CN102134204A - Preparation method of enclosed type poly-methyl poly-phenyl polyisocyanates capable of being unclosed at low temperature - Google Patents
Preparation method of enclosed type poly-methyl poly-phenyl polyisocyanates capable of being unclosed at low temperature Download PDFInfo
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- CN102134204A CN102134204A CN2011100615888A CN201110061588A CN102134204A CN 102134204 A CN102134204 A CN 102134204A CN 2011100615888 A CN2011100615888 A CN 2011100615888A CN 201110061588 A CN201110061588 A CN 201110061588A CN 102134204 A CN102134204 A CN 102134204A
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- polyphenyl polyisocyanate
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Abstract
The invention discloses a preparation method of enclosed type poly-methyl poly-phenyl polyisocyanates capable of being unclosed at low temperature, and relates to a preparation method of enclosed type poly-methyl poly-phenyl polyisocyanates. The invention solves the technical problem of relatively high unclosing temperature of the existing enclosed type isocyanate. The method comprises the following steps: firstly, dissolving 2, 4, 6-trichlorophenol in a polar solvent; and secondly, adding poly-methyl poly-phenyl polyisocyanates in a reactor, stirring for temperature rise under the protection of nitrogen, dropping in a trichlorophenol solution, continuing to stir for reaction for 3-7 hours; and then obtaining the enclosed type poly-methyl poly-phenyl polyisocyanates. The unclosing temperature of the enclosed type poly-methyl poly-phenyl polyisocyanates is lower than 70 DEG C, and the unclosing temperature in the polar solvent is lower than 65 DEG C. The method has the advantages of simple process, convenience for operation, and easiness for control.
Description
Technical field
The present invention relates to the preparation method of many methyl of dead front type polyphenyl polyisocyanate.
Background technology
Blocked isocyanate is meant-the NCO group is by a kind of compound that can not take off the encapsulant sealing of envelope reaction at normal temperatures.This compound is polymerization reaction take place not at room temperature, but at high temperature-the NCO group regenerate again and with the compound generation replacement(metathesis)reaction that contains reactive hydrogen.In recent years, because unique reactivity of blocked isocyanate, and requirement on environmental protection, the use of masked isocyanate sharply increases, and Application Areas is also more and more widely.At present, the deblocking temperature of common masked isocyanate is higher, and certain difficulty is arranged in actual applications.
Summary of the invention
The present invention will solve the deblocking temperature technical problems of high of existing masked isocyanate; But and provide the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking.
But the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking finishes by following step among the present invention: one, with 2,4, the 6-Trichlorophenol is dissolved in the polar solvent, obtains 2,4,6-Trichlorophenol solution; Two, many methyl polyphenyl polyisocyanate is added in the reactor; under nitrogen protection, stir and be warming up to 80～85 ℃; again by the mol ratio of isocyanate group and phenolic hydroxyl group be 1: 1～1.3 splash into that step 1 obtains 2; 4; 6-Trichlorophenol solution (needs 0.5～1h); continuation is at 80～85 ℃ of stirring reaction 3～7h, but promptly obtains many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking.Show deblocking temperature＜70 ℃ through hot analytical results, if in polar solvent deblocking temperature lower (＜65 ℃).The inventive method has that technology is simple, easy to operate, the advantage of easy control.
But the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking also can finish by following step among the present invention: one, with 2,4, the 6-Trichlorophenol is dissolved in the polar solvent, obtains 2,4,6-Trichlorophenol solution; Two, many methyl polyphenyl polyisocyanate is added in the reactor, under nitrogen protection, stir and be warming up to 80～85 ℃, again by the mol ratio of isocyanate group and phenolic hydroxyl group be 1: 1～1.3 splash into dropwise that step 1 obtains 2,4,6-Trichlorophenol solution (needs 0.5～1h), add dibutyl tin laurate then, continue, but promptly obtain many these Quito isocyanic ester of the many methyl of dead front type of low temperature deblocking at 80～85 ℃ of stirring reaction 3～7h; Wherein the consumption of dibutyl tin laurate described in the step 2 is 0.5%～1.5% of many methyl polyphenyl polyisocyanate quality.Show deblocking temperature＜70 ℃ through hot analytical results, if in polar solvent deblocking temperature lower (＜65 ℃).The inventive method has that technology is simple, easy to operate, the advantage of easy control.
Description of drawings
Fig. 1 is 2,4 of an embodiment 11, and the 6-Trichlorophenol seals the DSC spectrogram of many methyl polyphenyl polyisocyanate; Fig. 2 is an embodiment 11,4, and the 6-Trichlorophenol seals the TG/DTA spectrogram of many methyl polyphenyl polyisocyanate.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: but the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking finishes by following step in the present embodiment: and one, with 2,4, the 6-Trichlorophenol is dissolved in the polar solvent, obtains 2,4,6-Trichlorophenol solution; Two, many methyl polyphenyl polyisocyanate is added in the reactor; under nitrogen protection, stir and be warming up to 80～85 ℃; again by the mol ratio of isocyanate group and phenolic hydroxyl group be 1: 1～1.3 splash into dropwise that step 1 obtains 2; 4; 6-Trichlorophenol solution (needs 0.5～1h); continuation is at 80～85 ℃ of stirring reaction 3～7h, but promptly obtains many these Quito isocyanic ester of the many methyl of dead front type of low temperature deblocking.
Show deblocking temperature＜70 of many these Quito isocyanic ester of the many methyl of the dead front type that present embodiment makes ℃, its deblocking temperature in polar solvent lower (＜65 ℃) through hot analytical results.The inventive method has that technology is simple, easy to operate, the advantage of easy control.
Embodiment two: what present embodiment and embodiment one were different is: the described polar solvent of step 1 is a butanone, 1,4-dioxane or N, dinethylformamide.Other step is identical with embodiment one with parameter.
Embodiment three: what present embodiment was different with embodiment one or two is: step 1 is described 2,4, and the mass concentration of 6-Trichlorophenol solution is 50～95%.Other step is identical with embodiment one or two with parameter.
Embodiment four: what present embodiment was different with one of embodiment one to three is: the speed of the described stirring of step 2 is 500～1500r/min.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what present embodiment was different with one of embodiment one to three is: the mol ratio of described isocyanate group of step 2 and phenolic hydroxyl group is 1: 1.2.Other step is identical with one of embodiment one to three with parameter.
Embodiment six: but the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking finishes by following step in the present embodiment: and one, with 2,4, the 6-Trichlorophenol is dissolved in the polar solvent, obtains 2,4,6-Trichlorophenol solution; Two, many methyl polyphenyl polyisocyanate is added in the reactor, under nitrogen protection, stir and be warming up to 80～85 ℃, again by the mol ratio of isocyanate group and phenolic hydroxyl group be 1: 1～1.3 splash into dropwise that step 1 obtains 2,4,6-Trichlorophenol solution (needs 0.5～1h), add dibutyl tin laurate then, continue, but promptly obtain many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking at 80～85 ℃ of stirring reaction 3～7h; Wherein the consumption of dibutyl tin laurate described in the step 2 is 0.5%～1.5% of many methyl polyphenyl polyisocyanate quality.
Show deblocking temperature＜70 of many these Quito isocyanic ester of the many methyl of the dead front type that present embodiment makes ℃, its deblocking temperature in polar solvent lower (＜65 ℃) through hot analytical results.The inventive method has that technology is simple, easy to operate, the advantage of easy control.
Embodiment seven: what present embodiment and embodiment six were different is: the described polar solvent of step 1 is a butanone, 1,4-dioxane or N, dinethylformamide.Other step is identical with embodiment six with parameter.
Embodiment eight: what present embodiment was different with embodiment six or seven is: step 1 is described 2,4, and the mass concentration of 6-Trichlorophenol solution is 50～95%.Other step is identical with embodiment six or seven with parameter.
Embodiment nine: what present embodiment was different with one of embodiment six to eight is: the speed of the described stirring of step 2 is 500～1000r/min.Other step is identical with one of embodiment six to eight with parameter.
Embodiment ten: what present embodiment was different with one of embodiment six to nine is: the consumption of the described dibutyl tin laurate of step 2 is 1.2% of many methyl polyphenyl polyisocyanate quality.Other step is identical with one of embodiment six to nine with parameter.
Embodiment 11: but the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking finishes by following step in the present embodiment: one, with 12.422g2,4, the 6-Trichlorophenol is dissolved in the 12.422g butanone, obtains 2,4,6-Trichlorophenol solution; Two, many methyl of 8g polyphenyl polyisocyanate is added in the reactor; under nitrogen protection, be warming up to 80 ℃ with the stirring of 500r/min speed; again by the mol ratio of isocyanate group and phenolic hydroxyl group be splash into that step 1 obtains at 1: 11 2; 4,6-Trichlorophenol solution drips 0.5h consuming time; continuation is at 80 ℃ of stirring reaction 5h; promptly obtain 2,4, the 6-Trichlorophenol seals many methyl polyphenyl polyisocyanate.
2,4 of present embodiment preparation, the 6-Trichlorophenol seals many methyl polyphenyl polyisocyanate DSC curve as shown in Figure 1, and the TG/DTA curve is as shown in Figure 2.By Fig. 1 and Fig. 2 as can be known, by 2,4, the deblocking reaction that the 6-Trichlorophenol seals many methyl polyphenyl polyisocyanate product is a process of heat absorption, and the sealing product begins deblocking and discharges encapsulant in the time of 70 ℃.The existence of three strong electron-withdrawing group group chlorine atoms is arranged on the ortho para just because of phenolic hydroxyl group in the phenyl ring, make deblocking react easier generation, because of a little deblocking are more prone to.
2,4 of present embodiment preparation, it is as shown in table 1 that the 6-Trichlorophenol seals the deblocking temperature of many methyl polyphenyl polyisocyanate in different solvents:
Table 1
| Polar solvent | Acetone | Butanone | Chloroform |
| The deblocking temperature/℃ | 48 | 65 | 60 |
Embodiment 12: but the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking finishes by following step in the present embodiment: one, with 13.551g2,4, the 6-Trichlorophenol is dissolved in 13.551gN, in the dinethylformamide, obtain 2,4,6-Trichlorophenol solution; Two, many methyl of 8g polyphenyl polyisocyanate is added in the reactor, under nitrogen protection, stir and be warming up to 85 ℃, again by the mol ratio of isocyanate group and phenolic hydroxyl group be dropwise splash into that step 1 obtains at 1: 1.2 2,4,6-Trichlorophenol solution, drip 2,4,6-Trichlorophenol solution 0.75h consuming time adds the 0.04g dibutyl tin laurate then, continuation is at 85 ℃ of stirring reaction 3h, but promptly obtains many these Quito isocyanic ester of the many methyl of dead front type of low temperature deblocking; Wherein the consumption of dibutyl tin laurate described in the step 2 is 0.5% of many methyl polyphenyl polyisocyanate quality.
Through overheated analysis, the result shows that the deblocking temperature of many these Quito isocyanic ester of the many methyl of dead front type of present embodiment preparation is 70 ℃.
2,4 of present embodiment preparation, it is as shown in table 1 that the 6-Trichlorophenol seals the deblocking temperature of many methyl polyphenyl polyisocyanate in different solvents:
Table 2
| Polar solvent | Acetone | Butanone | Chloroform |
| The deblocking temperature/℃ | 28 | 60 | 28 |
Claims (10)
- But 1. the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking, but it is characterized in that the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking finishes by following step:One, with 2,4, the 6-Trichlorophenol is dissolved in the polar solvent, obtains 2,4,6-Trichlorophenol solution;Two, many methyl polyphenyl polyisocyanate is added in the reactor; under nitrogen protection, stir and be warming up to 80 ℃～85 ℃; again by the mol ratio of isocyanate group and phenolic hydroxyl group be 1: 1～1.3 splash into dropwise that step 1 obtains 2; 4; 6-Trichlorophenol solution; continuation is at 80 ℃～85 ℃ stirring reaction 3～7h, but promptly obtains many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking.
- 2. but the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking according to claim 1 is characterized in that the described polar solvent of step 1 is a butanone, 1,4-dioxane or N, dinethylformamide.
- 3. but the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking according to claim 2 is characterized in that step 1 is described 2,4, and the mass concentration of 6-Trichlorophenol solution is 50%～95%.
- 4. but according to the preparation method of many methyl of dead front type polyphenyl polyisocyanate of claim 1,2 or 3 described low temperature deblockings, the speed that it is characterized in that the described stirring of step 2 is 500～1500r/min.
- 5. but the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking according to claim 4, the mol ratio that it is characterized in that described isocyanate group of step 2 and phenolic hydroxyl group is 1: 1.2.
- But 6. the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking, but it is characterized in that the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking finishes by following step:One, with 2,4, it is butanone or 1 that the 6-Trichlorophenol is dissolved in polar solvent, the 4-dioxane or in, obtain 2,4,6-Trichlorophenol solution;Two, many methyl polyphenyl polyisocyanate is added in the reactor, under nitrogen protection, stir and be warming up to 80～85 ℃, again by the mol ratio of isocyanate group and phenolic hydroxyl group be 1: 1～1.3 splash into dropwise that step 1 obtains 2,4,6-Trichlorophenol solution, add dibutyl tin laurate then, continue, but promptly obtain many these Quito isocyanic ester of the many methyl of dead front type of low temperature deblocking at 80～85 ℃ of stirring reaction 3～7h; Wherein the consumption of dibutyl tin laurate described in the step 2 is 0.5%～1.5% of many methyl polyphenyl polyisocyanate quality.
- 7. but the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking according to claim 6 is characterized in that the described polar solvent of step 1 is a butanone, 1,4-dioxane or N, dinethylformamide.
- 8. but the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking according to claim 7 is characterized in that step 1 is described 2,4, and the mass concentration of 6-Trichlorophenol solution is 50%～95%.
- 9. but according to the preparation method of many methyl of dead front type polyphenyl polyisocyanate of claim 6,7 or 8 described low temperature deblockings, the speed that it is characterized in that the described stirring of step 2 is 500～1500r/min.
- 10. but the preparation method of many methyl of dead front type polyphenyl polyisocyanate of low temperature deblocking according to claim 9, the consumption that it is characterized in that the described dibutyl tin laurate of step 2 is 1.0%～1.2% of many methyl polyphenyl polyisocyanate quality.
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| CN2011100615888A CN102134204A (en) | 2011-03-15 | 2011-03-15 | Preparation method of enclosed type poly-methyl poly-phenyl polyisocyanates capable of being unclosed at low temperature |
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| CN2011100615888A CN102134204A (en) | 2011-03-15 | 2011-03-15 | Preparation method of enclosed type poly-methyl poly-phenyl polyisocyanates capable of being unclosed at low temperature |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417598A (en) * | 2011-11-16 | 2012-04-18 | 东北林业大学 | Preparation method for closed-type aliphatic-series isocyanate water dispersoid |
| CN103342822A (en) * | 2013-06-27 | 2013-10-09 | 东北林业大学 | Preparation method of trichlorophenol blocked isocyanate prepolymer micelle |
-
2011
- 2011-03-15 CN CN2011100615888A patent/CN102134204A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 娄春华 等: "三氯苯酚与PAPI封闭反应的条件", 《河北师范大学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417598A (en) * | 2011-11-16 | 2012-04-18 | 东北林业大学 | Preparation method for closed-type aliphatic-series isocyanate water dispersoid |
| CN103342822A (en) * | 2013-06-27 | 2013-10-09 | 东北林业大学 | Preparation method of trichlorophenol blocked isocyanate prepolymer micelle |
| CN103342822B (en) * | 2013-06-27 | 2014-12-17 | 东北林业大学 | Preparation method of trichlorophenol blocked isocyanate prepolymer micelle |
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Application publication date: 20110727 |