TDI) or methyl diphenylene diisocyanate in step 3 as improved
Middle one kind.
It is that organic acid is selected from formic acid, glacial acetic acid or oxalic acid in step 5 as improved.
Reaction equation of the present invention are as follows:
Beneficial effect
A kind of preparation method of the watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature of the present invention is in ice bath item
Isocyanate trimer and two amino in hydroxyethyl ethylenediamine are reacted under part, then recycle two isocyanide of aromatic series
The high reaction activity of acid esters reacts with remaining hydroxyl, forms the performed polymer of NCO sealing end, and hydrophily closing is then added
Agent trimethyl hydroxyethylammonium ethylenediamine, and neutralized with organic acid, obtain a kind of watersoluble closed type polyisocyanate of high deblocking temperature
Crosslinking agent, cathode electrophoresis dope and in terms of have broad application prospects.
Detailed description of the invention
Fig. 1 is a kind of infrared spectroscopy of the watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature.
Fig. 2 is the infrared light that a kind of watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature is honored as a queen through 180 DEG C of solutions
Spectrum.
Specific embodiment
Below with reference to the embodiment optimal technical scheme that the present invention will be described in detail.
Embodiment 1
It is whole to stir and carry out under nitrogen protection, it is step 1, under condition of ice bath, 21.0 parts of cyclohexanone and 12.9 parts are different
Isophorone diisocyanate tripolymer is added in four-hole boiling flask；Step 2, in 0.2h by 2.0 parts of cyclohexanone and 1.1 parts of hydroxyl
Ethylethylenediamine is added drop-wise in system, insulation reaction 0.5h；Step 3,3.0 parts of cyclohexanone is added and 3.5 parts of toluene two is different
Cyanate is warming up to 50 DEG C, continues insulation reaction 1.0h；Step 4,7.7 parts of trimethyl hydroxyethylammonium ethylenediamine is added in 0.3h,
Insulation reaction 3.0h, is cooled to room temperature；Step 5,5.7 parts of glacial acetic acid is added, stirs 0.2h, obtains a kind of high deblocking temperature
Watersoluble closed type polyisocyanate crosslinking agent.
1 gained crosslinking agent of embodiment, the room temperature storage time, solid content 50%, isocyanate content was more than 6 months
6.80%；FT-IR(KBr,cm-1): 3320 (N-H), 2930 (- CH3,-CH2), 1710 (C=O), 1540 (C-N), 1070 (C-
O-C)；Fig. 1 is a kind of infrared spectroscopy of the watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature obtained；Fig. 2 is one
The infrared spectroscopy that the watersoluble closed type polyisocyanate crosslinking agent of the high deblocking temperature of kind is honored as a queen through 180 DEG C of solutions.
Embodiment 2
It is whole that stirring carries out under nitrogen protection, step 1, under condition of ice bath, by 19.0 parts of Isosorbide-5-Nitrae-dioxane and
10.1 parts of hexamethylene diisocyanate trimers are added in four-hole boiling flask；Step 2, in 0.3h by 2.0 parts of Isosorbide-5-Nitrae-dioxies
Six rings and 1.1 parts of hydroxyethyl ethylenediamine are added drop-wise in system, insulation reaction 1.0h；Step 3,3.0 parts of Isosorbide-5-Nitrae-dioxy is added
Six rings and 5.0 parts of methyl diphenylene diisocyanate are warming up to 50 DEG C, continue insulation reaction 1.0h；Step 4, in 0.5h plus
Enter 8.0 parts of trimethyl hydroxyethylammonium ethylenediamine, insulation reaction 3.0h is cooled to room temperature；Step 5,9.0 parts of oxalic acid is added, stirs
0.3h is mixed, a kind of watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature is obtained.
2 gained crosslinking agent of embodiment, the room temperature storage time, solid content 50%, isocyanate content was more than 6 months
6.96%.
Claims (6)
1. a kind of watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature, it is characterised in that it has the following structure formula:
In formula:
R1=HCOO, CH3COO、HCOOCOO。
2. based on it is described in claim 1 it is a kind of it is high deblocking temperature watersoluble closed type polyisocyanate crosslinking agent and its preparation side
Method, it is characterised in that it is whole that stirring carries out, and each component weighs addition reaction system according to the mass fraction under nitrogen protection,
Step 1, under condition of ice bath, 18.0~21.0 parts of organic solvents and 9.7~13.3 parts of isocyanate trimers are added to four
In mouth flask；Step 2, in the hydroxyethyl ethylenediamine of 1.8~3.2 parts of organic solvents and 1.0~1.1 parts is dripped in 0.1~0.5h
It is added in system, 0.5~1.0h of reaction to NCO content reaches theoretical value；Step 3, be added 2.0~4.0 parts organic solvent and
3.5~5.0 parts of diisocyanate, is warming up to 40~50 DEG C, and 1.0~1.5h of insulation reaction makes NCO content reach theoretical value；
Step 4,7.7~8.0 parts of trimethyl hydroxyethylammonium ethylenediamine is added in 0.2~0.5h, 2.0~3.0h of insulation reaction is cooled to
Room temperature；Step 5,4.4~9.0 parts of organic acid is added, stirs 0.2~0.5h.
3. a kind of preparation side of the watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature according to claim 2
Method, which is characterized in that organic solvent is a kind of in butanone, cyclohexanone or Isosorbide-5-Nitrae-dioxane in experimentation.
4. a kind of preparation side of the watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature according to claim 2
Method, which is characterized in that isocyanate trimer is two isocyanide of hexamethylene diisocyanate trimer or isophorone in step 1
It is a kind of in acid esters tripolymer.
5. a kind of preparation side of the watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature according to claim 2
Method, which is characterized in that diisocyanate is a kind of in toluene di-isocyanate(TDI) or methyl diphenylene diisocyanate in step 3.
6. a kind of preparation side of the watersoluble closed type polyisocyanate crosslinking agent of high deblocking temperature according to claim 2
Method, which is characterized in that organic acid is selected from formic acid, glacial acetic acid or oxalic acid in step 5.
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| CN201710535295.6A CN109206591B (en) | 2017-07-06 | 2017-07-06 | Water-based blocked polyisocyanate crosslinking agent and preparation method thereof |
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| CN201710535295.6A CN109206591B (en) | 2017-07-06 | 2017-07-06 | Water-based blocked polyisocyanate crosslinking agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563561A (en) * | 2021-08-10 | 2021-10-29 | 广东科力德新材料有限公司 | Resin for cathode electrophoretic coating color paste, preparation method of resin and coating color paste |
Citations (4)
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|---|---|---|---|---|
| US4540765A (en) * | 1983-05-27 | 1985-09-10 | Bayer Aktiengesellschaft | Polyurethanes containing perfluoroalkyl groups and a process for their production |
| CN1572811A (en) * | 2003-06-23 | 2005-02-02 | 拜尔材料科学股份公司 | Blocked polyisocyanates |
| CN1813018A (en) * | 2003-06-27 | 2006-08-02 | 拜尔材料科学股份公司 | Blocked polyisocyanates |
| CN104448234A (en) * | 2014-12-08 | 2015-03-25 | 盐城工学院 | Waterborne blocked hyperbranched polyisocyanate cross-linking agent and preparation method thereof |
-
2017
- 2017-07-06 CN CN201710535295.6A patent/CN109206591B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540765A (en) * | 1983-05-27 | 1985-09-10 | Bayer Aktiengesellschaft | Polyurethanes containing perfluoroalkyl groups and a process for their production |
| CN1572811A (en) * | 2003-06-23 | 2005-02-02 | 拜尔材料科学股份公司 | Blocked polyisocyanates |
| CN1813018A (en) * | 2003-06-27 | 2006-08-02 | 拜尔材料科学股份公司 | Blocked polyisocyanates |
| CN104448234A (en) * | 2014-12-08 | 2015-03-25 | 盐城工学院 | Waterborne blocked hyperbranched polyisocyanate cross-linking agent and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| STEFAN BODE,等: "Blocked isocyanates: an efficient tool for post-polymerization modification of polymers", 《POLYMER CHEMISTRY》 * |
| 从建华，等: "聚氨基醇胺类染色织物耐洗色牢度提升剂的合成及应用", 《印染助剂》 * |
| 孙祥，等: "阳离子水性封闭型聚异氰酸酯交联剂的制备与性能", 《涂料工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113563561A (en) * | 2021-08-10 | 2021-10-29 | 广东科力德新材料有限公司 | Resin for cathode electrophoretic coating color paste, preparation method of resin and coating color paste |
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