CN103665366B - A kind of method of continuous synthesis polyethers - Google Patents
A kind of method of continuous synthesis polyethers Download PDFInfo
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- CN103665366B CN103665366B CN201310632534.1A CN201310632534A CN103665366B CN 103665366 B CN103665366 B CN 103665366B CN 201310632534 A CN201310632534 A CN 201310632534A CN 103665366 B CN103665366 B CN 103665366B
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Abstract
The invention discloses a kind of method of continuous synthesis polyethers, adopt two still two point mode continuously feeding, reactor 1,2 series connection, establish a feed points respectively, wherein reactor 1 feed points adds initiator, dmc catalyst and epoxy alkane compound continuously, synthesize reach design molecular weight 50% ~ 99% polyethers, then material exports to reactor 2 continuously by reactor 1, adds epoxy alkane compound continuously in reactor 2, and synthesis reaches the polyethers of design molecular weight.The inventive method products obtained therefrom had both reduced polymer hangover, significantly improved again low molecule conditions of streaking, had narrow molecular weight distribution.
Description
Technical field
The present invention relates to the method for continuous synthesis polyethers, particularly adopt the polyethers of high reactivity double metal cyanide catalyst continuous production narrow molecular weight distributions.
Background technology
The technique of use bimetallic cyaniding complex (DMC) catalyzer, continuous synthesis polyethers adds epoxy alkane compound, initiator and catalyzer continuously, derives the novel polyether synthesis technique of polyether product continuously.
A kind of continuous production method of polyethers is disclosed in patent documentation CN1310998C.Be characterized in that the reaction unit adopting multistage to be uniformly mixed groove reaches the object of continuous synthesis polyether glycol.But it is that multistage is uniformly mixed groove that the method exists required conversion unit, and reaction unit is complicated.
A kind of method of continuous production polyether glycol is disclosed in patent documentation CN101302287B.It is simple that the method has technical process, do not need " pre-activate " of carrying out catalyzer, olefin oxide only needs add at single entrance and can react rapidly, and can reach in next slaking reaction device and transform completely and do not need to remove the advantage of residual monomer.But the molecular weight distributing index of gained polyethers is wider.
A kind of continuous preparation method of polyether glycol is disclosed in patent documentation CN100497438C, principal feature drops into the initiator containing dmc catalyst in a kettle., with nitrogen sweep except air, vacuumize, stir, heat up, in reactor, add epoxy compounds continuously, make to reach induced pressure in reactor, when reactor temperature rising, pressure drop, continue to pass into epoxy compounds to reactor, keep reactor temperature to be 90 ~ 200 DEG C, pressure-0.05 ~ 1.0MPa.Then in reactor, add the initiator containing DMC catalysts and epoxy compounds in proportion continuously simultaneously.After reactor is full of, reactant flows into aging still and continues reaction, and the temperature of aging still remains on 100 ~ 180 DEG C.Contents In Polyether Polyol enters product storage tank by after aging still discharging.But the method is only that dmc catalyst is mixed with initiator, and when using conventional small molecular alcohol initiator as water, propylene glycol, glycerine etc., DMC is in contact with it and is easy to cause the activity of DMC to reduce, and loses activity even.And the method is single still single-point feeding process, small molecules hangover is larger.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of continuous synthesis polyethers, and the polyethers adopting the method to prepare both had decreased polymer hangover, significantly improved again low molecule conditions of streaking, had narrow molecular weight distribution characteristic.
Technical solution of the present invention adopts two still two point mode continuously feeding, reactor 1,2 series connection, establish a feed points respectively, wherein reactor 1 feed points adds initiator, dmc catalyst and epoxy alkane compound continuously, synthesize reach design molecular weight 50% ~ 99% polyethers, then material exports to reactor 2 continuously by reactor 1, add epoxy alkane compound continuously in reactor 2, synthesis reaches the polyethers of design molecular weight.
Specifically comprise the following steps:
(1) low molecular polyether and dmc catalyst are joined vacuum-drying in reactor 1, after drying completes, add epoxy alkane compound, carry out induced reaction, when reactor temperature rising, pressure drop, reaction induced success.It is 110 ~ 170 DEG C in temperature of reaction, preferably 120 ~ 150 DEG C, reaction pressure is 0 ~ 0.9MPa, preferably under 0.1 ~ 0.5MPa condition, epoxy alkane compound is joined continuously in this reactor 1, make the pfpe molecule amount in reactor 1 reach 50% ~ 99% of design molecular weight, preferably reach 70% ~ 95%.
(2) initiator, dmc catalyst and epoxy alkane compound are joined in reactor 1 in proportion continuously, make the pfpe molecule amount in reactor 1 reach molecular weight in step (1).
(3) reactor 1 is full of rear continuously to reactor 2 discharging, and add epoxy alkane compound continuously to reactor 2, make the pfpe molecule amount in reactor 2 reach design molecular weight, question response still 2 is full of rear continuous discharge simultaneously.
The number-average molecular weight of low molecular polyether is generally 200 ~ 3000 better.
Initiator described in the present invention is low molecular polyether or small molecular alcohol, and functionality is 1 ~ 8, and preferred functionality is 1 ~ 3; Single functionality polyether initiator number-average molecular weight is generally 32 ~ 1000, preferred molecular weight 32 ~ 500; Two functionality molecular weight are generally 72 ~ 2000, preferred molecular weight 72 ~ 400; Three-functionality-degree molecular weight is generally 92 ~ 3000, preferred molecular weight 92 ~ 400.Small molecular alcohol initiator refers to: single functionality is as the C such as methyl alcohol, ethanol
1-C
8alcohol, the C such as n-Octanol, triacontanol
8-C
30fatty alcohol, the unsaturated alcohol such as hexalin, vinyl carbinol etc., two functionality alcohol are as ethylene glycol, propylene glycol, and Isosorbide-5-Nitrae butyleneglycol, glycol ether or Triethylene glycol etc., three-functionality-degree alcohol is as glycerol etc.
Epoxy alkane compound described in the present invention is as propylene oxide, oxyethane or trimethylene oxide and composition thereof etc., preferred propylene oxide or propylene oxide ethylene oxide mixture.Its oxypropylene ethylene oxide mixture weight ratio is propylene oxide: oxyethane=100 ~ 10: 0 ~ 90, preferred propylene oxide: oxyethane=100 ~ 30: 0 ~ 70.
The inventive method adopts two still two point feeding manner continuous synthesis polyethers, and products obtained therefrom had both reduced polymer hangover, significantly improved again low molecule conditions of streaking, had narrow molecular weight distribution characteristic.
Accompanying drawing explanation
Fig. 1 is gained polyethers GPC spectrogram of the present invention.
Fig. 2 is prior art gained polyethers GPC spectrogram.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
The initiator 204 polyethers (polyoxypropyleneglycol of two functionality molecular weight 400 of 400g is added in 5 liters of reactors 1, lower same) and 0.060gDMC catalyzer, vacuum-drying, slowly adds 80g propylene oxide after drying completes, and maintains 130 DEG C and carries out induced reaction.Catalyzer induced activation is shown when temperature constantly raises constantly to decline with pressure.After having induced, maintain 130 DEG C, under 0.2MPa, in reactor 1, add 1420g propylene oxide continuously.Then pass into propylene oxide according to the speed of 4500g/h, the ratio being simultaneously 4: 15: 0.0006 in 204 polyether/epoxy resin propane/DMC weight ratios adds 204 polyethers and dmc catalyst.After question response still 1 is full of, material enters in reactor 2, and the temperature maintaining reactor 2 is 130 DEG C, and pressure is 0.2MPa, adds propylene oxide with the feed rate of 300g/h in reactor 2.Question response still 2 is full of rear continuous discharge, obtains polyoxypropyleneglycol product.Products obtained therefrom hydroxyl value is 56.08mgKOH/g, degree of unsaturation 0.0028mmol/g, molecular weight distributing index 1.030.
Embodiment 2
In 5 liters of reactors 1, add initiator butyl polyethers (molecular weight 400) and the 0.060gDMC catalyzer of 800g, vacuum-drying, slowly adds 80g propylene oxide after drying completes, and maintains 120 DEG C and carries out induced reaction.Catalyzer induced activation is shown when temperature constantly raises constantly to decline with pressure.After having induced, maintain 120 DEG C, under 0.1MPa, add 720g propylene oxide continuously.Then pass into propylene oxide according to the speed of 1815g/h, the ratio being simultaneously 0.74: 7.26: 0.0003 in propyl carbinol/propylene oxide/DMC weight ratio adds propyl carbinol and dmc catalyst.After question response still 1 is full of, material enters in reactor 2, and holding temperature is 120 DEG C, and pressure is 0.1MPa, adds propylene oxide with the feed rate of 500g/h in reactor 2.Question response still 2 is full of rear continuous discharge, obtains butyl polyether product.Products obtained therefrom hydroxyl value is 56.09mgKOH/g, degree of unsaturation 0.0029mmol/g, molecular weight distributing index 1.043.
Embodiment 3
In 5 liters of reactors 1, add allyl polyether (molecular weight 400) and the 0.060gDMC catalyzer of 400g, vacuum-drying, slowly adds 80g propylene oxide after drying completes, and maintains 110 DEG C and carries out induced reaction.Constantly decline with pressure when temperature constantly raises, show catalyzer induced activation.After having induced, maintain 110 DEG C, under 0.3MPa, add 1420g propylene oxide continuously.Then pass into propylene oxide according to the speed of 1842g/h, the ratio being simultaneously 0.58: 18.42: 0.0006 in vinyl carbinol/propylene oxide/DMC weight ratio adds vinyl carbinol and dmc catalyst.After question response still 1 is full of, material enters in reactor 2, and holding temperature is 110 DEG C, and pressure is 0.3MPa, adds propylene oxide with the speed of 100g/h in reactor 2.Question response still 2 is full of rear continuous discharge, obtains allyl polyether product.Products obtained therefrom hydroxyl value is 28.03mgKOH/g, molecular weight distributing index 1.045.
Embodiment 4
220 polyethers (the polyoxypropyleneglycol of two functionality molecular weight 2000 of 400g is added in 5 liters of reactors 1, lower same) and 0.060gDMC catalyzer, vacuum-drying, slowly adds 80g propylene oxide after drying completes, and maintains 150 DEG C and carries out induced reaction.Constantly decline with pressure when temperature constantly raises, show catalyzer induced activation.After having induced, maintain 150 DEG C, under 0.5MPa, add 1460g propylene oxide continuously.Then pass into propylene oxide according to the feed rate of 9624g/h, the ratio being simultaneously 0.76: 96.24: 0.003 in propanediol/propylene oxide/DMC weight ratio adds propylene glycol and dmc catalyst.After question response still 1 is full of, material enters in reactor 2, and maintaining temperature of reaction is 150 DEG C, and pressure is 0.5MPa, adds propylene oxide with the speed of 300g/h in reactor 2.Question response still 2 is full of rear continuous discharge, obtains polyoxypropyleneglycol product.Products obtained therefrom hydroxyl value is 11.20mgKOH/g, degree of unsaturation 0.0028mmol/g, molecular weight distributing index 1.058.
Embodiment 5
In 5 liters of reactors 1, add 204 polyethers and the 0.060gDMC catalyzer of 400g, vacuum-drying, slowly adds 80g propylene oxide after drying completes, and maintains 130 DEG C and carries out induced reaction.Constantly decline with pressure when temperature constantly raises, show catalyzer induced activation.After having induced, maintain 130 DEG C, 1420g propylene oxide, oxyethane (propylene oxide, oxyethane weight ratio are 4: 1) is added continuously under 0.2MPa, then pass into propylene oxide, oxyethane according to the feed rate of 4500g/h, the ratio being simultaneously 4: 12: 3: 0.0006 in 204/ propylene oxide/oxyethane/DMC weight ratio adds 204 polyethers and dmc catalyst.After question response still 1 is full of, material enters in reactor 2, the temperature maintaining reactor 2 is 130 DEG C, and pressure is 0.2MPa, adds propylene oxide, oxyethane (propylene oxide, oxyethane weight ratio are for 4: 1) with the feed rate of 300g/h in reactor 2.Question response still 2 is full of rear continuous discharge, obtains polyoxytrimethylene ethylene glycol product.Products obtained therefrom hydroxyl value is 56.09mgKOH/g, degree of unsaturation 0.0029mmol/g, molecular weight distributing index 1.052.
Embodiment 6
305 polyethers (the polyoxypropyleneglycol of three-functionality-degree molecular weight 500 of 500g is added in 5 liters of reactors 1, lower same) and 0.090gDMC catalyzer, vacuum-drying, slowly adds 100g propylene oxide after drying completes, and maintains 140 DEG C and carries out induced reaction.Constantly decline with pressure when temperature constantly raises, show catalyzer induced activation.After having induced, maintain 140 DEG C, under 0.2MPa, add 2100g propylene oxide continuously.Then pass into propylene oxide according to the speed of 4600g/h, the ratio being simultaneously 5: 23: 0.0006 in 305 polyether/epoxy resin propane/DMC weight ratios adds 305 polyethers and dmc catalyst.After question response still 1 is full of, material enters in reactor 2, and the temperature maintaining reactor 2 is 140 DEG C, and pressure is 0.2MPa, adds propylene oxide with the speed of 400g/h in reactor 2.Question response still 2 is full of rear continuous discharge, obtains polyoxytrimethylene triol product.Products obtained therefrom hydroxyl value is 55.97mgKOH/g, degree of unsaturation 0.0032mmol/g, molecular weight distributing index 1.054.
Embodiment 7
In 5 liters of reactors 1, add 204 polyethers and the 0.060gDMC catalyzer of 400g, vacuum-drying, slowly adds 80g propylene oxide after drying completes, and maintains 135 DEG C and carries out induced reaction.Catalyzer induced activation is shown when temperature constantly raises constantly to decline with pressure.After having induced, maintain 135 DEG C, under 0.5MPa, add 1420g propylene oxide continuously.Propylene oxide is passed into the speed of 5472g/h, the ratio being simultaneously 0.76: 18.24: 0.0006 according to the weight ratio of propanediol/propylene oxide/DMC adds propylene glycol and DMC, after question response still 1 is full of, material enters in reactor 2, the temperature maintaining reactor 2 is 135 DEG C, pressure is 0.5MPa, to add propylene oxide in the feed rate reactor 2 of 300g/h.Question response still 2 is full of rear continuous discharge, obtains polyoxypropyleneglycol product.Products obtained therefrom hydroxyl value is 56.20mgKOH/g, degree of unsaturation 0.0034mmol/g, molecular weight distributing index 1.056.
Embodiment 8
In 5 liters of reactors 1, add 220 polyethers and the 0.060gDMC catalyzer of 400g, vacuum-drying, slowly adds 80g propylene oxide after drying completes, and maintains 160 DEG C and carries out induced reaction.Catalyzer induced activation is shown when temperature constantly raises constantly to decline with pressure.After having induced, maintain 160 DEG C, under 0.4MPa, add 1420g propylene oxide, oxyethane (propylene oxide: oxyethane weight ratio is 3: 2) continuously.Then propylene oxide, oxyethane is passed into the speed of 9000g/h, add 220 polyethers and DMC according to the ratio of the weight ratio 4: 9: 6: 0.0006 of 220 polyether/epoxy resin propane/oxyethane/DMC simultaneously, after question response still 1 is full of, the temperature maintaining reactor 2 is 160 DEG C, pressure is 0.4MPa, adds propylene oxide, oxyethane (propylene oxide: oxyethane weight ratio is for 3: 2) with the feed rate of 300g/h in reactor 2.Question response still 2 is full of rear continuous discharge, obtains polyoxytrimethylene ethylene glycol product.Products obtained therefrom hydroxyl value is 11.09mgKOH/g, degree of unsaturation 0.0031mmol/g, molecular weight distributing index 1.062.
Embodiment 9
In 5 liters of reactors 1, add 305 polyethers and the 0.090gDMC catalyzer of 500g, vacuum-drying, slowly adds 100g propylene oxide after drying completes, and maintains 140 DEG C and carries out induced reaction.Catalyzer induced activation is shown when temperature constantly raises constantly to decline with pressure.After having induced, maintain 140 DEG C, under 0.3MPa, add 2100g propylene oxide continuously.Propylene oxide is passed into 5416g/h speed, the ratio being simultaneously 0.92: 27.08: 0.0006 according to glycerol/propylene oxide/DMC weight ratio adds glycerol and DMC, after question response still 1 is full of, material enters in reactor 2, the temperature maintaining reactor 2 is 140 DEG C, pressure is 0.3MPa, adds propylene oxide with the speed of 400g/h in reactor 2.Question response still 2 is full of rear continuous discharge, obtains polyoxytrimethylene triol product.Products obtained therefrom hydroxyl value is 56.05mgKOH/g, degree of unsaturation 0.0038mmol/g, molecular weight distributing index 1.061.
Embodiment 10
204 polyethers and the 30gDMC catalyzer of 200kg is added in the reactor 1 of 2 cubic metres, vacuum-drying, slowly adds 40kg propylene oxide after drying completes, and maintains 140 DEG C and carries out induced reaction, constantly decline with pressure when temperature constantly raises, show catalyzer induced activation.After having induced, maintain 130 DEG C, under 0.2MPa, add 710kg propylene oxide continuously.Then add propylene oxide according to the speed of 1500kg/h, the ratio being simultaneously 4: 15: 0.0006 with 204 polyether/epoxy resin propane/DMC weight ratios adds 204 polyethers and DMC.After question response still 1 is full of, material enters in reactor 2, and the temperature maintaining reactor 2 is 140 DEG C, and pressure is 0.2MPa, to add propylene oxide in the feed rate reactor 2 of 100kg/h.Question response still 2 is full of rear continuous discharge, obtains polyoxypropyleneglycol product.Products obtained therefrom hydroxyl value is 56.11mgKOH/g, degree of unsaturation 0.0038mmol/g, molecular weight distributing index 1.067.
Comparative example 1
In 5 liters of reactors 1, add 204 polyethers and the 0.060gDMC catalyzer of 400g, vacuum-drying, slowly adds 80g propylene oxide after drying completes, and maintains 130 DEG C and carries out induced reaction.Constantly decline with pressure when temperature constantly raises, show catalyzer induced activation.After having induced, maintain 130 DEG C, under 0.2MPa, add 1420g propylene oxide continuously.Then add propylene oxide according to the speed of 4800g/h, simultaneously with 204 polyether/epoxy resin propane/DMC to be weight ratio be 2: 8: 0.003 ratio add 204 polyethers and DMC.After question response still 1 is full of, material enters in reactor 2, and the temperature of maintenance is 130 DEG C, and pressure is 0.2MPa.Question response still 2 is full of rear continuous discharge, obtains polyoxypropyleneglycol product.Products obtained therefrom hydroxyl value is 55.41mgKOH/g, degree of unsaturation 0.0045mmol/g, molecular weight distributing index 1.109.
Comparative example 2
In 5 liters of reactors 1, add 305 polyethers and the 0.090gDMC catalyzer of 500g, vacuum-drying, slowly adds 100g propylene oxide after drying completes, and maintains 140 DEG C and carries out induced reaction.Catalyzer induced activation is shown when temperature constantly raises constantly to decline with pressure.After having induced, maintain 140 DEG C, under 0.2MPa, add 2100g propylene oxide continuously.Propylene oxide is added with the speed of 5000g/h, the ratio being simultaneously 5: 25: 0.0006 with 305 polyether/epoxy resin propane/DMC weight ratios adds 305 polyethers and DMC, and after question response still 1 is full of, material enters in reactor 2, the temperature maintaining reactor 2 is 140 DEG C, and pressure is 0.2MPa.Question response still 2 is full of rear continuous discharge, obtains polyoxytrimethylene triol product.Products obtained therefrom hydroxyl value is 56.37mgKOH/g, degree of unsaturation 0.0048mmol/g, molecular weight distributing index 1.121.
Each embodiment data are in table 1.
The each embodiment data of table 1
Claims (10)
1. the method for a continuous synthesis polyethers, adopt two still two point mode continuously feeding, reactor 1,2 series connection, establish a feed points respectively, wherein reactor 1 feed points adds initiator, dmc catalyst and epoxy alkane compound continuously, synthesize reach design molecular weight 50% ~ 99% polyethers, after reactor 1 is full of, material exports to reactor 2 continuously by reactor 1, add epoxy alkane compound continuously in reactor 2, synthesis reaches the polyethers of design molecular weight.
2. method according to claim 1, is characterized in that containing following steps:
(1) low molecular polyether and dmc catalyst are joined vacuum-drying in reactor 1, after drying completes, add epoxy alkane compound, carry out induced reaction, when reactor temperature rising, pressure drop, reaction induced success; Be 110 ~ 170 DEG C in temperature of reaction, reaction pressure is under 0 ~ 0.9MPa condition, is joined continuously by epoxy alkane compound in this reactor 1, makes the pfpe molecule amount in reactor 1 reach 50% ~ 99% of design molecular weight;
(2) initiator, dmc catalyst and epoxy alkane compound are joined in reactor 1 in proportion continuously, make the pfpe molecule amount in reactor 1 reach molecular weight in step (1);
(3) reactor 1 is full of rear continuously to reactor 2 discharging, and add epoxy alkane compound continuously to reactor 2, make the pfpe molecule amount in reactor 2 reach design molecular weight, question response still 2 is full of rear continuous discharge simultaneously.
3. method according to claim 2, it is characterized in that temperature of reaction is 120 ~ 150 DEG C, reaction pressure is 0.1 ~ 0.5MPa, and the pfpe molecule amount in reactor 1 reaches 70% ~ 95% of design molecular weight.
4. method according to claim 2, is characterized in that described initiator is low molecular polyether or small molecular alcohol.
5. method according to claim 4, is characterized in that the functionality of described initiator is 1 ~ 8.
6. method according to claim 5, is characterized in that described low molecular polyether single functionality molecular weight is 32 ~ 1000; Two functionality molecular weight are 72 ~ 2000; Three-functionality-degree molecular weight is 92 ~ 3000.
7. method according to claim 6, is characterized in that described low molecular polyether single functionality molecular weight is 32 ~ 500; Two functionality molecular weight are 72 ~ 400; Three-functionality-degree molecular weight is 92 ~ 400.
8. method according to claim 5, it is characterized in that described small molecular alcohol initiator refers to methyl alcohol, ethanol, n-Octanol, triacontanol, hexalin, vinyl carbinol, ethylene glycol, propylene glycol, Isosorbide-5-Nitrae butyleneglycol, glycol ether, Triethylene glycol or glycerol.
9. method according to claim 2, is characterized in that described epoxy alkane compound is propylene oxide, oxyethane or trimethylene oxide and composition thereof.
10. method according to claim 8, it is characterized in that described epoxy alkane compound is propylene oxide and ethylene oxide mixture, weight ratio is 100 ~ 10: 0 ~ 90.
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