CN1974630A - Prepn process of high and medium molecular weigh polyether allyl monoalcohol - Google Patents
Prepn process of high and medium molecular weigh polyether allyl monoalcohol Download PDFInfo
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- CN1974630A CN1974630A CN 200610097889 CN200610097889A CN1974630A CN 1974630 A CN1974630 A CN 1974630A CN 200610097889 CN200610097889 CN 200610097889 CN 200610097889 A CN200610097889 A CN 200610097889A CN 1974630 A CN1974630 A CN 1974630A
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Abstract
The high and medium molecular weight polyether allyl monoalcohol is prepared with single functionality degree polyether allyl monoalcohol with molecular weight of 300-1000 and containing double bond as initiating agent and epoxide as material, and through bubbling in inert atmosphere to degas and reaction at 100-160 deg.c and under the action of double metal cyanide catalyst. It has hydroxyl value of 11-28 mgKOH/g, double bond content of 0.2-0.48 mmol/g, water content of 30-40 ppm, and molecular weight of 2000-5000. The preparation process is simple and low in cost.
Description
Technical field
The present invention relates to the preparation method of a kind of middle and high molecular weight allyl polyether unit alcohol.
Background technology
Allyl polyether unit alcohol is main to be used special propertys such as two keys of polyether units alcohol and lubrication that the reaction of various active group provides the pure segment of polyether units, soft effect, good spreadability and emulsifying stability and is incorporated in the fine chemical product of various novel multifunctional.The allyl polyether unit alcohol that traditional technology is produced, if when having about propylene oxide more than 20% in the alkyl oxide, just can not prepare the polyether units alcohol of molecular weight at the middle and high molecular weight more than 2000, and in existing a lot of products, needing to contain the propylene oxide segment, this has just caused serious limitation.
The catalytic polyreaction of traditional KOH belongs to anionic reactive, and in polyreaction, chain initiation and chainpropagation is based on the rapid transfer of proton, and reaction is in case cause, and in the stage of initial growth, the speed of transfer reaction is very fast.Along with the further growth of molecular chain and the adding gradually of reaction mass, proton slows down owing to factor affecting such as being subjected to active group relative concentration step-down and the increase of system viscosity to the speed that macromolecular chain shifts, and causes the transformation efficiency of epoxide to reduce and the rate of side reactions quickening.A spot of propylene oxide is constantly reset and is allyl alcohol simultaneously, allyl alcohol is as a kind of new unsaturated starting raw material and the competition of original starting raw material, finally reach a certain balance, the further adding of propylene oxide can not make the total molecular weight of polyether units alcohol product increase under this condition, in other words, attempting to increase in the process of molecular weight, produce the oligopolymer competition of increasing low molecular weight substance and already present chainpropagation, and total number-average molecular weight of polyether units alcohol product does not increase, molecular weight distribution is broadened, and actual relative molecular weight is lower than theoretical molecular.
Summary of the invention
Technical problem to be solved by this invention is to exist in the conventional art when high-molecular-weight poly ether unit is pure in the preparation to be difficult to control the molecular weight double bond content corresponding with it with traditional Technology, cause the wild effect of derived product in follow-up product application, the production cost that has improved conventional process techniques in addition is too high.
The method that the purpose of this invention is to provide a kind of new middle and high molecular weight allyl polyether of preparation unit alcohol.When this method was used for epoxide polymerization, it was low to have bimetallic catalyst concentration in finished product, and inductive phase is short, and the allyl polyether unit alcohol that makes simultaneously has narrow molecular weight distribution, and molecular weight and degree of unsaturation are near the characteristics of theoretical value.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows:
The preparation method of a kind of middle and high molecular weight allyl polyether unit alcohol, it is to be that 400～1000 single functionality allyl polyether unit alcohol that contain two keys are initiator with molecular weight, with the epoxy compounds is raw material, the bubbling degassing under inert gas atmosphere, in the presence of catalyzer, react the middle and high molecular weight allyl polyether of generation unit alcohol under 100～160 ℃ temperature of reaction, used catalyzer is double metal cyanide (DMC) catalyzer.
The molecular weight preferable range of initiator is 400～1000, and the active hydrogen functional groups number is 1; Preferably adding scheme of epoxy compounds is to add in the reaction system in bubbling degassing back.The concentration preferable range of catalyzer in finished product is 30～200ppm; More preferably scope is 30～100ppm; The rare gas element preferred version is selected from least a in nitrogen, carbonic acid gas, the argon gas, and more preferably scheme is for being selected from nitrogen; The temperature preferable range of the bubbling degassing is 100～130 ℃, and more preferably scope is 100～120 ℃; The vacuum tightness preferable range of the bubbling degassing be-0.095～-0.075MPa, the bubbling time preferable range that outgases is 30～90 minutes, more preferably scope is 30～60 minutes; The epoxy compounds preferred version is one or more the mixture that is selected from oxyethane, propylene oxide, the butylene oxide ring.
Hydroxyl value with the allyl polyether unit alcohol of present method preparation is 11～28mgKOH/g, and double bond content is 0.2～0.48mmol/g, and water content is 30～40ppm, and molecular weight is 2000～5000.Present method technology is simple, and cost is low.
Embodiment
[embodiment 1]
The propylene oxide polymerization
With 90 gram initiator (M
n=400 polyoxytrimethylene allyl polyether unit alcohol) and 0.027 the gram DMC catalysts (trade mark is ZSN, purchase in Nanjing petrochemical industry research institute, down with) mixture joins in 1 liter the stainless steel voltage-resistant reactor, be evacuated to-0.080MPa, the bubbling degassing 60 minutes, pour nitrogen then to 1MPa, be evacuated to again-0.095MPa, be warming up to 100 ℃, add 30 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keeps temperature of reactor at 105～110 ℃, and (can see the inductive phase of catalyzer as) post-reactor pressure obviously reduced in 25 minutes, the temperature of keeping reactor adds 330 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, when the pressure of reactor no longer changes, show that reaction finishes, 32 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cooling obtains allyl polyether unit alcohol 445 grams.
By analysis: the hydroxyl value of allyl polyether unit alcohol is 28.10mgKOH/g, and double bond content is 0.48mmol/g, and water content is 30ppm, and molecular weight is 1999.
[embodiment 2]
The propylene oxide polymerization
With 90 gram initiator (M
n=400 polyoxytrimethylene allyl polyether unit alcohol) and 0.027 gram DMC catalysts mixture join in 1 liter the stainless steel voltage-resistant reactor, be evacuated to-0.085MPa, the bubbling degassing 60 minutes, pour nitrogen then to 1MPa, be evacuated to again-0.095MPa, be warming up to 100 ℃, add 30 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keep temperature of reactor at 105～110 ℃, (can see the inductive phase of catalyzer as) post-reactor pressure obviously reduced in 25 minutes, the temperature of keeping reactor adds 555 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, when the pressure of reactor no longer changes, show that reaction finishes, 32 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cooling obtains allyl polyether unit alcohol 660 grams.
By analysis: the hydroxyl value of allyl polyether unit alcohol is 18.75mgKOH/g, and double bond content is 0.322mmol/g, and water content is 40ppm, and molecular weight is 2992.
[embodiment 3]
The propylene oxide polymerization
With 90 gram initiator (M
n=400 polyoxytrimethylene allyl polyether unit alcohol) and 0.027 gram DMC catalysts mixture join in 1 liter the stainless steel voltage-resistant reactor, be evacuated to-0.085MPa, the bubbling degassing 30 minutes, pour nitrogen then to 1MPa, be evacuated to again-0.095MPa, be warming up to 100 ℃, add 30 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keep temperature of reactor at 105～110 ℃, (can see the inductive phase of catalyzer as) post-reactor pressure obviously reduced in 25 minutes, the temperature of keeping reactor adds 780 gram propylene oxide continuously under 105～110 ℃ situation, make reactor pressure be no more than 0.20MPa, after propylene oxide adds, when the pressure of reactor no longer changes, show that reaction finishes, 32 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cooling obtains allyl polyether unit alcohol 895 grams.
By analysis: the hydroxyl value of allyl polyether unit alcohol is 14.12mgKOH/g, and double bond content is 0.228mmol/g, and water content is 32ppm, and molecular weight is 3973.
[embodiment 4]
The propylene oxide polymerization
With 220 gram initiator (M
n=1000 polyoxytrimethylene allyl polyether unit alcohol) and 0.027 gram DMC catalysts mixture join in 1 liter the stainless steel voltage-resistant reactor, be evacuated to-0.085MPa, the bubbling degassing 60 minutes, pour nitrogen then to 1MPa, be evacuated to again-0.095MPa, be warming up to 100 ℃, add 30 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keep temperature of reactor at 105～110 ℃, (can see the inductive phase of catalyzer as) post-reactor pressure obviously reduced in 25 minutes, the temperature of keeping reactor adds 780 gram propylene oxide continuously under 105 ~ 110 ℃ situation, make reactor pressure be no more than 0.25MPa, after propylene oxide adds, when the pressure of reactor no longer changes, show that reaction finishes, 30 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cooling obtains allyl polyether unit alcohol 1092 grams.
By analysis: the hydroxyl value of allyl polyether unit alcohol is 14.22mgKOH/g, and double bond content is 0.231mmol/g, and water content is 35ppm, and molecular weight is 4545.
[embodiment 5]
Propylene oxide and oxyethane compare mixed polymerization with 3: 2 quality
With 90 gram initiator (M
n=400 polyoxytrimethylene allyl polyether unit alcohol) and 0.027 gram DMC catalysts mixture join in 1 liter the stainless steel voltage-resistant reactor, be evacuated to-0.085MPa, the bubbling degassing 60 minutes, pour nitrogen then to 1MPa, be evacuated to again-0.095MPa, be warming up to 100 ℃, add 30 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keep temperature of reactor at 105～110 ℃, (can see the inductive phase of catalyzer as) post-reactor pressure obviously reduced in 25 minutes, the temperature of keeping reactor adds 780 gram propylene oxide continuously under 105～110 ℃ situation, oxyethane mixture (mass ratio of propylene oxide and oxyethane is 3: 2), make reactor pressure be no more than 0.20MPa, propylene oxide, after the oxyethane mixture adds, when no longer changing, the pressure of reactor shows that reaction finishes, 40 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cooling obtains allyl polyether unit alcohol 889 grams.
By analysis: the hydroxyl value of allyl polyether unit alcohol is 13.75mgKOH/g, and double bond content is 0.229mmol/g, and water content is 40ppm, and molecular weight is 4080.
[embodiment 6]
The propylene oxide polymerization
With 90 gram initiator (M
n=400 polyoxytrimethylene allyl polyether unit alcohol) and 0.027 gram DMC catalysts mixture join in 1 liter the stainless steel voltage-resistant reactor, be evacuated to-0.085MPa, the bubbling degassing 60 minutes, pour nitrogen then to 1MPa, be evacuated to again-0.095MPa, be warming up to 100 ℃, add 30 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keep temperature of reactor at 105～110 ℃, (can see the inductive phase of catalyzer as) post-reactor pressure obviously reduced in 25 minutes, the temperature of keeping reactor adds 920 gram propylene oxide continuously under 105 ~ 110 ℃ situation, make reactor pressure be no more than 0.25MPa, after propylene oxide adds, when the pressure of reactor no longer changes, show that reaction finishes, 40 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cooling obtains allyl polyether unit alcohol 1030 grams.
By analysis: the hydroxyl value of allyl polyether unit alcohol is 12.26mgKOH/g, and double bond content is 0.21mmol/g, and water content is 35ppm, and molecular weight is 4578.
[embodiment 7]
Propylene oxide and oxyethane were with 3: 2 weight ratio mixed polymerization
With 90 gram initiator (M
n=400 polyoxytrimethylene allyl polyether unit alcohol) and 0.027 gram DMC catalysts mixture join in 1 liter the stainless steel voltage-resistant reactor, be evacuated to-0.085MPa, the bubbling degassing 60 minutes, pour nitrogen then to 1MPa, be evacuated to again-0.095MPa, be warming up to 100 ℃, add 30 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keep temperature of reactor at 105～110 ℃, (can see the inductive phase of catalyzer as) post-reactor pressure obviously reduced in 25 minutes, the temperature of keeping reactor adds 1005 gram propylene oxide continuously under 105～110 ℃ situation, oxyethane mixture (mass ratio of propylene oxide and oxyethane is 3: 2), make reactor pressure be no more than 0.20MPa, propylene oxide, after the oxyethane mixture adds, when no longer changing, the pressure of reactor shows that reaction finishes, 55 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cooling obtains allyl polyether unit alcohol 1124 grams.
By analysis: the hydroxyl value of allyl polyether unit alcohol is 11.3mgKOH/g, and double bond content is 0.208mmol/g, and water content is 40ppm, and molecular weight is 4965.
[embodiment 8]
Propylene oxide and butylene oxide ring were with 3: 2 weight ratio mixed polymerization
With 90 gram initiator (M
n=400 polyoxytrimethylene allyl polyether unit alcohol) and 0.027 gram DMC catalysts mixture join in 1 liter the stainless steel voltage-resistant reactor, be evacuated to-0.085MPa, the bubbling degassing 60 minutes, pour nitrogen then to 1MPa, be evacuated to again-0.095MPa, be warming up to 100 ℃, add 50 gram propylene oxide, reactor pressure rises to 0.20MPa rapidly, keep temperature of reactor at 105～110 ℃, (can see the inductive phase of catalyzer as) post-reactor pressure obviously reduced in 25 minutes, the temperature of keeping reactor adds 760 gram propylene oxide continuously under 105～110 ℃ situation, the butylene oxide ring mixture, make reactor pressure be no more than 0.20MPa, propylene oxide, after the butylene oxide ring mixture adds, when no longer changing, the pressure of reactor shows that reaction finishes, 45 minutes total reaction times, vacuumize and remove the unreacted residual monomer, cooling obtains allyl polyether unit alcohol 880 grams.
By analysis: the hydroxyl value of allyl polyether unit alcohol is 13.36mgKOH/g, and double bond content is 0.220mmol/g, and water content is 40ppm, and molecular weight is 4200.
Claims (6)
1. the preparation method of a middle and high molecular weight allyl polyether unit alcohol, it is characterized in that: it is to be that 400～1000 single functionality allyl polyether unit alcohol that contain two keys are initiator with molecular weight, with the epoxy compounds is raw material, under inert gas atmosphere, in the presence of catalyzer, react the middle and high molecular weight allyl polyether of generation unit alcohol under 100～160 ℃ temperature of reaction, described catalyzer is a DMC catalysts.
2. preparation method according to claim 1 is characterized in that: the concentration range of described catalyzer in finished product is 30～200ppm.
3. preparation method according to claim 1 is characterized in that: the concentration range of described catalyzer in finished product is 30～100ppm.
4. preparation method according to claim 1 is characterized in that: described rare gas element is selected from a kind of in nitrogen, carbonic acid gas, the argon gas.
5. preparation method according to claim 1 is characterized in that: described rare gas element is for being selected from nitrogen.
6. preparation method according to claim 1 is characterized in that: described epoxy compounds is selected from one or more the mixture in oxyethane, propylene oxide, the butylene oxide ring.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200610097889 CN1974630A (en) | 2006-11-20 | 2006-11-20 | Prepn process of high and medium molecular weigh polyether allyl monoalcohol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885839B (en) * | 2009-05-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing blocked allyl polyether |
| CN106750241A (en) * | 2017-02-06 | 2017-05-31 | 山东诺威新材料有限公司 | The preparation method of the allyl polyether polyalcohol of secondary hydroxyl end-blocking |
| CN107510960A (en) * | 2017-08-21 | 2017-12-26 | 沈阳浩博实业有限公司 | A kind of high-molecular-weight poly ether defoaming agent and preparation method thereof |
-
2006
- 2006-11-20 CN CN 200610097889 patent/CN1974630A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885839B (en) * | 2009-05-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing blocked allyl polyether |
| CN106750241A (en) * | 2017-02-06 | 2017-05-31 | 山东诺威新材料有限公司 | The preparation method of the allyl polyether polyalcohol of secondary hydroxyl end-blocking |
| CN107510960A (en) * | 2017-08-21 | 2017-12-26 | 沈阳浩博实业有限公司 | A kind of high-molecular-weight poly ether defoaming agent and preparation method thereof |
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