CN100497438C - Continuous preparation method for polyether glycol - Google Patents
Continuous preparation method for polyether glycol Download PDFInfo
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- CN100497438C CN100497438C CNB2007100255848A CN200710025584A CN100497438C CN 100497438 C CN100497438 C CN 100497438C CN B2007100255848 A CNB2007100255848 A CN B2007100255848A CN 200710025584 A CN200710025584 A CN 200710025584A CN 100497438 C CN100497438 C CN 100497438C
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Abstract
The invention is a continuous preparation method of the polyether polyol; the starting reagent containing the DMC catalyst is added into the reaction kettle; the air is removed with nitrogen; the method is to vacuum, stir, raise the temperature, and the epoxy compound is continuously added into the reaction kettle to make the reaction kettle have the inducing pressure; when the temperature is raised and the pressure is lowered in the reaction kettle, the epoxy compound is continued to to be added into the reaction kettle; the temperature is kept in the reaction between 90 and 200 Celsius system, the pressure between minus 0.05 and 1.0 MPa. Then the starting reagent containing the bimetallic cyanide catalyst and the epoxy compound are added into the reaction kettle according to the proportion at the same time. When the reaction kettle is full, the reaction materials flow into the aging kettle to continue to react; the temperature of the aging kettle is kept between 100 and 180 Celsius system. The polyether polyol product enters the product storage tank after being discharged out of the aging kettle. The polyether polyol produced in the method of the invention has the narrow molecular weight distribution, the low non-saturation degree and the stable quality; the method can use the polyether polyol of the low molecular weight as the starting reagent, and can also directly use the small-molecule polyol as the starting reagent.
Description
Technical field
The present invention relates to prepare the method for polyether glycol, specifically, is a kind of continuously preparing poly ethoxylated polyhydric alcohol method.
Background technology
Polyether glycol is mainly used in the polyurethane material field, is used to produce flexible PU foam, hard bubbles and goods such as polyurethane coating, tackiness agent, seal gum, elastomerics, and its consumption accounts for about 80% of polyether glycol production.Polyether glycol also is mainly used in aspects such as producing suds-stabilizing agent, defoamer, emulsion splitter and lubricant in addition.
It is strong that double metal cyanide (DMC) catalyzer has catalytic activity, speed of response is fast, characteristics such as can react at a lower temperature, had the following advantages by the polyether glycol of DMC preparation: the scope of number-average molecular weight regulation and control is wide, can prepare high molecular weight polyether; The product degree of unsaturation is low, can reach below the 0.005mmol/g, and wherein monohydroxy-alcohol content is extremely low, and the product functionality is near theoretical value; Narrow molecular weight distribution, viscosity is lower etc.Polyether glycol can use several different methods to make, and mainly is divided into batch process and continous way method.There are many drawbacks in batch production, mainly is that the reactive tank utilization ratio is low, and the production cycle is long, the quality index instability between each batch etc.In addition, in interrupter method, shortcoming of DMC catalyzed polymerization system ubiquity: can not be directly during polymerization with small molecules polyvalent alcohols such as propylene glycol, glycerol as initiator, otherwise will be arranged a very long inductive phase in initial reaction stage.Generally need prepare the low molecular polyether polyvalent alcohol as initiator by base catalysis.As realize the serialization production of polyether glycol, then can improve usage ratio of equipment to a great extent, shorten the production cycle and reduce the energy consumption of producing.In addition, serialization is produced polyether glycol and can be obtained more stable product quality.
Along with the development of polyurethane industrial and continually developing of new product, the quality of this important source material of polyether glycol is also had higher requirement.Degree of unsaturation is one of important indicator of weighing the polyether glycol quality, in the building-up process of polyether glycol, exist the epoxide isomerization to generate the side reaction of vinyl carbinol, cause the generation of the monohydroxy-alcohol of low relative molecular mass, thereby reduced the average molecular mass and the functionality of polyether glycol.This-unit's alcohol can play multiple adverse influence in polyurethane material is synthetic.As: it has limited the growth of urethane relative molecular weight, to the physical and mechanical property generation detrimentally affect of end article.It also can reduce the weathering resistance of urethane, easily produces degraded etc. under uviolizing.In addition, molecular weight distribution is that the science of the long polymolecularity of polymer molecule chain structure medium chain is measured, can be from the quality of profound reflection polyether glycol.The sterie configuration of the viscosity of polyether glycol product and molecular weight, molecular chain and the width of molecular weight distribution relation is very big, and wide its viscosity of product of molecular weight distribution was also just big more when number-average molecular weight was identical.
Summary of the invention
The continuous preparation method that the purpose of this invention is to provide a kind of polyether glycol has narrow molecular weight distribution, characteristics that degree of unsaturation is low by the polyethers of this method preparation is polynary.More outstanding is the invention provides and a kind ofly can directly use the small molecules polyvalent alcohol to prepare the method for polyether glycol as initiator under dmc catalyst catalysis.
Adopt tank reactor among the present invention and should comprise feeding unit, reactor, aging of product still, optionally add raw material premix still and product after-treatment device.Aging of product still can be selected single still, preferentially selects a plurality of aging still series connection to use, as shown in Figure 1.
Technical scheme of the present invention is as follows:
A kind of continuous preparation method of polyether glycol, it is made up of the following step:
Step 4. is after reactor is full of, and reactant flows out from the reactor top, enters aging still from the bottom, continues reaction, and the temperature of aging still remains on 100～180 ℃,
The continuous preparation method of above-mentioned polyether glycol, described step 2, preferred temperature is 100～180 ℃, preferred pressure is 0～0.8MPa.
The continuous preparation method of above-mentioned polyether glycol, described step 3, preferred temperature is 100～160 ℃, preferred pressure is 0～0.8MPa.
The continuous preparation method of above-mentioned polyether glycol, described step 2 feed the quality of epoxy compounds and can regulate according to the size of the molecular weight of the polyether glycol of required preparation.
The continuous preparation method of above-mentioned polyether glycol, added initiator is the low molecular polyether polyvalent alcohol in the described step 3, or the small molecules polyvalent alcohol.
The continuous preparation method of above-mentioned polyether glycol, described step 4, the preferred temperature of aging still is 110～170 ℃.
The continuous preparation method of above-mentioned polyether glycol, described step 4, aging still can be with a plurality of aging still series connection, to guarantee that product has enough digestion times in reactive system.
The continuous preparation method of above-mentioned polyether glycol, described reactor and aging still preferably have external circulating device, and the outfit recycle pump can the flow direction as requested circulate reaction solution therein.
The continuous preparation method of above-mentioned polyether glycol can be equipped with cooling system on the external circulating device of described reactor and aging still, is used for the control of temperature of charge in reactor and the aging still.
Material feeding mode of the present invention can have multiple.Can select charging behind epoxide, catalyzer, the initiator premix, be more prone to select with raw material be divided into two streams be epoxide as first streams, the mixture of catalyzer and initiator is distinguished charging as second streams.Epoxide is selected by the charging of reactor upper inlet among the present invention, and initiator then can be selected also can select via the charging of outer circulation upper inlet via the charging of reactor inlet.
The above-mentioned epoxide that uses is the mixture of oxyethane, propylene oxide or its different ratios.
Initiator is divided into two portions among the present invention: initially add the initiator A of reactor and the initiator B that adds continuously.Wherein initiator A is the low molecular polyether polyvalent alcohol, and its hydroxyl value needs through refinement treatment between 50～500mgKOH/g, strict control K wherein
+, Na
+Ion content.Only the operation starting stage need a small amount of initiator A in the entire reaction system, reactive system will no longer need to add initiator A after starting.Initiator B can equally select the low molecular polyether polyvalent alcohol for use with initiator A, and its hydroxyl value also need be passed through refinement treatment between 50～500mgKOH/g, strict control K wherein
+, Na
+Ion content.The more important thing is that initiator B also can be the small molecules polyvalent alcohol as propylene glycol, dipropylene glycol, ethylene glycol, a condensed ethandiol, glycerine, TriMethylolPropane(TMP) or the like, preferably uses propylene glycol, glycerine.What need during the serialization of initiator B after reactive system starts produced not stop adds in the reactor, and aequum is bigger.
The dmc catalyst concentration of above-mentioned use also is segmented into two kinds of scopes according to initiator, in the stage that reactive system starts, need the polyaddition reaction in the still under fast speeds, to carry out, can select higher catalyst concn this moment, its scope is 5～200ppm, 5～100ppm more preferably, preferably scope is 10～40ppm.Reactive system starts the back need add catalyzer when adding initiator, epoxide continuously, the concentration of catalyzer in product of this moment can be low slightly than previous stage.Can in advance catalyzer be dispersed in the initiator, add reactor with the initiator successive.
Reacting kettle inner pressure of the present invention is chosen in-0.05～1.0MPa between, between preferred 0～0.8MPa.In patent CN1620474A, propose preferably under higher pressure, to react, can accomplish not have gas-phase reaction in the reaction system during vapour pressure when the reaction system internal pressure is higher than used epoxide in this temperature of reaction, can obtain narrower molecular weight distribution this moment.But this reaction under high pressure is difficult in actual production realize and control that we tend to select for use the reaction pressure near actual production among the present invention under the narrower prerequisite of assurance product molecular weight distribution.
Optional a wider range of temperature of reaction among the present invention is the unloading phase of reactive system, for obtaining faster speed of reaction and shortening inductive phase, be chosen in induced reaction under the comparatively high temps, and have experiment to find that low temperature induction gained polyether glycol viscosity is big slightly, molecular weight distribution is wide slightly.This phase temperature scope is selected 90～200 ℃, preferred 100～180 ℃.The reaction startup is finished and is steadily added the temperature range that can select behind epoxide and the initiator and required to decide by the required quality product that reaches.The degree of unsaturation and the temperature of reaction of product are closely related, are guaranteeing to select lesser temps to help the reduction of product degree of unsaturation as much as possible in the speed of reaction stably.This phase temperature scope is chosen in 90～180 ℃, preferred 100～160 ℃.When reactor is full of the still selection temperature high slightly than reactor after the overflow discharging to aging of product still, is worn out, preferred 110～170 ℃.
Adopt full still overflow discharge method among the present invention, the input speed of reactive system equates with discharging speed.Can represent the residence time of reaction mass in reactive system with discharging speed or input speed, the residence time is related to the quality of polyether glycol product, also has influence on the efficient of production.For the different reactive system of capacity, tend to select different input speeds to guarantee certain residence time.Be that the preferred input speed of lab scale reactor of 3L is 0.5～10Kg/h to capacity for example, more excellent is 1.0～8.0Kg/h.
A significant advantage of the present invention is can be initiator with the low molecular polyether polyvalent alcohol both, can be initiator directly more with the small molecules polyvalent alcohol, when being initiator with the small molecules polyvalent alcohol, for avoiding the passivation of small molecules polyvalent alcohol, should guarantee that the amount of small molecules polyvalent alcohol in reactor should be no more than in the reactor 1% of total inventory to catalyzer.
The present invention compared with prior art its product has the following advantages:
The polyether glycol of narrow molecular weight distribution is prepared in 1 employing with respect to comparatively simple reactive system of prior art and safer, actual working condition.
2 adopt above-mentioned production unit and condition to prepare the polyether glycol with low-unsaturation-degree.
3 use dmc catalyst can directly adopt the small molecules polyvalent alcohol to prepare polyether glycol as initiator under above equipment and condition.
Constant product quality is carried out steadily in the long-time investigation reaction of 4 warps.
Description of drawings
Fig. 1 is the equipment of the continuous preparation method of polyether glycol of the present invention, the synoptic diagram of flow process, and wherein: 1 is the epoxide inlet; 2 is catalyzer, initiator or its mixture inlet; 3 is recycle pump; 4 is reactor; 5,6 are aging still; 7 is static mixer; 8,9 is agitator; 10,11 is discharge port; 12 is sparger.
Embodiment
Preparation equipment and flow process are got quantitative catalyzer and are dispersed among the 0.5Kg low molecular weight polyols N204 (two functionality, hydroxyl value 350mgKOH/g) as shown in Figure 1, and it is added the lab scale reactor, and vacuum is with N
2Replace 1-2 time, keep N
2Pressure is 0.1MPa, heats, stirs, is warming up to 135 ℃; Get quantitative catalyzer and be dispersed among the 4Kg low molecular weight polyols N204, it is stored up in the storage tank of 5L then.Reactor is warming up to 150 ℃ a certain amount of propylene oxide (PO) successive is pressed in the reactor with nitrogen, induces when making reacting kettle inner pressure reach 0.35MPa, when temperature in the kettle rises, pressure descends, induces successfully.Open outer circulation, continue to feed PO to the little still of serialization.When feeding the PO total mass when reaching 2.6Kg, open the charging volume pump respectively with the N204/ catalyst mixture of PO and the aforementioned 5L of placing storage tank by a certain percentage, certain speed pumps into reaction kettle for reaction.Reactor is full of the back by the extremely aging still of overflow discharging.Treat to be cooled to 150 ℃ of reactions behind the system stability.Products obtained therefrom hydroxyl value 55.13mgKOH/g, degree of unsaturation 0.005mmol/g, molecular weight distribution 1.07.
Adopting above-mentioned N204 is initiator, and reaction process is treated to be cooled to 130 ℃ of reactions behind the system stability, products obtained therefrom hydroxyl value 55.51mgKOH/g, degree of unsaturation 0.0033mmol/g, molecular weight distribution 1.06. with embodiment 1
Get quantitative catalyzer and be dispersed among the 0.5Kg low molecular weight polyols N204 (two functionality, hydroxyl value 350mgKOH/g), and it is added the lab scale reactor, vacuum is with N
2Replace 1-2 time, keep N
2Pressure is 0.1MPa, heats, stirs, is warming up to 135 ℃; Get quantitative catalyzer and be dispersed in the 2Kg propylene glycol, it is stored up in the storage tank of 5L then.Reactor is warming up to 170 ℃ a certain amount of propylene oxide (PO) successive is pressed in the reactor with nitrogen, induces when making reacting kettle inner pressure reach 0.35MPa, when temperature in the kettle rises, pressure descends, induces successfully.Open outer circulation, continue to feed PO to the little still of serialization.When feeding the PO total mass when reaching 2.6Kg, open the charging volume pump respectively with the propylene glycol/catalyst mixture of PO and the aforementioned 5L of placing storage tank by a certain percentage, certain speed pumps into reaction kettle for reaction.Reactor is full of the back by the extremely aging still of overflow discharging.Treat to be cooled to 150 ℃ of reactions behind the system stability.Products obtained therefrom hydroxyl value 39.80mgKOH/g, degree of unsaturation 0.005mmol/g, molecular weight distribution 1.09.
Embodiment 4
Get quantitative catalyzer and be dispersed among the 0.5Kg low molecular weight polyols N305 (three-functionality-degree, hydroxyl value 293mgKOH/g), and it is added the lab scale reactor, vacuum is with N
2Replace 1-2 time, keep N
2Pressure is 0.1MPa, heats, stirs, is warming up to 135 ℃; Get quantitative catalyzer and be dispersed among the 4Kg N305, it is stored up in the storage tank of 5L then.Reactor is warming up to 170 ℃ a certain amount of propylene oxide (PO) successive is pressed in the reactor with nitrogen, induces when making reacting kettle inner pressure reach 0.35MPa, when temperature in the kettle rises, pressure descends, induces successfully.Open outer circulation, continue to feed PO to the little still of serialization.When feeding the PO total mass when reaching 2.1Kg, open the charging volume pump respectively with the N305/ catalyst mixture of PO and the aforementioned 5L of placing storage tank by a certain percentage, certain speed pumps into reaction kettle for reaction.Reactor is full of the back by the extremely aging still of overflow discharging.Treat to be cooled to 150 ℃ of reactions behind the system stability.Products obtained therefrom hydroxyl value 55.83mgKOH/g, degree of unsaturation 0.0041mmol/g, molecular weight distribution 1.08.
Get quantitative catalyzer and be dispersed among the 0.5Kg low molecular weight polyols N305 (three-functionality-degree, hydroxyl value 293mgKOH/g), and it is added the lab scale reactor, vacuum is with N
2Replace 1-2 time, keep N
2Pressure is 0.1MPa, heats, stirs, is warming up to 135 ℃; Get quantitative catalyzer and be dispersed in the 4Kg glycerine, it is stored up in the storage tank of 5L then.Reactor is warming up to 170 ℃ a certain amount of propylene oxide (PO) successive is pressed in the reactor with nitrogen, induces when making reacting kettle inner pressure reach 0.35MPa, when temperature in the kettle rises, pressure descends, induces successfully.Open outer circulation, continue to feed PO to the little still of serialization.When feeding the PO total mass when reaching 2.1Kg, open the charging volume pump respectively with the glycerine/catalyst mixture of PO and the aforementioned 5L of placing storage tank by a certain percentage, certain speed pumps into reaction kettle for reaction.Reactor is full of the back by the extremely aging still of overflow discharging.Treat to be cooled to 125 ℃ of reactions behind the system stability.Products obtained therefrom hydroxyl value 49.97mgKOH/g, degree of unsaturation 0.0017mmol/g, molecular weight distribution 1.05.
Get quantitative catalyzer and be dispersed among the 0.5Kg low molecular weight polyols N305 (three-functionality-degree, hydroxyl value 293mgKOH/g), and it is added the lab scale reactor, vacuum is with N
2Replace 1-2 time, keep N
2Pressure is 0.1MPa, heats, stirs, is warming up to 135 ℃; Get quantitative catalyzer and be dispersed among the 4Kg N305, it is stored up in the storage tank of 5L then.Reactor is warming up to 170 ℃ of mixture successive with a certain amount of PO and oxyethane (EO) and is pressed in the reactor with nitrogen, induces when making reacting kettle inner pressure reach 0.35MPa, when temperature in the kettle rises, pressure descends, induces successfully.Open outer circulation, continue to feed PO/EO to the little still of serialization.When feeding the PO/EO total mass when reaching 2.1Kg, open the charging volume pump respectively with the N305/ catalyst mixture of PO/EO and the aforementioned 5L of placing storage tank by a certain percentage, certain speed pumps into reaction kettle for reaction.Reactor is full of the back by the extremely aging still of overflow discharging.Treat to be cooled to 150 ℃ of reactions behind the system stability.Products obtained therefrom hydroxyl value 56.32mgKOH/g, degree of unsaturation 0.0046mmol/g, molecular weight distribution 1.06.
Claims (8)
1. the continuous preparation method of a polyether glycol is characterized in that it is made up of the following step:
Step 1. in reactor, drop into contain DMC catalysts the low molecular polyether polyvalent alcohol as initiator, use the nitrogen sweep deacration, vacuumize, stir, be warming up to 150～180 ℃, add epoxy compounds continuously from the reactor bottom, make reacting kettle inner pressure reach 0.01～1.0MPa, carry out reaction induced
Step 2. is when reactor temperature rises, pressure descends, reaction induced success continues to feed epoxy compounds to reactor, and keeping reactor temperature is 90～200 ℃, pressure-0.05～1.0MPa, until the quality of the epoxy compounds that feeds reach target product requirement
Step 3. adds initiator and the epoxy compounds that contains DMC catalysts simultaneously in proportion continuously in reactor, keeping the temperature in the still is 90～180 ℃, pressure-0.05～1.0MPa,
Step 4. is after reactor is full of, and reactant flows out from the reactor top, enters aging still from the bottom, continues reaction, and the temperature of aging still remains on 100～180 ℃,
Step 5. is after aging still is full of, and the polyether glycol product flows out from aging still top continuously, enters the product storage tank.
2. the continuous preparation method of polyether glycol according to claim 1 is characterized in that: the temperature in described step 2 reactor is 100～180 ℃, and pressure is 0～0.8MPa.
3. the continuous preparation method of polyether glycol according to claim 1 is characterized in that: the temperature in described step 3 reactor is 100～160 ℃, and pressure is 0～0.8MPa.
4. the continuous preparation method of polyether glycol according to claim 1, it is characterized in that: added initiator is the low molecular polyether polyvalent alcohol in the described step 3, or the small molecules polyvalent alcohol.
5. the continuous preparation method of polyether glycol according to claim 1 is characterized in that: described step 4, the temperature of aging still is 110～170 ℃.
6. the continuous preparation method of polyether glycol according to claim 1 is characterized in that: described step 4, aging still is with two or more aging stills series connection, to guarantee that product has enough residence time in reactive system.
7. the continuous preparation method of polyether glycol according to claim 1 is characterized in that: described reactor and aging still have external circulating device, and are equipped with recycle pump and make flow direction circulation therein from bottom to top in still that reaction solution can be as requested.
8. the continuous preparation method of polyether glycol according to claim 8 is characterized in that: be furnished with cooling system on described reactor and the aging still external circulating device, be used for the control of temperature of charge in reactor and the aging still.
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101161700B (en) * | 2007-08-17 | 2010-05-19 | 胡冰 | Method for producing polyether |
| CN103384692A (en) * | 2011-02-24 | 2013-11-06 | 国际壳牌研究有限公司 | Process and reactor system for the preparation of polyether polyols |
| CN102875796B (en) * | 2012-10-16 | 2015-03-04 | 山东蓝星东大化工有限责任公司 | Method for improving activity of double metal cyanide (DMC) catalyst used for producing polyether polyol |
| CN103694465B (en) * | 2013-11-25 | 2016-06-01 | 黎明化工研究设计院有限责任公司 | The method for continuously synthesizing of a kind of polyethers |
| CN105153382A (en) * | 2015-07-09 | 2015-12-16 | 江苏擎宇化工科技有限公司 | Continuous production method of polymer surfactant for pesticides |
| CN105273181A (en) * | 2015-11-24 | 2016-01-27 | 抚顺东科精细化工有限公司 | Continuous technology for producing polycarboxylate superplasticizer monomer polyether through one-step method |
| CN106397280A (en) * | 2016-11-23 | 2017-02-15 | 张家港格瑞特化学有限公司 | Preparation method of sodium lauroylmethyl taurate |
| EP3533820B1 (en) * | 2017-10-12 | 2021-04-07 | Kureha Corporation | Continuous production method and continuous production device for aromatic cyclic oligomer, and production method for aromatic polymer |
| CN110483759A (en) * | 2019-09-18 | 2019-11-22 | 福建省天骄化学材料有限公司 | A kind of preparation method of low VOC polyether polyol |
| CN111518268B (en) * | 2020-05-28 | 2022-09-16 | 万华化学集团股份有限公司 | Preparation method of polyether polyol |
| CN113429557B (en) * | 2021-06-21 | 2022-07-12 | 万华化学集团股份有限公司 | Continuous preparation method of low-viscosity polyether polyol |
| CN114832759B (en) * | 2022-04-27 | 2024-01-02 | 浙江皇马科技股份有限公司 | High molecular weight polyether and preparation method and system thereof |
| CN115304761B (en) * | 2022-08-11 | 2023-12-12 | 山东一诺威新材料有限公司 | Polyester ether polyol for high-performance polyurethane waterproof coating and preparation method thereof |
| CN115181259B (en) * | 2022-08-11 | 2024-04-09 | 万华化学集团股份有限公司 | Method for continuously preparing polyether |
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Address after: No.158, Fenghua Road, Jiangbei new district, Nanjing, Jiangsu Province Patentee after: JIANGSU ZHONGSHAN CHEMICAL Co.,Ltd. Address before: 210038 No. 46, Xin Xin Road, Qixia District, Jiangsu, Nanjing Patentee before: JIANGSU ZHONGSHAN CHEMICAL Co.,Ltd. |
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Effective date of registration: 20220207 Address after: No. 158, Fenghua Road, Jiangbei new area, Nanjing, Jiangsu 210038 Patentee after: Jiangsu Zhongshan new material Co.,Ltd. Address before: No. 158, Fenghua Road, Jiangbei new area, Nanjing, Jiangsu 210038 Patentee before: JIANGSU ZHONGSHAN CHEMICAL Co.,Ltd. |