CN101948410A - Phenol blocking isophorone diisocyanate monomer adduct and preparation method thereof - Google Patents
Phenol blocking isophorone diisocyanate monomer adduct and preparation method thereof Download PDFInfo
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- CN101948410A CN101948410A CN2010102427770A CN201010242777A CN101948410A CN 101948410 A CN101948410 A CN 101948410A CN 2010102427770 A CN2010102427770 A CN 2010102427770A CN 201010242777 A CN201010242777 A CN 201010242777A CN 101948410 A CN101948410 A CN 101948410A
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- isophorone diisocyanate
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Abstract
The invention relates to a phenol blocking isophorone diisocyanate monomer adduct and a preparation method thereof. The phenol sealed isophorone diisocyanate monomer adduct comprises the following materials in parts by weight: 2-15 parts of phenol, 5-20 parts of isophorone diisocyanate and 60-100 parts of ethyl acetate or xylene solvent. The blocking isophorone diisocyanate monomer adduct is used for a modified component of water paint, can obviously increase the rheology and the storage stability of the water paint and prolongs a quality guarantee period.
Description
Technical field
The present invention relates to paint field, be specifically related to phenol sealing isophorone diisocyanate monomer affixture and preparation method thereof.
Background technology
Urethane is one of six big synthetic materialss of excellent property, and as the main raw material of synthesis of polyurethane, isocyanate-monomer is poisonous, contains isocyanate groups (NCO, the structural formula-N=C=O), thereby chemical property is very active of height unsaturated double-bond.-N=C=O and nucleophilic reagent have high reaction activity and high, and be very active under this system normal temperature, can't exist with the single component form, has to the component that reacts to each other easily separately, and remix together during use; Isophorone diisocyanate monomer quality guaranteed period weak point is easy to autohemagglutination and forms dimer, tripolymer, polymer, thereby influences its activity simultaneously; Very responsive to raw material such as solvent, resin and on-the-spot airborne moisture before polyurethane coating solidifies, (NCO) group can generate the ureas material with the active H reaction in the water, brings a lot of difficulties for the application of polyurethane coating in the isocyanic ester.We thirst for utilizing the height reactive behavior of isocyanic ester very much; The poison, the secondary negative influence that bring because of its activity before wishing again simultaneously to use are temporarily restrained.This just needs to seek a kind of method, allow in the isocyanic ester (NCO) group temporarily loses activity, can normally preserve at normal temperatures, and needn't worry that it is rotten, add and to mix with the water and other raw materials that contain active H man-hour, and needn't worry that it can react, the coating of making can prolonged preservation.This just needs a kind of novel block isocyanic ester of development research, and the active group of isocyanic ester (NCO) is closed, loses activity under normal temperature condition, stoped the effect to it of water or other active groups.This isocyanic ester that is closed is can be under normal temperature and water and various ambient containing hydrogen condition processed and preserve, when needs use this isocyanic ester active, apply certain condition (heating, catalyzer), (chemical bond NCO) will rupture for end-capping reagent and active group, discharge (NCO) active group, thereby the activity of recovery isocyanic ester once more.
Summary of the invention
The objective of the invention is for solve in the polyurethane coating monomer isophorone diisocyanate reactive behavior big, to problems such as moisture-sensitive, phenol sealing isophorone diisocyanate monomer affixture and preparation method thereof is provided.
The object of the present invention is achieved like this:
A kind of phenol sealing isophorone diisocyanate monomer affixture, it is characterized in that: the feedstock production that comprises following parts by weight forms:
Phenol 2-15 part
Isophorone diisocyanate 5-20 part
Ethyl acetate or xylene solvent 60-100 part.
A kind of preparation method of phenol sealing isophorone diisocyanate monomer affixture is characterized in that: comprise following steps:
(1) takes by weighing 2-15 part end-capping reagent phenol and be dissolved in 20-40 part ethyl acetate or the xylene solvent, make end-capping reagent solution;
(2) 5-20 part isophorone diisocyanate monomer is dissolved in 40-60 part ethyl acetate or the xylene solvent, makes monomer solution;
(3) under 50-120 ℃ of agitation condition, monomer solution joined in the end-capping reagent solution react, obtain insoluble phenol sealing isophorone diisocyanate monomer affixture.
Also comprise following steps afterwards in above-mentioned steps (3): the insoluble affixture of gained is separated from solvent.
The insoluble affixture of gained is also comprised following steps after separating from solvent: the affixture of separating is dried under 0.05-0.09MPa vacuum, 30-150 ℃ condition, dispel residual solvent, obtain powdery phenol sealing isophorone diisocyanate monomer affixture.
This preparation method adopts phenol closed isocyanic ester monomer under certain condition, thus obtain at normal temperatures can stable existence closure isocyanate-monomer affixture.
Compared with prior art, the present invention has following outstanding advantage: (1) adopts end-capping reagent phenol directly the isophorone diisocyanate monomer to be carried out end-blocking, need not to make earlier base polyurethane prepolymer for use as, carries out end-blocking again, and need not catalyzer can make, and technology is simple.(2) reaction is addition reaction, one-step synthesis, and no coupling product both had been convenient to reclaim, and can not cause environmental pollution because of the recovery problem that by product produces again.(3) because the gained affixture is highly stable, can not only save and not degenerate in wet environment, the coating property of making is stable, even can directly directly add in water-borne coatings.(4) the used end-capping reagent of the present invention is a phenol, has at aspects such as synthon, synthetic rubber, plastics, dyestuff and coating widely to use, and separating is honored as a queen still can play a role in component, the impurity of having avoided the use because of end-capping reagent to bring to component.(5) this phenol sealing isophorone diisocyanate monomer affixture can be widely used in fields such as material of construction, transportation equipment, hardware, automotive industry, machinery, telecommunication equipment, pipeline industry, coating and printing ink laking agent.
The end-capping reagent phenol that the present invention uses has widely at aspects such as synthon, synthetic rubber, plastics, dyestuff and coating and to use, and separating is honored as a queen still can play a role in component, the impurity of having avoided the use because of end-capping reagent to bring to component.Closure isocyanate-monomer affixture of the present invention is used for the altered contents of water-borne coatings, can obviously improve rheological, the stability in storage of water-borne coatings, extends the shelf life.
Embodiment
A kind of phenol sealing isophorone diisocyanate monomer affixture, it is characterized in that: the feedstock production that comprises following parts by weight forms: phenol 2-15 part, isophorone diisocyanate 5-20 part, ethyl acetate or xylene solvent 60-100 part.
A kind of preparation method of phenol sealing isophorone diisocyanate monomer affixture is characterized in that: comprise following steps: take by weighing 2-15 part end-capping reagent phenol and be dissolved in 20-40 part ethyl acetate or the xylene solvent, make end-capping reagent solution; 5-20 part isophorone diisocyanate monomer is dissolved in 40-60 part ethyl acetate or the xylene solvent, makes monomer solution; Under 50-120 ℃ of agitation condition, monomer solution dropwise added in the end-capping reagent solution react, obtain insoluble phenol sealing isophorone diisocyanate monomer affixture.
The insoluble affixture of gained is separated from solvent.The insoluble affixture of gained is also comprised following steps after separating from solvent: the affixture of separating is dried under 0.05-0.09MPa vacuum, 30-150 ℃ condition, dispel residual solvent, obtain powdery phenol sealing isophorone diisocyanate monomer affixture.
Phenol sealing isophorone diisocyanate of the present invention has good storage stability and post-treatment, is a kind of white powder solid; This product does not have waste water in preparation process, waste gas, trash discharge, and the solvent flashing that produces in the oven dry reclaims through condenser condenses.
For the ease of understanding the present invention, the present invention is further described below in conjunction with embodiment.
Embodiment 1: get phenol 2g and drop among ethyl acetate or the xylene solvent 40g, stir up to whole dissolvings; Getting isophorone diisocyanate 20g puts among ethyl acetate or the xylene solvent 60g and to stir up to whole dissolvings; Above-mentioned two kinds of solution are mixed, be warmed up to 50 ℃ gradually, stir, reaction under refluxad, 50 ℃ of controlled temperature, reaction stopped heating through 5 hours.In cooling tank, be cooled to normal temperature, crystallization in static 10 hours, crystallisate is separated through whizzer, putting into vacuum drying oven dried 4 hours under 150 ℃ of temperature, make that organic solvent content carries out secondary drying then less than 3% in the material under 150 ℃ of temperature, make in the material organic solvent content less than 1%, grind with mortar, promptly get phenol sealing isophorone diisocyanate.
Embodiment 2: get phenol 15g and drop among ethyl acetate or the xylene solvent 40g, stir up to whole dissolvings; Getting isophorone diisocyanate 5g puts among the solvent 60g and to stir up to whole dissolvings; Above-mentioned two kinds of solution are mixed, be warmed up to 120 ℃ gradually, stir, reaction under refluxad, 80 ℃ of controlled temperature, reaction stopped heating through 5 hours.In cooling tank, be cooled to normal temperature, crystallization in static 10 hours, crystallisate is separated through whizzer, putting into vacuum drying oven dried 4 hours under 30 ℃ of temperature, make that organic solvent content carries out secondary drying then less than 3% in the material under 30 ℃ of temperature, make in the material organic solvent content less than 1%, grind with mortar, promptly get phenol sealing isophorone diisocyanate.
Embodiment 3: get phenol 15g and drop among ethyl acetate or the xylene solvent 20g, stir up to whole dissolvings; Getting isophorone diisocyanate 5g puts among ethyl acetate or the xylene solvent 40g and to stir up to whole dissolvings; Above-mentioned two kinds of solution are mixed, be warmed up to 120 ℃ gradually, stir, reaction under refluxad, 80 ℃ of controlled temperature, reaction stopped heating through 5 hours.In cooling tank, be cooled to normal temperature, crystallization in static 10 hours, crystallisate is separated through whizzer, putting into vacuum drying oven dried 4 hours under 30 ℃ of temperature, make that organic solvent content carries out secondary drying then less than 3% in the material under 30 ℃ of temperature, make in the material organic solvent content less than 1%, grind with mortar, promptly get phenol sealing isophorone diisocyanate.
Embodiment 4: get phenol 2g and drop among ethyl acetate or the xylene solvent 20g, stir up to whole dissolvings; Getting isophorone diisocyanate 20g puts among ethyl acetate or the xylene solvent 40g and to stir up to whole dissolvings; Above-mentioned two kinds of solution are mixed, be warmed up to 50 ℃ gradually, stir, reaction under refluxad, 50 ℃ of controlled temperature, reaction stopped heating through 5 hours.In cooling tank, be cooled to normal temperature, crystallization in static 10 hours, crystallisate is separated through whizzer, putting into vacuum drying oven dried 4 hours under 150 ℃ of temperature, make that organic solvent content carries out secondary drying then less than 3% in the material under 150 ℃ of temperature, make in the material organic solvent content less than 1%, grind with mortar, promptly get phenol sealing isophorone diisocyanate.
Embodiment 5: get phenol 6g and drop among ethyl acetate or the xylene solvent 30g, stir up to whole dissolvings; Getting isophorone diisocyanate 10g puts among ethyl acetate or the xylene solvent 50g and to stir up to whole dissolvings; Above-mentioned two kinds of solution are mixed, be warmed up to 80 ℃ gradually, stir, reaction under refluxad, 80 ℃ of controlled temperature, reaction stopped heating through 5 hours.In cooling tank, be cooled to normal temperature, crystallization in static 10 hours, crystallisate is separated through whizzer, putting into vacuum drying oven dried 4 hours under 120 ℃ of temperature, make that organic solvent content carries out secondary drying then less than 3% in the material under 120 ℃ of temperature, make in the material organic solvent content less than 1%, grind with mortar, promptly get phenol sealing isophorone diisocyanate.
Embodiment 6: get phenol 8g and drop among ethyl acetate or the xylene solvent 30g, stir up to whole dissolvings; Getting isophorone diisocyanate 10g puts among ethyl acetate or the xylene solvent 40g and to stir up to whole dissolvings; Above-mentioned two kinds of solution are mixed, be warmed up to 120 ℃ gradually, stir, reaction under refluxad, 80 ℃ of controlled temperature, reaction stopped heating through 5 hours.In cooling tank, be cooled to normal temperature, crystallization in static 10 hours, crystallisate is separated through whizzer, putting into vacuum drying oven dried 4 hours under 60 ℃ of temperature, make that organic solvent content carries out secondary drying then less than 3% in the material under 70 ℃ of temperature, make in the material organic solvent content less than 1%, grind with mortar, promptly get phenol sealing isophorone diisocyanate.
Embodiment 7: get phenol 12g and drop among ethyl acetate or the xylene solvent 35g, stir up to whole dissolvings; Getting isophorone diisocyanate 15g puts among the solvent 45g and to stir up to whole dissolvings; Above-mentioned two kinds of solution are mixed, be warmed up to 120 ℃ gradually, stir, reaction under refluxad, 80 ℃ of controlled temperature, reaction stopped heating through 5 hours.In cooling tank, be cooled to normal temperature, crystallization in static 10 hours, crystallisate is separated through whizzer, putting into vacuum drying oven dried 4 hours under 60 ℃ of temperature, make that organic solvent content carries out secondary drying then less than 3% in the material under 70 ℃ of temperature, make in the material organic solvent content less than 1%, grind with mortar, promptly get phenol sealing isophorone diisocyanate.
Embodiment 8: get phenol 14g and drop among ethyl acetate or the xylene solvent 25g, stir up to whole dissolvings; Getting isophorone diisocyanate 18g puts among the solvent 50g and to stir up to whole dissolvings; Above-mentioned two kinds of solution are mixed, be warmed up to 110 ℃ gradually, stir, reaction under refluxad, 100 ℃ of controlled temperature, reaction stopped heating through 5 hours.In cooling tank, be cooled to normal temperature, crystallization in static 10 hours, crystallisate is separated through whizzer, putting into vacuum drying oven dried 4 hours under 100 ℃ of temperature, make that organic solvent content carries out secondary drying then less than 3% in the material under 90 ℃ of temperature, make in the material organic solvent content less than 1%, grind with mortar, promptly get phenol sealing isophorone diisocyanate.
Embodiment 9: get phenol 3g and drop among ethyl acetate or the xylene solvent 35g, stir up to whole dissolvings; Getting isophorone diisocyanate 8g puts among the solvent 46g and to stir up to whole dissolvings; Above-mentioned two kinds of solution are mixed, be warmed up to 110 ℃ gradually, stir, reaction under refluxad, 100 ℃ of controlled temperature, reaction stopped heating through 5 hours.In cooling tank, be cooled to normal temperature, crystallization in static 10 hours, crystallisate is separated through whizzer, putting into vacuum drying oven dried 4 hours under 100 ℃ of temperature, make that organic solvent content carries out secondary drying then less than 3% in the material under 90 ℃ of temperature, make in the material organic solvent content less than 1%, grind with mortar, promptly get phenol sealing isophorone diisocyanate.
Claims (4)
1. a phenol seals isophorone diisocyanate monomer affixture, and it is characterized in that: the feedstock production that comprises following parts by weight forms:
Phenol 2-15 part
Isophorone diisocyanate 5-20 part
Ethyl acetate or xylene solvent 60-100 part.
2. the preparation method of phenol sealing isophorone diisocyanate monomer affixture is characterized in that: comprise following steps:
(1) takes by weighing 2-15 part end-capping reagent phenol and be dissolved in 20-40 part ethyl acetate or the xylene solvent, make end-capping reagent solution;
(2) 5-20 part isophorone diisocyanate monomer is dissolved in 40-60 part ethyl acetate or the xylene solvent, makes monomer solution;
(3) under 50-120 ℃ of agitation condition, monomer solution joined in the end-capping reagent solution react, obtain insoluble phenol sealing isophorone diisocyanate monomer affixture.
3. the preparation method of phenol sealing isophorone diisocyanate monomer affixture according to claim 2 is characterized in that: also comprise following steps afterwards in above-mentioned steps (3): the insoluble affixture of gained is separated from solvent.
4. the preparation method of phenol sealing isophorone diisocyanate monomer affixture according to claim 3, it is characterized in that: also comprise following steps after the insoluble affixture of gained is separated from solvent: the affixture of separating is dried under 0.05-0.09MPa vacuum, 30-150 ℃ condition, dispel residual solvent, obtain powdery phenol sealing isophorone diisocyanate monomer affixture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010242777 CN101948410B (en) | 2010-08-03 | 2010-08-03 | Phenol blocking isophorone diisocyanate monomer adduct and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010242777 CN101948410B (en) | 2010-08-03 | 2010-08-03 | Phenol blocking isophorone diisocyanate monomer adduct and preparation method thereof |
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| CN101948410A true CN101948410A (en) | 2011-01-19 |
| CN101948410B CN101948410B (en) | 2013-06-05 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936210A (en) * | 2012-11-15 | 2013-02-20 | 中南林业科技大学 | 2,4-toluene diisocyanate and preparation method and application thereof |
| CN105152981A (en) * | 2015-09-07 | 2015-12-16 | 江苏泰仓农化有限公司 | PBMDI production process |
| CN112266339A (en) * | 2020-10-23 | 2021-01-26 | 湖南云科化工有限公司 | Preparation method of blocked isocyanate |
| CN116239756A (en) * | 2023-01-03 | 2023-06-09 | 万华化学集团股份有限公司 | Polyisocyanate composition stable in visible light and application thereof |
-
2010
- 2010-08-03 CN CN 201010242777 patent/CN101948410B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| H. KOTHANDARAMAN ET AL: "Synthesis and Thermal Dissociation of Phenol- and Naphthol-Blocked Diisocyanates", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 熊万斌等: "异氰酸酯封闭及其解封闭反应的研究", 《上海涂料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936210A (en) * | 2012-11-15 | 2013-02-20 | 中南林业科技大学 | 2,4-toluene diisocyanate and preparation method and application thereof |
| CN105152981A (en) * | 2015-09-07 | 2015-12-16 | 江苏泰仓农化有限公司 | PBMDI production process |
| CN112266339A (en) * | 2020-10-23 | 2021-01-26 | 湖南云科化工有限公司 | Preparation method of blocked isocyanate |
| CN116239756A (en) * | 2023-01-03 | 2023-06-09 | 万华化学集团股份有限公司 | Polyisocyanate composition stable in visible light and application thereof |
| CN116239756B (en) * | 2023-01-03 | 2024-08-16 | 万华化学集团股份有限公司 | Polyisocyanate composition stable in visible light and application thereof |
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| CN101948410B (en) | 2013-06-05 |
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