CN1189497C - Method for preparing polyurea polybasic alcohol - Google Patents
Method for preparing polyurea polybasic alcohol Download PDFInfo
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- CN1189497C CN1189497C CNB031268242A CN03126824A CN1189497C CN 1189497 C CN1189497 C CN 1189497C CN B031268242 A CNB031268242 A CN B031268242A CN 03126824 A CN03126824 A CN 03126824A CN 1189497 C CN1189497 C CN 1189497C
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Abstract
The present invention provides a method for preparing polyurea polybasic alcohol, which uses the raw materials of polyether polyol, hydrazine hydrate and isocyanate. The present invention comprises: (1) a part of polyether polyol and the hydrazine hydrate are mixd and stirred for 1 to 15 minutes; (2) the rest polyether polyol is mixed with the isocyanate and uniformly shaken for 30 seconds to 5 minutes; (3) a mixture obtained from the step (2) is added to a mixture obtained from the step (1) within 30 seconds to 3 minutes, and the mixtures are uniformly stirred and mixed; a system simultaneously generates an exothermic reaction, and a temperature quickly rises up; (4) after the temperature is cooled to normal temperature, the exothermic system is pumped into a vacuum state under the pressure of-0.2 to-0.1MPa at the temperature of 90 to 120 DEG C, and residual monomers are eliminated to obtain a polyether polyol product. The present invention uses a simple device to synthesize the polyether polyol within short time, and production efficiency is high; the present invention has the advantages of simple operation in a synthetic process, easy control and low production cost, and the prepared product has the advantages of low viscosity and high stability.
Description
Technical field
The present invention relates to a kind of preparation method of polyvalent alcohol, particularly a kind of preparation method of polyurea polylol.
Background technology
Polyurea polylol (PHD) is a kind of white or cream-coloured liquid that contains polyurea dispersions, viscosity higher is arranged.It was released in 1980, was mainly used in layered product, except the characteristics with common filling polyether glycol, also had many other advantages: favorable reproducibility; Work range is wide; Also can make porous plastics pass through combustion experiment without fire retardant; Improve the foam bearing load; Increase the initial gelation rate of foam, strengthen the stability that foam rises.In the prior art, two kinds of methods of the general employing of preparation polyurea polylol: intermittent type or continuous production method.The batch production method mainly is isocyanic ester progressively to be added drop-wise in polyvalent alcohol/polyamine mixed system with slow speed to make polyurea polylol under stirring fast, utilize the polyurea polylol solid content 10% of interrupter method preparation in the laboratory, viscosity is at (German Patent 1 more than 10000mPas/25 ℃, 260,142, United States Patent (USP) 3325421), the shortcoming that this batch production method exists is a long reaction time, the control difficulty is big, poor reproducibility, the polyurea polylol product instability of producing, viscosity is higher.Continuous production method mainly be simultaneously with polyamine, polyvalent alcohol and isocyanic ester by special type (for example UFS type machine of Hennecke company), utilize pump to squeeze into mixing section (for example the speed of squeezing into of polyamine, polyvalent alcohol and isocyanic ester is respectively 4800g/min, 1014g/min and 290g/min) at high speed with different speed, through high-speed stirring and moment mixing, reaction is carried out very soon and is flowed out polyurea polylol from discharge port; The polyurea polylol solid content that the industrialization continuous processing is produced is generally 20%, United States Patent (USP) 4,089, and 835 disclose continuous processing, and to produce solid content be 10% polyurea polylol, viscosity is about 2500mPas/25 ℃.All mentioning at United States Patent (USP) 4761434, United States Patent (USP) 4093569, United States Patent (USP) 4184990, United States Patent (USP) 4092275, United States Patent (USP) 5332763, United States Patent (USP) 4042537 in addition uses continuous processing to prepare PHD.But this method requires to use special equipment, and the production investment cost is huge, and common lab or factory are difficult to satisfy the requirement of its reaction conditions.Above-mentioned two kinds of methods all are unfavorable for studying polyurea polylol more widely, are unfavorable for the further promotion and application of polyurea polylol.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, provide that a kind of working condition is simple, resultant velocity is fast, the preparation method of the polyurea polylol of good product performance.
Purpose of the present invention is achieved through the following technical solutions: the raw material of employing is polyether glycol, hydrazine hydrate and isocyanic ester, wherein the weight ratio of the weight of isocyanic ester and hydrazine and polyether glycol is 0.05～0.45 (being that solid content is 5%～45%), and the mol ratio of isocyanic ester and hydrazine is 0.8～1.2; Its preparation method comprises following step:
(1) shake up 30 seconds after part polyether glycol and isocyanic ester are mixed～5 minutes, preferred 30 seconds～2 minutes, the mol ratio of described part polyether glycol and isocyanic ester was 0.5～2;
(2) residual polyether polyol being mixed the back with hydrazine hydrate stirred 1～15 minute; Preferred 5～10 minutes;
(3) mixture that step (1) is obtained added in the mixture that step (2) obtains in 30 seconds～3 minutes and stirs, and mixed, and system generation thermopositive reaction this moment temperature rises rapidly;
(4) after the temperature for the treatment of the heat release system drops to normal temperature ,-0.2～-0.1MPa, temperature vacuumize under 90～120 ℃ the condition, removes residual monomer, obtains the polyurea polylol product.
In the described step (2), can add organic solvents such as entry or toluene, dimethylbenzene, acetone, benzene as required as dispersion agent.
In the described step (3), churning time can be preferred 10～60 minutes.
In the described step (4), the pressure when vacuumizing is preferred-and 0.1MPa, time of vacuumizing are 2～3 hours.
The present invention compared with prior art has following advantage and effect: (1) can synthesize polyurea polylol with comparatively easy device within a short period of time, and resultant velocity is fast, the production efficiency height; (2) building-up process control simple to operate, easy, favorable reproducibility does not need to use special equipment, and production cost is lower; (3) prepared lower, the good stability of polyurea polylol viscosity; Adopt the prepared urethane foam of this polyurea polylol, have advantages of high bearing capacity and good flame retardancy, can reach from putting out level.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
Add the polyether glycol (330N) of 262g and the hydrazine hydrate (content is 80%) of 11.5g in four-hole boiling flask, connect thermometer and stirring arm, continuously stirring is 5 minutes at normal temperatures; In 30 seconds inherent said mixtures, add the 30.5g isocyanic ester that mixed after shaking up 1 minute and the mixture of 101.6g polyether glycol then, continue again to stir 30 minutes, this system generation thermopositive reaction, temperature rises rapidly; After treating that the heat release system temperature drops to normal temperature, connect the condensing reflux pipe, be to vacuumize 2.5 hours under 110 ℃ the condition at pressure for-0.1MPa, temperature, remove residual monomer, get final product to such an extent that solid content (be in the raw material isocyanic ester and the weight of hydrazine and the weight percent of polyether glycol) is 10% polyurea polylol product.
It is 3 hours that this preparation technology reacts the used time, and the polyurea polylol that obtains is a milky white liquid; Adopting NDJ-1 type rotary viscosimeter instrument to record its viscosity is 4300mpas; Adopt LG-10-24 type whizzer to carry out centrifugation half an hour, do not produce precipitation with the rotating speed of 12000 commentaries on classics/S.
Embodiment 2
The polyether glycol (330N), the hydrazine hydrate (content is 80%) of 11.5g and the water (as dispersion agent) of 40.6g that in four-hole boiling flask, add 262g, connect thermometer and stirring arm, continuously stirring is 10 minutes at normal temperatures, added 30.5g isocyanic ester and the 101.6g polyether glycol that has mixed after shaking up 2 minutes in 1 minute in the inherent said mixture then, continue again to stir 20 minutes, this system generation thermopositive reaction, temperature rises rapidly; After treating that the heat release system temperature drops to normal temperature, connecting the condensing reflux pipe, is to vacuumize 3 hours under 105 ℃ the condition for-0.1MPa, temperature at pressure, removes residual monomer, gets final product to such an extent that solid content is 10% polyurea polylol product.
It is 3.5 hours that this preparation technology reacts the used time, and the polyurea polylol that obtains is a milky white liquid.Adopting NDJ-1 type rotary viscosimeter instrument to record viscosity is 2400mpas; Adopt LG-10-24 type whizzer to carry out centrifugation half an hour, do not produce precipitation with the rotating speed of 12000 commentaries on classics/S.
Embodiment 3
The polyether glycol (330N), the hydrazine hydrate (content is 80%) of 11.5g and the toluene (as dispersion agent) of 40.6g that in four-hole boiling flask, add 262g, connect thermometer and stirring arm, continuously stirring is 15 minutes at normal temperatures, added 30.5g isocyanic ester and the 101.6g polyether glycol that has mixed after shaking up 3 minutes in 45 seconds in the inherent said mixture then, continue to stir 45 minutes, the temperature of this thermopositive reaction system rises rapidly again; After treating that the heat release system temperature drops to normal temperature, connecting the condensing reflux pipe, is to vacuumize 2 hours under 120 ℃ the condition for-0.1MPa, temperature at pressure, removes residual monomer, gets final product to such an extent that solid content is 10% polyurea polylol product.
It is 3.5 hours that this preparation technology reacts the used time, and the polyurea polylol that obtains is a milky white liquid.Adopting NDJ-1 type rotary viscosimeter instrument to record viscosity is 3000mpas; Adopt LG-10-24 type whizzer to carry out centrifugation half an hour, do not produce precipitation with the rotating speed of 12000 commentaries on classics/S.
Embodiment 4
In four-hole boiling flask, add the polyether glycol (330N) of 189.3g and the hydrazine hydrate (content is 80%) of 23g, connect thermometer and stirring arm, continuously stirring is 10 minutes at normal temperatures, added 61g isocyanic ester and the 174.3g polyether glycol that has mixed after shaking up 1 minute in 40 seconds in the inherent said mixture then, continue to stir 60 minutes, the temperature of this thermopositive reaction system rises rapidly; After treating that the heat release system temperature drops to normal temperature, connecting the condensing reflux pipe, is to vacuumize 2 hours under 100 ℃ the condition for-0.1MPa, temperature at pressure, removes residual monomer, gets final product to such an extent that solid content is 20% polyurea polylol product.
It is 3 hours that this preparation technology reacts the used time, and the polyurea polylol that obtains is a milky white liquid.Adopting NDJ-1 type rotary viscosimeter instrument to record viscosity is 7500mpas; Adopt LG-10-24 type whizzer to carry out centrifugation half an hour, do not produce precipitation with the rotating speed of 12000 commentaries on classics/S.
Embodiment 5
In four-hole boiling flask, added after water (as the dispersion agent) mixing of the hydrazine hydrate (content is 80%) of polyether glycol (330N), 11.5g of 94.7g and 9.3g at normal temperatures continuously stirring 5 minutes, added 30.5g isocyanic ester and the 50.8g polyether glycol that has mixed after shaking up 1 minute in 1 minute in the inherent said mixture then, continue to stir 30 minutes, the temperature of this thermopositive reaction system rises rapidly; After treating that the heat release system temperature drops to normal temperature, connecting the condensing reflux pipe, is to vacuumize 2 hours under 105 ℃ the condition for-0.1MPa, temperature at pressure, removes residual monomer, gets final product to such an extent that solid content is 25% polyurea polylol product.
It is 3 hours that this preparation technology reacts the used time, and the polyurea polylol that obtains is a milky white liquid.Adopting NDJ-1 type rotary viscosimeter instrument to record viscosity is 7200mpas; Adopt LG-10-24 type whizzer to carry out centrifugation half an hour, do not produce precipitation with the rotating speed of 12000 commentaries on classics/S.
Claims (6)
1, a kind of preparation method of polyurea polylol, the raw material of employing is polyether glycol, hydrazine hydrate and isocyanic ester, wherein the weight ratio of the weight of isocyanic ester and hydrazine and polyether glycol is 0.05～0.45, and the mol ratio of isocyanic ester and hydrazine is 0.8～1.2; It is characterized in that comprising following step:
(1) shake up 30 seconds after part polyether glycol and isocyanic ester are mixed～5 minutes, the mol ratio of described part polyether glycol and isocyanic ester is 0.5～2;
(2) residual polyether polyol being mixed the back with hydrazine hydrate stirred 1～15 minute;
(3) mixture that step (1) is obtained added in the mixture that step (2) obtains in 30 seconds～3 minutes and stirs, and mixed, and system generation thermopositive reaction this moment temperature rises rapidly;
(4) after the temperature for the treatment of the heat release system drops to normal temperature ,-0.2～-0.1MPa, temperature vacuumize under 90～120 ℃ the condition, removes residual monomer, obtains the polyurea polylol product.
2, the preparation method of polyurea polylol according to claim 1 is characterized in that: in the described step (2), add entry or toluene, dimethylbenzene, acetone, benzene as dispersion agent.
3, the preparation method of polyurea polylol according to claim 1 is characterized in that: in the described step (2), polyether glycol and hydrazine hydrate were mixed the back continuously stirring 5～10 minutes.
4, the preparation method of polyurea polylol according to claim 1 is characterized in that: in the described step (1), shake up 30 seconds after polyether glycol and isocyanic ester mixed～2 minutes.
5, the preparation method of polyurea polylol according to claim 1 is characterized in that: in the described step (3), the mixture that step (1) is obtained continues to stir 10～60 minutes after pouring the mixture that step (2) obtains into.
6, the preparation method of polyurea polylol according to claim 1 is characterized in that: in the described step (4), the pressure when vacuumizing is 2～3 hours for-0.1MPa, time of vacuumizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031268242A CN1189497C (en) | 2003-06-12 | 2003-06-12 | Method for preparing polyurea polybasic alcohol |
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| CNB031268242A CN1189497C (en) | 2003-06-12 | 2003-06-12 | Method for preparing polyurea polybasic alcohol |
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| CN1470547A CN1470547A (en) | 2004-01-28 |
| CN1189497C true CN1189497C (en) | 2005-02-16 |
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| CNB031268242A Expired - Fee Related CN1189497C (en) | 2003-06-12 | 2003-06-12 | Method for preparing polyurea polybasic alcohol |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102391453B (en) * | 2011-08-31 | 2013-04-10 | 山东蓝星东大化工有限责任公司 | Preparation method of aliphatic polyurea polymer |
| CN106117501A (en) * | 2016-07-30 | 2016-11-16 | 淄博德信联邦化学工业有限公司 | Fire-retardant polyurea polylol and preparation method thereof |
| CN109096462B (en) * | 2018-07-09 | 2020-11-10 | 江苏长顺高分子材料研究院有限公司 | Composition of low-aldehyde polyether polyol and preparation method thereof |
| CN109438669B (en) * | 2018-12-20 | 2021-01-19 | 江苏长顺高分子材料研究院有限公司 | Low-VOC polyurethane foam with high sound absorption performance and application thereof |
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