CN1247664C - Process for preparing high solid content polyurea polyol - Google Patents
Process for preparing high solid content polyurea polyol Download PDFInfo
- Publication number
- CN1247664C CN1247664C CN 03140323 CN03140323A CN1247664C CN 1247664 C CN1247664 C CN 1247664C CN 03140323 CN03140323 CN 03140323 CN 03140323 A CN03140323 A CN 03140323A CN 1247664 C CN1247664 C CN 1247664C
- Authority
- CN
- China
- Prior art keywords
- solids content
- high solids
- minutes
- preparation
- polyurea polylol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a preparation method for polyurea polyol having the high content of solid. Raw materials utilized by the present invention comprise polyether polyol, hydrazine hydrate and isocyanate. The present invention comprises: (1)dihydric alcohol is added to a part of polyether polyol which is mixed with the hydrazine hydrate 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 a temperature of 90 to 120 DEG C, and residual monomers are eliminated to obtain a polyether polyol product. The polyether polyol prepared by the present invention has the advantages of high content of solid, low viscosity and high stability, and the present invention has the advantages of simple production devices, low production cost, simple operation and favorable repeatability in a synthesis process.
Description
Technical field
The present invention relates to a kind of preparation method of polyvalent alcohol, particularly a kind of preparation method of high solids content polyurea polylol.
Background technology
Polyurea polylol (PHD) was released in 1980, was a kind of white or cream-coloured liquid that contains polyurea dispersions and viscosity higher.Polyurea polylol can be used for producing urethane foam, is had advantages of high bearing capacity and good flame retardancy and can be widely used in fields such as furniture, automobile, train, aircraft, boats and ships by its urethane foam of producing.Wherein, the polyurea polylol of high solids content (solid content is 25%～45%) is for the polyurea polylol of low-solid content (solid content is 10%～20%), have better performance: it not only can increase substantially the foam bearing load, can also improve the flame retardant properties of porous plastics.The solid content of the polyurea polylol product of existing method preparation is lower or viscosity is too high, employing interrupter method for example its solid content major part of polyurea polylol of USP3325421, GER 1260142, USP 4595709, USP 4107102 preparations is 10%～15%, viscosity is up to more than 10000mPas/25 ℃ simultaneously, long reaction time, the control difficulty is big, poor reproducibility, the polyurea polylol product instability of producing, less to the flame retardant properties help of foam bearing load and porous plastics; Industrialization continuous processing for example its solid content of polyurea polylol of USP 4761434, USP 4184990, USP 4092275, USP 5332763, USP 4042537 productions is generally 20%, but need to adopt special type (for example UFS type machine of Hennecke company), the production investment cost is huge, have only German Bayer company and U.S. Mobay company to have the ability to adopt the industrialization continuous processing to produce polyurea polylol at present, common lab or factory are difficult to reach its reaction requirement; At home, institute of Nanjing petrochemical industry plastic molding and processing plant and Fudan University once adopted hydration polyamine N-1 system to prepare solid content lower (solid content only is 18%), the JS-350 polyurea polylol of viscosity about 3300mPas/25 ℃.In the process of preparation high solids content polyurea polylol, owing to have than poly-hydroxy and participate in reaction, cause the viscosity of reaction system higher, make and obtain gel and can not get dispersion or obtain the very large dispersion of viscosity in initial reaction stage, finally cause the polyurea polylol viscosity of high solids content too high, pump delivery difficulty, metering are forbidden and can't used on general foaming machine.So how to become the focal issue of more and more being paid close attention to easy method acquisition high solids content and low viscous polyurea polylol.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, the preparation method of the high solids content polyurea polylol that provide that a kind of working condition is simple, good product performance, solid content height (solid content is 25%～45%) and viscosity is lower.
Purpose of the present invention is achieved through the following technical solutions: the raw material of employing comprises polyether glycol, hydrazine hydrate and isocyanic ester, wherein the weight ratio of the weight of isocyanic ester and hydrazine and polyether glycol is 0.25～0.45 (being that solid content is 25%～45%), and the mol ratio of isocyanic ester and hydrazine is 0.8～1.2; Its preparation method comprises following step:
(1) with the part polyether glycol with after hydrazine hydrate mixes, add dibasic alcohol as dispersion agent, stirred then 1～15 minute; The consumption of described dibasic alcohol is 1%～20% of a gross weight;
(2) after being mixed, residual polyether polyol and isocyanic ester shake up 30 seconds～5 minutes;
(3) mixture that step (2) is obtained added in 30 seconds～3 minutes in the mixture that step (1) obtains, and mixed; 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, can obtain high solids content polyurea polylol product.
In the described step (1), preferred 5～10 minutes of churning time; The consumption of dibasic alcohol is preferably 5%～10% of gross weight; The dibasic alcohol preferred molecular weight is lower than 200 dibasic alcohol, preferably selects in ethylene glycol, propylene glycol or the butyleneglycol any.
The mol ratio of residual polyether polyol and isocyanic ester is 0.5～2 in the described step (2), preferred 30 seconds～2 minutes of the time that shakes up.
In the described step (3), preferred 10～60 minutes of churning time.
In the described step (4), the pressure when vacuumizing is preferred-and 0.1MPa, time of vacuumizing are 2～3 hours.
In the raw material, generally between 20～60, functional group is between 2～4 for the hydroxyl value of polyether glycol, and molecular weight is between 2000～8000, and primary hydroxyl is more is advisable; Generally select the 330N polyether glycol for use.
In the raw material, isocyanic ester can be aliphatic isocyanates or aromatic polyisocyanate, as m-benzene diisocyanate, PPDI, polymethine polyphenyl polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene diisocyanate, ditan 4,4 '-or 2,4-or 2,2 '-vulcabond, hexamethylene-diisocyanate etc.; Generally select 2 for use, 4-and 2, the mixture of 6-tolylene diisocyanate.
The principle that the present invention prepares the high solids content polyurea polylol is: add an amount of dibasic alcohol as dispersion agent in reaction system, dibasic alcohol is as the intermediary of close amine and parent's alcohol, make hydrazine hydrate better be dispersed in the polyether glycol, impel hydrazine hydrate and isocyanic ester fully to react, reducing unnecessary crosslinking reaction takes place, stop the cross-linking products that generates to form the aggregate of bulk, reduce the partially hydrated hydrazine of product embedding and influence the stoichiometry of reaction, reduced the viscosity of product when improving the product solid content; In reaction process, stir simultaneously, make particle trend towards forming slick near-spherical form, improve particulate size, dispersiveness and particle shape by plasticising mechanism.
The present invention compared with prior art has following advantage and effect: the polyurea polylol solid content height that (1) is prepared, and viscosity is lower, good stability, the urethane foam that adopts this polyurea polylol to make has advantages of high bearing capacity and good flame retardancy, can reach from putting out level; (2) can use comparatively easy production equipment, production cost is lower; (3) building-up process is simple to operate, favorable reproducibility.
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 330N polyether glycol, 10g propylene glycol (account for gross weight 4.6%) of 102.8g and the hydrazine hydrate (hydrazine content is 80%) of 25.8g in four-hole boiling flask, connect thermometer and stirring arm, continuously stirring is 5 minutes at normal temperatures; Adding the 42.7g isocyanic ester that has mixed after shaking up 1 minute in 30 seconds in the inherent said mixture then (is 2,4-and 2, the mixture of 6-tolylene diisocyanate, wherein mol ratio 2,4-tolylene diisocyanate: 2,6-tolylene diisocyanate=4: 1) and the mixture of 42.7g polyether glycol, continue again to stir 45 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 2 hours under 115 ℃ the condition for-0.1MPa, temperature at pressure, removes residual monomer, gets final product to such an extent that solid content is 35% high solids content polyurea polylol product.
The high solids content polyurea polylol that obtains is a milky white liquid, and adopting NDJ-1 type rotary viscosimeter instrument to record its viscosity is 4100mpas; 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
Add the 330N polyether glycol, 20g propylene glycol (account for gross weight 7.8%) of 135.3g and the hydrazine hydrate (hydrazine content is 80%) of 15.3g in four-hole boiling flask, connect thermometer and stirring arm, at room temperature continuously stirring is 15 minutes; Adding the 46.8g isocyanic ester that has mixed after shaking up 45 seconds in 30 seconds in the inherent said mixture then (is 2,4-and 2, the mixture of 6-tolylene diisocyanate, wherein mol ratio 2,4-tolylene diisocyanate: 2,6-tolylene diisocyanate=4: 1) and the mixture of 46.8g polyether glycol, continue again to stir 25 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 100 ℃ the condition for-0.1MPa, temperature at pressure, removes residual monomer, gets final product to such an extent that solid content is 30% high solids content polyurea polylol product.
The high solids content polyurea polylol that obtains is a milky white liquid, and adopting NDJ-1 type rotary viscosimeter instrument to record its viscosity is 4600mpas; 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
Add the 330N polyether glycol, 20g butyleneglycol (account for gross weight 8.8%) of 90.6g and the hydrazine hydrate (hydrazine content is 80%) of 20.7g in four-hole boiling flask, connect thermometer and stirring arm, continuously stirring is 8 minutes at normal temperatures; Adding the 54.9g isocyanic ester that has mixed after shaking up 2 minutes in 30 seconds in the inherent said mixture then (is 2,4-and 2, the mixture of 6-tolylene diisocyanate, wherein mol ratio 2,4-tolylene diisocyanate: 2,6-tolylene diisocyanate=4: 1) and the mixture of 54.9g polyether glycol, continue again to stir 50 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 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 45% high solids content polyurea polylol product.
The high solids content polyurea polylol that obtains is a milky white liquid, and adopting NDJ-1 type rotary viscosimeter instrument to record its viscosity is 7100mpas; 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
Add the hydrazine hydrate (hydrazine content is 80%) of 330N polyether glycol, 20g butyleneglycol (accounting for gross weight 9.2%) and the 25.8g of 102.8g in four-hole boiling flask, connect thermometer and stirring arm, continuously stirring is 5 minutes at normal temperatures; Adding the 42.7g isocyanic ester that has mixed after shaking up 1 minute in 30 seconds in the inherent said mixture then (is 2,4-and 2, the mixture of 6-tolylene diisocyanate, wherein mol ratio 2,4-tolylene diisocyanate: 2,6-tolylene diisocyanate=4: 1) and the mixture of 42.7g polyether glycol, continue again to stir 45 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 2 hours under 115 ℃ the condition for-0.1MPa, temperature at pressure, removes residual monomer, gets final product to such an extent that solid content is 35% high solids content polyurea polylol product.
The high solids content polyurea polylol that obtains is a milky white liquid, and 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 5
Add the hydrazine hydrate (hydrazine content is 80%) of 330N polyether glycol, 30g ethylene glycol (accounting for gross weight 11%) and the 15.3g of 135.3g in four-hole boiling flask, connect thermometer and stirring arm, continuously stirring is 15 minutes at normal temperatures; Adding the 46.8g isocyanic ester that has mixed after shaking up 45 seconds in 30 seconds in the inherent said mixture then (is 2,4-and 2, the mixture of 6-tolylene diisocyanate, wherein mol ratio 2,4-tolylene diisocyanate: 2,6-tolylene diisocyanate=4: 1) and the mixture of 46.8g polyether glycol, continue again to stir 25 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 100 ℃ the condition for-0.1MPa, temperature at pressure, removes residual monomer, gets final product to such an extent that solid content is 30% high solids content polyurea polylol product.
The high solids content polyurea polylol that obtains is a milky white liquid, and adopting NDJ-1 type rotary viscosimeter instrument to record its viscosity is 4100mpas; 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 6
Add the 330N polyether glycol, 35g ethylene glycol (account for gross weight 14%) of 90.6g and the hydrazine hydrate (hydrazine content is 80%) of 20.7g in four-hole boiling flask, connect thermometer and stirring arm, continuously stirring is 8 minutes at normal temperatures; Adding the 54.9g isocyanic ester that has mixed after shaking up 2 minutes in 30 seconds in the inherent said mixture then (is 2,4-and 2, the mixture of 6-tolylene diisocyanate, wherein mol ratio 2,4-tolylene diisocyanate: 2,6-tolylene diisocyanate=4: 1) and the mixture of 54.9g polyether glycol, continue again to stir 50 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 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 45% high solids content polyurea polylol product.
The high solids content polyurea polylol that obtains is a milky white liquid, and adopting NDJ-1 type rotary viscosimeter instrument to record its 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.
Embodiment 7
Add the 330N polyether glycol, 45g ethylene glycol (account for gross weight 17%) of 102.8g and the hydrazine hydrate (hydrazine content is 80%) of 25.8g in four-hole boiling flask, connect thermometer and stirring arm, continuously stirring is 5 minutes at normal temperatures; Adding the 42.7g isocyanic ester that has mixed after shaking up 1 minute in 30 seconds in the inherent said mixture then (is 2,4-and 2, the mixture of 6-tolylene diisocyanate, wherein mol ratio 2,4-tolylene diisocyanate: 2,6-tolylene diisocyanate=4: 1) and the mixture of 42.7g polyether glycol, continue again to stir 45 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 2 hours under 115 ℃ the condition for-0.1MPa, temperature at pressure, removes residual monomer, gets final product to such an extent that solid content is 35% high solids content polyurea polylol product.
The high solids content polyurea polylol that obtains is a milky white liquid, and adopting NDJ-1 type rotary viscosimeter instrument to record its viscosity is 2200mpas; 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 8
Add the 330N polyether glycol, 95g ethylene glycol (account for gross weight 20%) of 189.3g and the hydrazine hydrate (hydrazine content is 80%) of 23g in four-hole boiling flask, connect thermometer and stirring arm, continuously stirring is 10 minutes at normal temperatures; Adding the 61g isocyanic ester that has mixed after shaking up 30 seconds in 30 seconds in the inherent said mixture then (is 2,4-and 2, the mixture of 6-tolylene diisocyanate, wherein mol ratio 2,4-tolylene diisocyanate: 2,6-tolylene diisocyanate=4: 1) and the mixture of 101.6g polyether glycol, 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, 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 25% high solids content polyurea polylol product.
The high solids content polyurea polylol that obtains is a milky white liquid, and adopting NDJ-1 type rotary viscosimeter instrument to record its viscosity is 1450mpas; 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 (9)
1, a kind of preparation method of high solids content polyurea polylol, the raw material that adopts comprises polyether glycol, hydrazine hydrate and isocyanic ester, wherein the weight ratio of the weight of isocyanic ester and hydrazine and polyether glycol is 0.25～0.45, and the mol ratio of isocyanic ester and hydrazine is 0.8～1.2; It is characterized in that comprising following step:
(1) 62.3%～74.3% the polyether glycol that will account for the polyether glycol total amount adds dibasic alcohol as dispersion agent with after hydrazine hydrate mixes, and stirs then 1～15 minute; The consumption of described dibasic alcohol is 1%～20% of polyether glycol, hydrazine hydrate and an isocyanic ester gross weight;
(2) after being mixed, residual polyether polyol and isocyanic ester shake up 30 seconds～5 minutes;
(3) mixture that step (2) is obtained added in 30 seconds～3 minutes in the mixture that step (1) obtains, and mixed; 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 high solids content polyurea polylol product.
2, the preparation method of high solids content polyurea polylol according to claim 1 is characterized in that: the mol ratio of residual polyether polyol and isocyanic ester is 0.5～2 in the described step (2).
3, the preparation method of high solids content polyurea polylol according to claim 1 is characterized in that: described dibasic alcohol is that molecular weight is lower than 200 dibasic alcohol.
4, the preparation method of high solids content polyurea polylol according to claim 3 is characterized in that: it is in ethylene glycol, propylene glycol or the butyleneglycol any that described molecular weight is lower than 200 dibasic alcohol.
5, the preparation method of high solids content polyurea polylol according to claim 1 is characterized in that: the consumption of described dibasic alcohol is 5%～10% of polyether glycol, hydrazine hydrate and an isocyanic ester gross weight.
6, the preparation method of high solids content polyurea polylol according to claim 1 is characterized in that: in the described step (1), polyether glycol is mixed the back and adds dibasic alcohol as dispersion agent with hydrazine hydrate, stirred then 5～10 minutes.
7, the preparation method of high solids content polyurea polylol according to claim 1 is characterized in that: in the described step (2), shake up 30 seconds after polyether glycol and isocyanic ester mixed～2 minutes.
8, the preparation method of high solids content polyurea polylol according to claim 1 is characterized in that: in the described step (3), the mixture that step (2) is obtained continues to stir 10～60 minutes after pouring the mixture that step (1) obtains into.
9, the preparation method of high solids content 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 |
|---|---|---|---|
| CN 03140323 CN1247664C (en) | 2003-08-29 | 2003-08-29 | Process for preparing high solid content polyurea polyol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03140323 CN1247664C (en) | 2003-08-29 | 2003-08-29 | Process for preparing high solid content polyurea polyol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1491969A CN1491969A (en) | 2004-04-28 |
| CN1247664C true CN1247664C (en) | 2006-03-29 |
Family
ID=34240282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03140323 Expired - Fee Related CN1247664C (en) | 2003-08-29 | 2003-08-29 | Process for preparing high solid content polyurea polyol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1247664C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107226899A (en) * | 2017-06-28 | 2017-10-03 | 常州武城服饰有限公司 | A kind of imitated wood material and preparation method thereof |
| CN116574230A (en) * | 2023-03-30 | 2023-08-11 | 佛山市惠安家居用品有限公司 | Flame-retardant sound-insulation sponge and preparation method thereof |
-
2003
- 2003-08-29 CN CN 03140323 patent/CN1247664C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1491969A (en) | 2004-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1129620C (en) | Polyurethane prepolymer compositions, foams made therefrom and methods of making each thereof | |
| CN1084755C (en) | Low-viscosity polymeric polyols, process for their preparation and their use for manufacture of polyurethane foams | |
| EP1163290A2 (en) | Diol latex compositions and modified condensation polymers | |
| CN102993406B (en) | Preparation method of high-transparency UV resistant curing polyurethane-zinc oxide nano composite resin | |
| JPH0541648B2 (en) | ||
| JPS6150091B2 (en) | ||
| CN112675794A (en) | Liquid crystal microcapsule and preparation method thereof | |
| AU727418B2 (en) | Polyisocyanate based xerogels | |
| CN1253490C (en) | Method for preparing fire-retardant polyether by cyanuramide | |
| CN1247664C (en) | Process for preparing high solid content polyurea polyol | |
| CN113861394B (en) | Preparation method of poly (terephthalic acid) -adipic acid-butanediol copolyester | |
| JPS63225349A (en) | Aqueous composition of thermal reaction type | |
| EP0062598B1 (en) | Storage flowable polypropylene ether urethane composition | |
| CN1189497C (en) | Method for preparing polyurea polybasic alcohol | |
| US4273901A (en) | Dispersible vinylidene chloride polymer microgel powders as additives for polymers | |
| EP0971965B1 (en) | Polyisocyanate based xerogels | |
| JPH06329837A (en) | Production of polymer-bound rubber chemical | |
| US4232129A (en) | Dispersible vinylidene chloride polymer microgel powders as additives for urethane polymer foam | |
| CN114854009B (en) | Polyimide foam and preparation method thereof | |
| US5173530A (en) | Stable dispersions of polyols containing polyvinylchloride | |
| JP3254710B2 (en) | Method for producing powdery polyurethane resin | |
| CN1041165A (en) | But foamable polymer that polyphenylene oxide and vinyl aromatic compounds are made and its production and application | |
| JPH05148338A (en) | Modified polyisocyanates and their manufacture | |
| JPH04117456A (en) | Aqueous silicone emulsion composition and preparation of silicone powder therefrom | |
| JP2734080B2 (en) | Non-aqueous dispersion type resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Guangzhou Longtang Polyurethane Co., Ltd. Assignor: South China University of Technology Contract fulfillment period: 2008.1.1 to 2014.1.1 contract change Contract record no.: 2009440000547 Denomination of invention: Process for preparing high solid content polyurea polyol Granted publication date: 20060329 License type: Exclusive license Record date: 2009.7.2 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.1.1 TO 2014.1.1; CHANGE OF CONTRACT Name of requester: GUANGZHOU LONG TANG POLYURETHANE CO.,LTD. Effective date: 20090702 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060329 Termination date: 20140829 |
|
| EXPY | Termination of patent right or utility model |