CN101967227A - Synthetic method of slow resilience foam polyether polyol - Google Patents
Synthetic method of slow resilience foam polyether polyol Download PDFInfo
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- CN101967227A CN101967227A CN 201010295124 CN201010295124A CN101967227A CN 101967227 A CN101967227 A CN 101967227A CN 201010295124 CN201010295124 CN 201010295124 CN 201010295124 A CN201010295124 A CN 201010295124A CN 101967227 A CN101967227 A CN 101967227A
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- synthetic method
- low resilience
- resilience urethane
- polyether glycol
- urethane foam
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Abstract
The invention relates to a synthetic method of slow resilience foam polyether polyol, which is characterized by adopting a polyalcohol compound as an initiator, and taking alkali metal as a catalyst and acetic anhydride as an end sealing agent to polymerize with epoxy compound at the pressure of 0-0.5 MPa and at the temperature of 50-150 DEG C to obtain the slow resilience foam polyether polyol. The process is convenient for workers to operate; the technical index is easy to control; and the prepared new-type slow resilience foam polyether polyol can be used for various slow resilience foam products, and has the characteristic of smaller hardness change at the condition of temperature change.
Description
Technical field
The present invention relates to a kind of synthetic method of low resilience urethane foam resilient foam body polyether glycol, belong to chemical field.
Background technology
As everyone knows, rebound degree low, be that slow elastic flexible polyurethane foam is used as absorbing body, shock absorber and uses.In addition, body is pressed be evenly distributed, reduce the changing of the relative positions of sense of fatigue and bottom surface.
In the conventional art, in order to obtain to have good ground rebound resilience and the less low resilience flexible foams of the rising of the hardness under the low temperature under the room temperature, the general admixtured polyether polyvalent alcohol that uses, average functionality numerical digit 1.54.5 comprising 32～80 weight %, hydroxyl value is the polyvalent alcohol of 140～300mgKOH/g, like this, can make a kind of polyurethane flexible foam body, this foam is in-50 ℃～-25 ℃ temperature range, and in 30～55 temperature range, has at least more than one second-order transition temperature respectively.
But the special polyol more than 2 kinds that the mixing hydroxyl value of above-mentioned technology in the past is different forms in the method for flexible foam body, and existence can not fully suppress the problem corresponding to the changes in hardness of temperature variation.。
In the conventional art, also can the rebound resilience (rebound degree) of polyurethane elastomer be descended by blending softening agent in the flexible foam body, by adding the softening agent of appropriate amount, can obtain the flexible foam body of desirable low-resilience to a certain degree, but, the softening agent that adds can volatilize in use, might be sucked by human body, so can not use harmful material.In addition, softening agent may stripping when foams are washed, and is difficult to keep the low-resilience of foams behind the repetitive scrubbing.
Summary of the invention
According to the prior art deficiency, technical problem to be solved by this invention is: a kind of synthetic method of low resilience urethane foam resilient foam body polyether glycol is provided, and the polyether glycol that makes is used for the preparation of low resilience urethane foam resilient foam body, has under the situation of temperature variation the changes in hardness features of smaller.
The technical solution adopted for the present invention to solve the technical problems is: the synthetic method that a kind of low resilience urethane foam resilient foam body polyether glycol is provided, it is characterized in that adopting multicomponent alcoholics compound as initiator, at 0-0.5Mpa pressure, under the 50-150 ℃ of temperature, with basic metal is catalyzer, dried with acetic acid is end-capping reagent, carries out polymerization with epoxy compounds and obtains.
Described multicomponent alcoholics compound is the mixture that one or more arbitrary proportions in ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerine, tetramethylolmethane, Xylitol, sorbyl alcohol, N.F,USP MANNITOL, sucrose, the glycoside are formed.
Described polyol compound is a glycerine.
Described reaction pressure is 0.1-0.4Mpa, and temperature of reaction is 80-110 ℃.
Described base metal catalysts is selected from the mixture of one or more compositions in sodium methylate, sodium ethylate, sodium hydroxid, the potassium hydroxide, and the addition of base metal catalysts is 0.3% of a raw materials quality summation.
Described base metal catalysts adopts potassium hydroxide.
Described end-capping reagent is selected from acetic acid, maleic anhydride or acetic anhydride, wherein preferred acetic anhydride.
The ratio that described end-capping reagent accounts for the molar mass of multicomponent alcoholics compound is 2: 1.
Described epoxide is the mixture of propylene oxide and oxyethane, and the consumption of epoxy compounds is 12.5% of total inventory, and the epoxy compounds total mass accounts for the 97%-99% of total inventory.
The invention has the beneficial effects as follows: this technology is convenient to workman's operation, and technical indicator is controlled easily; And the novel low resilience urethane foam resilient foam body polyether glycol that makes can be used in various low resilience urethane foam resilient foam goods, has under the situation of temperature variation the changes in hardness features of smaller.
Embodiment
Embodiment 1
In 5 liters of stainless steel stills, add 82g glycerine, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, be evacuated to-0.098Mpa, airtight suction 12g potassium hydroxide, be warming up to 80 ℃, begin to add propylene oxide and oxyethane, keep 50-60 ℃ of temperature in the kettle, pressure 0-0.1Mpa, add 3428g propylene oxide and 490g oxyethane continuously, after charging finishes, the interior pressure reacted 2 hours, the vacuum removal unreacted is propylene oxide and oxirane monomers completely, adding 24g phosphoric acid neutralizes, use cloth formula funnel that material is filtered then, the filtrate that obtains is added in the reactor again, and add the 200g deionized water and the 8g Magnesium Silicate q-agent stirs, yet vacuum hydro-extraction 2 hours, keep 103-107 ℃ of temperature in the kettle, use cloth formula funnel that material is filtered once more then, add the filtrate that obtains in the reactor again, add the 182g acetic anhydride, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, keep 100-110 ℃ of temperature in the kettle, reacted 1 hour, cooling discharge can obtain product A.Analysis indexes is as follows: hydroxyl value 38.5mgKOH/g moisture: 0.08% viscosity 450mpa.s/25 ℃ pH value: 6.3.
Embodiment 2
In 5 liters of stainless steel stills, add 40g glycerine and 42g Diethylene Glycol, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, be evacuated to-0.098Mpa, airtight suction 8g potassium hydroxide and 4g sodium ethylate, be warming up to 80 ℃, begin to add propylene oxide and oxyethane, keep 70-80 ℃ of temperature in the kettle, pressure 0.1-0.2Mpa, add 3428g propylene oxide and 490g oxyethane continuously, after charging finishes, the interior pressure reacted 2 hours, the vacuum removal unreacted is propylene oxide and oxirane monomers completely, adding 24g phosphoric acid neutralizes, use cloth formula funnel that material is filtered then, the filtrate that obtains is added in the reactor again, and add the 200g deionized water and the 8g Magnesium Silicate q-agent stirs, yet vacuum hydro-extraction 2 hours, keep 103-107 ℃ of temperature in the kettle, use cloth formula funnel that material is filtered once more then, add the filtrate that obtains in the reactor again, add the 182g maleic anhydride, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, keep 100-110 ℃ of temperature in the kettle, reacted 1 hour, cooling discharge can obtain product A.Analysis indexes is as follows: hydroxyl value 38.5mgKOH/g moisture: 0.08% viscosity 450mpa.s/25 ℃ pH value: 6.3.
Embodiment 3
In 5 liters of stainless steel stills, add 31g propylene glycol and 20g ethylene glycol, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, be evacuated to-0.098Mpa, airtight suction 6g potassium hydroxide and 6g sodium methylate, be warming up to 80 ℃, begin to add propylene oxide and oxyethane, keep 80-90 ℃ of temperature in the kettle, pressure 0.2-0.3Mpa, add 3456g propylene oxide and 494g oxyethane continuously, after charging finishes, the interior pressure reacted 2 hours, the vacuum removal unreacted is propylene oxide and oxirane monomers completely, adding 24g phosphoric acid neutralizes, use cloth formula funnel that material is filtered then, the filtrate that obtains is added in the reactor again, and add the 200g deionized water and the 8g Magnesium Silicate q-agent stirs, yet vacuum hydro-extraction 2 hours, keep 103-107 ℃ of temperature in the kettle, use cloth formula funnel that material is filtered once more then, add the filtrate that obtains in the reactor again, add 137g acetic acid, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, keep 100-110 ℃ of temperature in the kettle, reacted 1 hour, cooling discharge can obtain product A.Analysis indexes is as follows: hydroxyl value 19.2mgKOH/g moisture: 0.09% viscosity 550mpa.s/25 ℃ pH value: 6.5.
Embodiment 4
In 5 liters of stainless steel stills, add the 135.75g tetramethylolmethane, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, be evacuated to-0.098Mpa, airtight suction 12g sodium hydroxide, be warming up to 80 ℃, begin to add propylene oxide and oxyethane, keep 100-110 ℃ of temperature in the kettle, pressure 0.3-0.4Mpa, add 3381g propylene oxide and 483g oxyethane continuously, after charging finishes, the interior pressure reacted 2 hours, the vacuum removal unreacted is propylene oxide and oxirane monomers completely, adding 24g phosphoric acid neutralizes, use cloth formula funnel that material is filtered then, the filtrate that obtains is added in the reactor again, and add the 200g deionized water and the 8g Magnesium Silicate q-agent stirs, yet vacuum hydro-extraction 2 hours, keep 103-107 ℃ of temperature in the kettle, use cloth formula funnel that material is filtered once more then, add the filtrate that obtains in the reactor again, add the 204g acetic anhydride, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, keep 100-110 ℃ of temperature in the kettle, reacted 1 hour, cooling discharge can obtain product A.Analysis indexes is as follows: hydroxyl value 58mgKOH/g moisture: 0.07% viscosity 650mpa.s/25 ℃ pH value: 6.5.
Embodiment 5
In 5 liters of stainless steel stills, add 54.5g glycerine, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, be evacuated to-0.098Mpa, airtight suction 12g potassium hydroxide, be warming up to 80 ℃, begin to add propylene oxide and oxyethane, keep 130-140 ℃ of temperature in the kettle, pressure 0.4-0.5Mpa, add 3452g propylene oxide and 493g oxyethane continuously, after charging finishes, the interior pressure reacted 2 hours, the vacuum removal unreacted is propylene oxide and oxirane monomers completely, adding 24g phosphoric acid neutralizes, use cloth formula funnel that material is filtered then, the filtrate that obtains is added in the reactor again, and add the 200g deionized water and the 8g Magnesium Silicate q-agent stirs, yet vacuum hydro-extraction 2 hours, keep 103-107 ℃ of temperature in the kettle, use cloth formula funnel that material is filtered once more then, add the filtrate that obtains in the reactor again, add the 120.8g acetic anhydride, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, keep 100-110 ℃ of temperature in the kettle, reacted 1 hour, cooling discharge can obtain product A.Analysis indexes is as follows: hydroxyl value 25.5mgKOH/g moisture: 0.08% viscosity 850mpa.s/25 ℃ pH value: 6.5.
Embodiment 6
In 5 liters of stainless steel stills, add the 40.9g tripropylene glycol, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, be evacuated to-0.098Mpa, airtight suction 12g potassium hydroxide, be warming up to 80 ℃, begin to add propylene oxide and oxyethane, keep 140-150 ℃ of temperature in the kettle, pressure 0.1-0.2Mpa, add 3465g propylene oxide and 495g oxyethane continuously, after charging finishes, the interior pressure reacted 2 hours, the vacuum removal unreacted is propylene oxide and oxirane monomers completely, adding 24g phosphoric acid neutralizes, use cloth formula funnel that material is filtered then, the filtrate that obtains is added in the reactor again, and add the 200g deionized water and the 8g Magnesium Silicate q-agent stirs, yet vacuum hydro-extraction 2 hours, keep 103-107 ℃ of temperature in the kettle, use cloth formula funnel that material is filtered once more then, add the filtrate that obtains in the reactor again, add the 90.7g acetic anhydride, carry out nitrogen replacement, survey in the still oxygen level less than 100ppm after, keep 100-110 ℃ of temperature in the kettle, reacted 1 hour, cooling discharge can obtain product A.Analysis indexes is as follows: hydroxyl value 19.2mgKOH/g moisture: 0.06% viscosity 1250mpa.s/25 ℃ pH value: 6.7.
Slow resilience polyether glycol based on embodiment 1 to embodiment 6 preparation carries out frothing test, describes by the use properties to polyethers of showing (one) comparative experiments data:
Table one is each embodiment comparative illustration data
As table (one) finding, use the present invention (embodiment one) institute synthetic low resilience urethane foam resilient foam body polyether glycol, can be used for preferably in the preparation of absorbing body and shock absorber, especially be suitable for being applicable to that temperature variation is big, but the field of having relatively high expectations for foam hardness, solve general slow resilience polyethers because temperature variation causes the bigger problem of foams changes in hardness greatly, had good economic and social benefit.
Claims (9)
1. the synthetic method of a low resilience urethane foam resilient foam body polyether glycol is characterized in that adopting multicomponent alcoholics compound as initiator, at 0-0.5Mpa pressure, under the 50-150 ℃ of temperature, with basic metal is catalyzer, and dried with acetic acid is end-capping reagent, carries out polymerization with epoxy compounds and obtains.
2. the synthetic method of low resilience urethane foam resilient foam body polyether glycol according to claim 1 is characterized in that described multicomponent alcoholics compound is the mixture that one or more arbitrary proportions in ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerine, tetramethylolmethane, Xylitol, sorbyl alcohol, N.F,USP MANNITOL, sucrose, the glycoside are formed.
3. the synthetic method of low resilience urethane foam resilient foam body polyether glycol according to claim 2 is characterized in that described polyol compound is a glycerine.
4. the synthetic method of low resilience urethane foam resilient foam body polyether glycol according to claim 1 is characterized in that described reaction pressure is 0.1-0.4Mpa, and temperature of reaction is 80-110 ℃.
5. the synthetic method of low resilience urethane foam resilient foam body polyether glycol according to claim 1, it is characterized in that described base metal catalysts is selected from the mixture of one or more compositions in sodium methylate, sodium ethylate, sodium hydroxid, the potassium hydroxide, the addition of base metal catalysts is 0.3% of a raw materials quality summation.
6. the synthetic method of low resilience urethane foam resilient foam body polyether glycol according to claim 5 is characterized in that described base metal catalysts adopts potassium hydroxide.
7. the synthetic method of low resilience urethane foam resilient foam body polyether glycol according to claim 1 is characterized in that described end-capping reagent is selected from acetic acid, maleic anhydride or acetic anhydride, wherein preferred acetic anhydride.
8. the synthetic method of low resilience urethane foam resilient foam body polyether glycol according to claim 1 is characterized in that the ratio that described end-capping reagent accounts for the molar mass of multicomponent alcoholics compound is 2: 1.
9. the synthetic method of low resilience urethane foam resilient foam body polyether glycol according to claim 1, it is characterized in that described epoxide is the mixture of propylene oxide and oxyethane, and the quality of the shared mixture of oxyethane is 12.5%, and the epoxy compounds total mass accounts for the 97%-99% of total inventory.
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| CN 201010295124 CN101967227B (en) | 2010-09-28 | 2010-09-28 | Synthetic method of slow resilience foam polyether polyol |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102875794A (en) * | 2012-10-16 | 2013-01-16 | 山东蓝星东大化工有限责任公司 | Hard bubble polyether polyol and preparation method thereof |
| CN103554472A (en) * | 2013-10-31 | 2014-02-05 | 淄博德信联邦化学工业有限公司 | Preparation method of unsaturated high-activity polyether polyol |
| CN104231258A (en) * | 2014-10-11 | 2014-12-24 | 淄博德信联邦化学工业有限公司 | Polyether defoaming agent and preparation method thereof |
| CN105461915A (en) * | 2015-12-24 | 2016-04-06 | 山东一诺威新材料有限公司 | Polyester-polyether polyol for microporous PU (polyurethane) shoe sole and preparation method of polyester-polyether polyol as well as PU shoe sole stock solution prepared from polyester-polyether polyol and preparation method of PU shoe sole stock solution |
| CN109438690A (en) * | 2018-11-13 | 2019-03-08 | 耿佃勇 | Novel unsaturated polyether polyol |
| CN110402263A (en) * | 2017-03-15 | 2019-11-01 | 科思创有限公司 | Viscoelastic polyurethane foam with reduced temperature sensitivity |
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| CN101220145A (en) * | 2008-01-24 | 2008-07-16 | 中国石油技术开发公司 | Method for producing low interfacial tension polyalcohol polyether |
| CN101463125A (en) * | 2008-12-27 | 2009-06-24 | 山东蓝星东大化工有限责任公司 | Method for synthesizing high activity rigid foam polyether polyatomic alcohol for spraying |
| US20090318656A1 (en) * | 2006-08-03 | 2009-12-24 | Klaus Poellmann | Polyetheramine Macromonomers Comprising Two Neighboring Hydroxyl Groups And Their Use For Producing Polyurethanes |
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Patent Citations (3)
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| US20090318656A1 (en) * | 2006-08-03 | 2009-12-24 | Klaus Poellmann | Polyetheramine Macromonomers Comprising Two Neighboring Hydroxyl Groups And Their Use For Producing Polyurethanes |
| CN101220145A (en) * | 2008-01-24 | 2008-07-16 | 中国石油技术开发公司 | Method for producing low interfacial tension polyalcohol polyether |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875794A (en) * | 2012-10-16 | 2013-01-16 | 山东蓝星东大化工有限责任公司 | Hard bubble polyether polyol and preparation method thereof |
| CN103554472A (en) * | 2013-10-31 | 2014-02-05 | 淄博德信联邦化学工业有限公司 | Preparation method of unsaturated high-activity polyether polyol |
| CN103554472B (en) * | 2013-10-31 | 2016-04-20 | 淄博德信联邦化学工业有限公司 | The preparation method of degree of unsaturation polyether polyol with high activity |
| CN104231258A (en) * | 2014-10-11 | 2014-12-24 | 淄博德信联邦化学工业有限公司 | Polyether defoaming agent and preparation method thereof |
| CN105461915A (en) * | 2015-12-24 | 2016-04-06 | 山东一诺威新材料有限公司 | Polyester-polyether polyol for microporous PU (polyurethane) shoe sole and preparation method of polyester-polyether polyol as well as PU shoe sole stock solution prepared from polyester-polyether polyol and preparation method of PU shoe sole stock solution |
| CN105461915B (en) * | 2015-12-24 | 2018-02-23 | 山东一诺威新材料有限公司 | Micropore PU soles polyesterether polyols, its preparation method and its PU soles systems of preparation and the preparation method of PU soles systems |
| CN110402263A (en) * | 2017-03-15 | 2019-11-01 | 科思创有限公司 | Viscoelastic polyurethane foam with reduced temperature sensitivity |
| CN110402263B (en) * | 2017-03-15 | 2022-06-07 | 科思创有限公司 | Viscoelastic polyurethane foams with reduced temperature sensitivity |
| CN109438690A (en) * | 2018-11-13 | 2019-03-08 | 耿佃勇 | Novel unsaturated polyether polyol |
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