CN104004178A - Sucrose polyether polyol, preparation method and application thereof - Google Patents
Sucrose polyether polyol, preparation method and application thereof Download PDFInfo
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- CN104004178A CN104004178A CN201410159270.7A CN201410159270A CN104004178A CN 104004178 A CN104004178 A CN 104004178A CN 201410159270 A CN201410159270 A CN 201410159270A CN 104004178 A CN104004178 A CN 104004178A
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Abstract
The invention discloses a sucrose polyether polyol, a preparation method and application thereof. The sucrose polyether polyol includes the following components by weight: 180-210 parts of sucrose, 15-30 parts of polyol, 1-5 parts of a catalyst, and 600-660 parts of an epoxide. The preparation method comprises the steps of: adding the sucrose, the polyol and the catalyst into an outer circulation device equipped high pressure reaction kettle, stirring the materials evenly, then adding the epoxide continuously to undergo ring opening polymerization reaction; and when the adding amount of the epoxide reaches over 20%, starting the outer circulation device. The preparation method provided by the invention has the characteristics of small epoxide residue and high product yield up to over 99.2%. The prepared polyether polyol product has good quality, and the prepared bubbles are delicate, and have good dimensional stability and adhesion, as well as good heat insulation effect.
Description
Technical field
The present invention relates to polyurethane field, relate in particular to a kind of sucrose polyether glycol and its preparation method and application.
Background technology
The production of existing hard polyurethane foam polyether glycol generally adopts intermittently autoclave to produce, due to the impact of alr mode in production process, make the residual volume of epoxide can not complete reaction, a part of unreacted epoxide is discharged from micromolecular name, be discharged in other absorbing mediums or be directly discharged in environment, not only having caused pollution but also wasted resource.We know that the resource environment of today is very severe, and waste can not be allowed to, and has following shortcoming: (1) causes the remnants of epoxide based on this its original production method; (2) bring problem to the discharge of absorption epoxide; (3) wasted resource; (4) brought negative impact to environment; (5) due to the remnants of epoxide, affect to the physicals of polyurethane foam, the issue requiring based on current national building energy conservation, in conjunction with the good heat insulation effect of polyurethane foam, polyurethane coating combination material consumption is increased, along with the output of rigid-foam polyether polyol is increasing gradually, in polyether glycol, the residual problem of epoxide urgently needs to solve so, and the remnants of epoxide have had influence on the quality of polyether glycol, and affect environment, bring negative impact to environmental protection.
Summary of the invention
Technical problem to be solved by this invention is can not use the reactor with outer circulation in the generative process in order to overcome the polyether glycol taking sucrose as initiator in prior art, make mixing of materials inhomogeneous, cause epoxide to have remnants, easily cause the defect of environmental pollution and waste resource, and a kind of sucrose polyether glycol and its preparation method and application is provided.The production that in the present invention, the preparation method of sucrose polyether glycol has overcome the polyether glycol taking sucrose as initiator in former technique cannot be used the difficult point of external circulating device, and the reaction conversion ratio that can make epoxide has one and significantly improves (bringing up to more than 99.2% by 98%), improve the emission problem of residual epoxy compound, solve environmental issue, and improve the yield of product, in a disguised form increase the rate of profit of product, reduce remaining epoxide discharge, made environmental protection and benefit doulbe-sides' victory.
The present invention solves the problems of the technologies described above by the following technical programs:
The invention provides a kind of preparation method of sucrose polyether glycol, its raw material packet contains the following component in weight part: 180~210 parts of sucrose, 15~30 parts of polyvalent alcohols, 1~5 part of catalyzer, 600~660 parts of epoxide; It comprises the steps: described sucrose, polyvalent alcohol and catalyzer to join in the autoclave that is provided with external circulating device, stirs, and then adds continuously epoxide to carry out ring-opening polymerization; When the add-on of epoxide reaches 20% when above, open external circulating device.
Wherein, described external circulating device can be the conventional various external circulating devices that use in this area, preferably comprises canned-motor pump and interchanger.
Wherein, described autoclave preferably also comprises a top shower nozzle.Open external circulating device when epoxide add-on reaches 20% when above, make material via outer circulation pipeline, through exchanger heat exchange, spray in still via top shower nozzle at reactor top, make mixing of materials homogeneous reaction abundant.
Wherein, the temperature of described reaction is preferably 80~110 DEG C, and the pressure of described reaction is preferably 0.1~0.6MPa.
Wherein, described catalyzer can be the conventional various catalyzer that use in this area, is preferably alkaline matter, is more preferably one or more in potassium hydroxide, dimethylamine, Trimethylamine 99, dodecyl ammonia and tridecyl amine.
Wherein, described polyvalent alcohol can be the conventional various polyvalent alcohols that use in this area, preferably comprises dibasic alcohol and/or trivalent alcohol; Described dibasic alcohol is preferably one or more in Diethylene Glycol, ethylene glycol and propylene glycol, and described trivalent alcohol is preferably glycerol.
Wherein, described epoxide can be the conventional various epoxide that use in this area, preferably comprises one or more in oxyethane, propylene oxide and epoxy chloropropane.
Wherein, the rotating speed of described stirring is preferably 30~85rpm.
Contriver finds through large quantity research, when epoxide add-on reaches 20% when above, can open external circulating device, being conducive to reaction carries out, improve reaction yield, improve polyether glycol quality, reduce the residual volume of epoxide (oxyethane, propylene oxide, epoxy chloropropane).
In preparation method of the present invention, after described reaction finishes, can also add post-treatment agent.Described post-treatment agent preferably comprises acidic substance, more preferably comprises acetic acid and/or phosphoric acid.
The present invention also provides the sucrose being made by above-mentioned preparation method polyether glycol.
Wherein, the hydroxyl value of described sucrose polyether glycol is preferably 380~440mgKOH/g, and the viscosity of described sucrose polyether glycol under 25 DEG C of conditions is preferably 6600~11200mPas.
The present invention also provides a kind of preparation method of hard-foam polyurethane, and it comprises the steps: above-mentioned sucrose polyether glycol to mix with isocyanic ester, foaming.
Wherein, described isocyanic ester can be the conventional various isocyanic ester that use in this area, the isocyanic ester PM-200 preferably producing for Yantai Wanhua Polyurethane Co., Ltd.
Wherein, the mass ratio of described sucrose polyether glycol and described isocyanic ester is preferably 1:(1~1.05).
Wherein, the method for described foaming and condition can be method and the condition of this area routine.Described foaming preferably adopts high pressure painting foaming machine.The temperature of described foaming is preferably 20~25 DEG C.
The present invention also provides a kind of hard-foam polyurethane being made by above-mentioned preparation method.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is: preparation method of the present invention (1) equipment is simple and convenient; (2) epoxide remnants are little, high can the reaching more than 99.2% of yield of product; (3) Contents In Polyether Polyol quality is good, and made foam exquisiteness, has good dimensional stability and cohesiveness, high insulating effect; (4) in production process, waste water and low-boiling-point substance can obtain certain utilization and control; (5) polyether glycol production efficiency is high, has shortened the production cycle.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to ordinary method and condition, or selects according to catalogue.
Unless otherwise indicated, following material all adopts mass parts.
Embodiment 1
The composition of raw materials that the present embodiment adopts is as follows:
Preparation method: above-mentioned sucrose, polyether glycol and catalyzer are added to the autoclave with external circulating device, and this external circulating device comprises canned-motor pump and interchanger.Stir, then add continuously epoxide to carry out ring-opening polymerization, temperature of reaction is controlled at 95~105 DEG C, and pressure is less than 0.4MPa; When the add-on of epoxide reaches 128 parts of 20%() when above, unlatching external circulating device.
The hydroxyl value of the sucrose polyether glycol that the present embodiment obtains is 415mgKOH/g, and viscosity is 6600mPas.
The sucrose polyether glycol viscosity generating is higher, and yield is 99.21%, and outward appearance is light yellow transparent thick liquid.
Embodiment 2
The composition of raw materials that the present embodiment adopts is as follows:
Preparation method: above-mentioned sucrose, polyether glycol and catalyzer are added to the autoclave with external circulating device, and this external circulating device comprises canned-motor pump and interchanger.Stir, then add continuously epoxide to carry out ring-opening polymerization, temperature of reaction is controlled at 95~105 DEG C, and pressure is less than 0.4MPa; When the add-on of epoxide reaches 126 parts of 20%() when above, unlatching external circulating device.After epoxide adds, keep temperature of reaction slaking 3 hours, then row pressure, to 0Pa, adds post-treatment agent, removes unreacted epoxide monomer after neutralization.
The hydroxyl value of the sucrose polyether glycol that the present embodiment obtains is 440mgKOH/g, and viscosity is 11200mPas.
The sucrose polyether glycol viscosity generating is higher, and yield is 99.2%, and outward appearance is light yellow transparent thick liquid.
Comparative example 1
The composition of raw materials that this comparative example adopts is as follows:
Preparation method: above-mentioned sucrose, polyether glycol and catalyzer are added to the autoclave with external circulating device, and this external circulating device comprises canned-motor pump and interchanger.Stir, then add continuously epoxide to carry out ring-opening polymerization, temperature of reaction is controlled at 95-105 DEG C, and pressure is less than 0.4MPa; When the add-on of epoxide reaches 94.5 parts of 15%() when above, open external circulating device, open 2 times, due to the sucrose reaction process that caused pump congestion affects, after twice, reaction is normally.After epoxide adds, keep temperature of reaction slaking 3 hours, then row pressure, to 0Pa, adds post-treatment agent, carries out post-processing operation.
The hydroxyl value of the sucrose polyether glycol that this comparative example obtains is 450mgKOH/g, and viscosity is 10200mPas.Can find out owing to opening outer circulation opportunity relatively early, affect the hydroxyl value index of product, make the hydroxyl value of product excessive, and to make its yield be 98.8%, material viscosity is lower, has very big-difference with respect to same recipe result on different conversion units.
Comparative example 2
The composition of raw materials that this comparative example adopts is as follows:
Preparation method: above-mentioned sucrose, polyether glycol and catalyzer are added to the autoclave with external circulating device, and this external circulating device comprises canned-motor pump and interchanger.Stir, then add continuously epoxide to carry out ring-opening polymerization, temperature of reaction is controlled at 95-105 DEG C, and pressure is less than 0.4MPa; When the add-on of epoxide reaches 63 parts of 10%() time, external circulating device opened.Outer circulation pump stops up, and termination of pumping processing, does not adopt outer circulation pump, after epoxide adds, keeps temperature of reaction slaking 3 hours, and then row pressure, to 0Pa, adds post-treatment agent, carries out post-processing operation.
The hydroxyl value of the sucrose polyether glycol that this comparative example obtains is 460mgKOH/g, and viscosity is 10000mPas.Can find out owing to opening outer circulation opportunity relatively early, affect the hydroxyl value index of product, and to make its yield be 98.6%, material viscosity is lower, has very big-difference with respect to same recipe result on different conversion units.
Comparative example 3
The composition of raw materials that this comparative example adopts is as follows:
Preparation method: above-mentioned sucrose, polyether glycol and catalyzer are added to the autoclave with external circulating device, and this external circulating device comprises canned-motor pump and interchanger.Stir, then add continuously epoxide to carry out ring-opening polymerization, temperature of reaction is controlled at 95-105 DEG C, and pressure is less than 0.4MPa; When the add-on of epoxide reaches 10%(63 part) time, external circulating device opened.Outer circulation pump stops up, termination of pumping processing, and rear outer circulation is because obstruction can't afford to drive, and external circulating device breaks, do not adopt outer circulation pump, after epoxide adds, keep temperature of reaction slaking 5 hours, then row pressure, to 0Pa, adds post-treatment agent, carries out post-processing operation.
The hydroxyl value of the sucrose polyether glycol that this comparative example obtains is 460mgKOH/g, and viscosity is 9200mPas, and material outward appearance obviously has slightly turbid.Can find out owing to opening outer circulation opportunity relatively early, affect the hydroxyl value index of product, and to make its receipts be 98.1%, material viscosity is lower, has very big-difference with respect to same recipe result on different conversion units.
Comparative example 4
The composition of raw materials that this comparative example adopts is as follows:
Preparation method: above-mentioned sucrose, polyether glycol and catalyzer are added with (without external circulating device) in common autoclave, stir, then add continuously epoxide to carry out ring-opening polymerization, temperature of reaction is controlled at 95-105 DEG C, and pressure is less than 0.4MPa; After epoxide adds, keep temperature of reaction slaking 3 hours.
The hydroxyl value of the sucrose polyether glycol that this comparative example obtains is 419mgKOH/g, and viscosity is 5800mPas.
Effect embodiment
Use 1 part of the synthetic sucrose polyether glycol of above-described embodiment, with the mixture of 1 part of isocyanic ester (the isocyanic ester PM-200 that Yantai Wanhua Polyurethane Co., Ltd produces), through high pressure painting whipping agent machine, after high pressure mixing, 25 DEG C of foamings.The performance of the polyurethane products that obtain is as shown in table 1 below.
Table 1
As seen from the above table, the polyurethane products excellent performance that the sucrose polyether glycol that adopts the present invention to make prepares, the polyurethane products that its compressive strength is better than producing in prior art.
Claims (10)
1. a preparation method for sucrose polyether glycol, its raw material packet contains the following component in weight part: 180~210 parts of sucrose, 15~30 parts of polyvalent alcohols, 1~5 part of catalyzer, 600~660 parts of epoxide; It comprises the steps: described sucrose, polyvalent alcohol and catalyzer to join in the autoclave that is provided with external circulating device, stirs, and then adds continuously epoxide to carry out ring-opening polymerization; When the add-on of epoxide reaches 20% when above, open external circulating device.
2. preparation method as claimed in claim 1, is characterized in that, described external circulating device comprises canned-motor pump and interchanger;
And/or described autoclave also comprises a top shower nozzle.
3. preparation method as claimed in claim 1, is characterized in that, the temperature of described reaction is 80~110 DEG C, and the pressure of described reaction is 0.1~0.6MPa; The rotating speed of described stirring is 30~85rpm.
4. preparation method as claimed in claim 1, is characterized in that, described catalyzer is alkaline matter; And/or described polyvalent alcohol comprises dibasic alcohol and/or trivalent alcohol; And/or described epoxide comprises one or more in oxyethane, propylene oxide and epoxy chloropropane.
5. preparation method as claimed in claim 4, is characterized in that, described alkaline matter is one or more in potassium hydroxide, dimethylamine, Trimethylamine 99, dodecyl ammonia and tridecyl amine; Described dibasic alcohol is one or more in Diethylene Glycol, ethylene glycol and propylene glycol, and described trivalent alcohol is glycerol.
6. the sucrose polyether glycol that the preparation method as described in any one in claim 1~5 makes.
7. sucrose polyether glycol as claimed in claim 6, is characterized in that, the hydroxyl value of described sucrose polyether glycol is 380~440mgKOH/g, and the viscosity of described sucrose polyether glycol under 25 DEG C of conditions is 6600~11200mPas.
8. a preparation method for hard-foam polyurethane, it comprises the steps: the sucrose polyether glycol as described in claim 6 or 7 to mix with isocyanic ester, foaming.
9. preparation method as claimed in claim 8, is characterized in that, described isocyanic ester is isocyanic ester PM-200;
And/or the mass ratio of described sucrose polyether glycol and described isocyanic ester is 1:(1~1.05);
And/or described foaming adopts high pressure painting foaming machine to foam; The temperature of described foaming is 20~25 DEG C.
10. the hard-foam polyurethane being made by the preparation method described in claim 8 or 9.
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Cited By (5)
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CN105601902A (en) * | 2016-01-14 | 2016-05-25 | 浙江皇马科技股份有限公司 | Synthetic method of sucrose polyoxypropylene |
CN105801832A (en) * | 2014-12-31 | 2016-07-27 | 上海东大化学有限公司 | Degradable polyether polyol, and raw-material composition and preparation method thereof |
CN108070081A (en) * | 2017-12-01 | 2018-05-25 | 耿佃勇 | The preparation method of high functionality Sucrose polyethers |
CN108261422A (en) * | 2018-01-09 | 2018-07-10 | 广西大学 | A kind of drug for inhibiting tumor cell proliferation |
CN114062357A (en) * | 2021-12-15 | 2022-02-18 | 上海东大化学有限公司 | Method for rapidly detecting polyether raw material sugar |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105801832A (en) * | 2014-12-31 | 2016-07-27 | 上海东大化学有限公司 | Degradable polyether polyol, and raw-material composition and preparation method thereof |
CN105601902A (en) * | 2016-01-14 | 2016-05-25 | 浙江皇马科技股份有限公司 | Synthetic method of sucrose polyoxypropylene |
CN108070081A (en) * | 2017-12-01 | 2018-05-25 | 耿佃勇 | The preparation method of high functionality Sucrose polyethers |
CN108261422A (en) * | 2018-01-09 | 2018-07-10 | 广西大学 | A kind of drug for inhibiting tumor cell proliferation |
CN114062357A (en) * | 2021-12-15 | 2022-02-18 | 上海东大化学有限公司 | Method for rapidly detecting polyether raw material sugar |
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