CN1293113C - Method for preparing polyether glycol in use for hard bubble of polyurethane in non-freon foaming system - Google Patents
Method for preparing polyether glycol in use for hard bubble of polyurethane in non-freon foaming system Download PDFInfo
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- CN1293113C CN1293113C CNB2005100465071A CN200510046507A CN1293113C CN 1293113 C CN1293113 C CN 1293113C CN B2005100465071 A CNB2005100465071 A CN B2005100465071A CN 200510046507 A CN200510046507 A CN 200510046507A CN 1293113 C CN1293113 C CN 1293113C
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Abstract
The present invention relates to a method for preparing full-water foaming polyether polylol, particularly to a method for preparing polyether polylol used for non-freon foaming system polyurethane hard foams, which belongs to the technical field of chemical engineering. The present invention is characterized in that an anion matching polymerization reaction is carried out by using furfuryl alcohol, nitrogen containing compounds and dihydric alcohol as composition initiators, using alkali metal hydroxides as catalysts and adding oxyalkylene at the reaction temperature of 95 to 120 DEG C and under the reaction pressure of-0.096MPa to 0.5MPa; the polyether polylol optimum for non-freon foaming system and full-water foaming system polyurethane hard foams can be prepared by neutralization, refining and filtration. The present invention introduces oxirane into the molecule structure of the polyether polylol to make products of the polyether polylol have the advantages of viscosity reduction, activity improvement and reinforced intersoiubility with water. The present invention has the advantages of simple production technology and high technical content, and the polyether polylol is an ideal product for non-freon foaming systems.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of preparation method of full water foamed polyether glycol, particularly a kind of preparation method of non-freon foaming system use for hard bubble of polyurethane polyether glycol.
Background technology
Characteristics such as hard polyurethane foaming plastics has that insulation effect is good, specific tenacity is big, electric property, chemical resistance and soundproof effect are superior, be widely used as heat-insulating material, structured material and synthetic wood or the like, these characteristics cause polyurethane rigid foam plastic to become one of modern industry kind with fastest developing speed.At present, hard polyurethane foam now has been penetrated into many fields such as building, petrochemical complex, freezing and refrigeration, shipbuilding, vehicle, aviation, machinery, instrument as thermal insulation material and structured material.Along with developing rapidly of polyurethane industrial; fluorine Lyons (CFC class) whipping agent has caused the great attention of national governments and relevant department to the destruction of atmospheric ozone layer; be the environment of protecting the mankind to depend on for existence; scientists has been developed the foaming technique in a series of replacement fluorine Lyons, and following several aspect is arranged:
1, first kind substitute is hydrogenated chloride fluorine alkane (HCFC), as a dichlorotrifluoroethane (HCFC-123) and a trifluorotrichloroethane (HCFC-141b), in these two kinds of compound molecules hydrogen atom is arranged all, can decompose in the lower region after entering atmosphere, to the ozone-depleting ability is the 3-10% of fluoro trichloromethane, but because this class whipping agent cost is expensive, in formulating of recipe, adopt " half fluorine " technology, to reduce consumption.Hydrogenated chloride fluorine alkane (HCFC) has solvability to some ABS and high-impact polystyrene, and this has brought inconvenience for the application in some fields.
2, the second class substitute is cyclopentanes (HC), its foaming system has than low thermal conductivity and ageing resistance, but it is a kind of combustible and explosive articles, not only in use wants exactissima diligentia safety, and will transform the on-the-spot equipment of whole foaming, to ensure safety in production.
3, the 3rd class substitute is carbonic acid gas (CO
2) foaming system, the advantage of carbonic acid gas is that economy is easy to get, and the ODP of carbonic acid gas is 0, does not almost have Greenhouse effect, but has the long and satisfied long term dimensional stability of people in addition of thermal conductivity height, demould time, also causes the shortcoming that foams shrink easily.
4, the 4th class substitute is full water foamed system, water at first generates carbonic acid gas with isocyanate reaction as whipping agent in foaming, carbonic acid gas plays the effect of whipping agent, water is as the most cheap raw material, be used in the foaming system, the carbonic acid gas that its reaction generates is not only nontoxic, and the ODP of carbonic acid gas is 0, its requirement to polyether glycol in the foaming system be viscosity low, good intermiscibility is arranged, so the structure of polyether glycol is had special requirement.The most promising in the foaming system of above-mentioned a few class replacement fluorine Lyons is full water foamed system, is very important so develop the polyether glycol that uses in the full water foamed system.
Summary of the invention
The present invention has overcome the defective of above-mentioned existence, and purpose is for a kind of preparation method with non-freon foaming system use for hard bubble of polyurethane polyether glycol that viscosity is low, technology is simple, use properties is good is provided.
Preparation method's content Description of non-freon foaming system use for hard bubble of polyurethane polyether glycol of the present invention:
The preparation method of non-freon foaming system use for hard bubble of polyurethane polyether glycol of the present invention, it is characterized in that: be to be compound initiator with sugar alcohol, nitrogenous compound, dibasic alcohol, with the alkali metal hydrogen oxygen compound is catalyzer, add olefin oxide and carry out the anionic coordinate polymerization reaction, temperature of reaction is 95～120 ℃, reaction pressure is-0.096MPa～0.5MPa, again through neutralization, refining, filter, make the use for hard bubble of polyurethane polyether glycol of suitable full water foamed system of non-freon foaming system;
Preparation non-freon foaming system use for hard bubble of polyurethane polyether glycol comprises the following steps:
1, preparation crude polyoxyalkylene polyol
By weight, in polymeric kettle, add concentration and be 0.2～0.6 part of 48% alkali metal hydroxide, 12～25 parts of sugar alcohols, 7.5～9.5 parts of nitrogenous compounds, 3～10 parts of dibasic alcohol, after stirring is warmed up to 95 ℃, add 55～70 parts of epoxy compoundss continuously, constant 115 ℃ of slakings 1～2 hour then to pressure,-0.092MPa, temperature is to outgas 1 hour under 115 ℃ of conditions, the nitrogen vacuum breaker adds 10～25 parts of epoxy compoundss more continuously, and slaking is constant to pressure, the degassing makes crude polyoxyalkylene polyol;
2, prepare smart polyether glycol
By weight, to in and add 100 parts of crude polyoxyalkylene polyols in the still, be warming up to 80～110 ℃, add 0.4～0.5 part of deionized water, 0.12～0.20 part of neutralizing acid, 0.00～0.14 part of pyrophosphate salt, 100～110 ℃ were stirred 0.5 hour down, 110～120 ℃ were stirred 1 hour down, after the dehydration, added 0.00～0.25 part of finishing agent, stirred 0.5 hour down at 110～120 ℃, add 0.00～0.15 part in oxidation inhibitor again, be cooled to 80 ℃ of filtrations, make non-freon foaming system use for hard bubble of polyurethane polyether glycol.
Above-mentioned alkali metal hydroxide comprises: potassium hydroxide or sodium hydroxide or lithium hydroxide; Sugar alcohol comprises: sucrose or Sionit or N.F,USP MANNITOL sugar or glucose; Nitrogenous compound comprises: Monoethanolamine MEA BASF or diethanolamine or trolamine or quadrol; Dibasic alcohol comprises: water or glycol ether or propylene glycol or dipropylene glycol; Epoxide comprises: propylene oxide and oxyethane; Neutralizing acid comprises: phosphoric acid or oxalic acid or acetate; Pyrophosphate salt comprises: tetra-sodium hydrogen sodium or tetra-sodium hydrogen calcium; Finishing agent comprises: diatomite or atlapulgite or hexa-magnesium silicate; Oxidation inhibitor comprises: 2,6-ditertbutylparacresol.
The present invention introduces oxyethane in the polyether glycol molecular structure, the polyether glycol product viscosity is reduced, activity increases, the mutual solubility enhancing of polyether glycol product and water, production technique of the present invention is simple, with high content of technology, is non-fluorine Lyons foaming system ideal polyether glycol product.
Embodiment
Embodiment one
Non-freon foaming system use for hard bubble of polyurethane polyether glycol of the present invention is to realize like this, input concentration is 48% potassium hydroxide 8.5g in the 5L reactor, sucrose 585g, diethanolamine 355g, deionized water 146g, after stirring is warmed up to 95 ℃, add continuously propylene oxide 2520g, slaking 1～2 hour is constant to pressure under 115 ℃ of conditions then ,-0.092MPa, temperature is to outgas 1 hour under 115 ℃ of conditions, the nitrogen vacuum breaker adds oxyethane 388g more continuously, and slaking is constant to pressure, the degassing makes crude polyoxyalkylene polyol;
Crude polyoxyalkylene polyol is cooled to 100 ℃, add deionized water 18g, concentration is 85% phosphoric acid 5.6g, tetra-sodium hydrogen sodium 48g, stirred 0.5 hour down for 105 ℃ in temperature, 115 ℃ were stirred 1 hour down ,-0.092MPa, temperature is to dewater 1.5 hours under 115 ℃ of conditions, vacuum breaker, add hexa-magnesium silicate 0.8g, stirred 0.5 hour down for 110 ℃, add oxidation inhibitor 2,6-ditertbutylparacresol 4g again in temperature, stirred 0.5 hour, be cooled to 80 ℃, filter, make the hard polyether glycol of non-freon system.
Embodiment two
Input concentration is 48% potassium hydroxide 19g in the 5L reactor, sucrose 600g, sorbyl alcohol 200g, glycol ether 400g stirs and heats up vacuum hydro-extraction, behind moisture content＜1%, add propylene oxide 2400g continuously, slaking 1～2 hour is constant to pressure under 115 ℃ of conditions then,-0.092Mpa, temperature is to outgas 1 hour the nitrogen vacuum breaker under 115 ℃ of conditions, add oxyethane 400g more continuously, slaking is constant to pressure, and the degassing makes crude polyoxyalkylene polyol;
Crude polyoxyalkylene polyol is cooled to 100 ℃, adding concentration is 85% phosphoric acid 6.5g, stirred 0.5 hour down for 105 ℃ in temperature, 115 ℃ were stirred 1 hour down, add hexa-magnesium silicate 0.8g, stirred 0.5 hour down for 110 ℃, be cooled to 80 ℃ in temperature, filter, make the hard polyether glycol of non-freon system.
Claims (4)
1, a kind of preparation method of non-freon foaming system use for hard bubble of polyurethane polyether glycol, it is characterized in that: be to be compound initiator with sugar alcohol, nitrogenous compound, dibasic alcohol, with the alkali metal hydrogen oxygen compound is catalyzer, add olefin oxide and carry out the anionic coordinate polymerization reaction, temperature of reaction is 95～120 ℃, reaction pressure is-0.096MPa～0.5MPa, again through neutralization, refining, filter, make the use for hard bubble of polyurethane polyether glycol of suitable full water foamed system of non-freon foaming system;
Preparation non-freon foaming system use for hard bubble of polyurethane polyether glycol comprises the following steps:
(1), preparation crude polyoxyalkylene polyol
By weight, in polymeric kettle, add concentration and be 0.2～0.6 part of 48% alkali metal hydroxide, 12～25 parts of sugar alcohols, 7.5～9.5 parts of nitrogenous compounds, 3～10 parts of dibasic alcohol, after stirring is warmed up to 95 ℃, add 55～70 parts of epoxy compoundss continuously, constant 115 ℃ of slakings 1～2 hour then to pressure,-0.092MPa, temperature is to outgas 1 hour under 115 ℃ of conditions, the nitrogen vacuum breaker adds 10～25 parts of epoxy compoundss more continuously, and slaking is constant to pressure, the degassing makes crude polyoxyalkylene polyol;
(2), prepare smart polyether glycol
By weight, to in and add 100 parts of crude polyoxyalkylene polyols in the still, be warming up to 80～110 ℃, add 0.4～0.5 part of deionized water, 0.12～0.20 part of neutralizing acid, 0.00～0.14 part of pyrophosphate salt, 100～110 ℃ were stirred 0.5 hour down, 110～120 ℃ were stirred 1 hour down, after the dehydration, added 0.00～0.25 part of finishing agent, stirred 0.5 hour down at 110～120 ℃, add 0.00～0.15 part in oxidation inhibitor again, be cooled to 80 ℃ of filtrations, make non-freon foaming system use for hard bubble of polyurethane polyether glycol.
2, the preparation method of non-freon foaming system use for hard bubble of polyurethane polyether glycol according to claim 1, it is characterized in that: said alkali metal hydroxide comprises: potassium hydroxide or sodium hydroxide or lithium hydroxide; Sugar alcohol comprises: sucrose or Sionit or N.F,USP MANNITOL sugar or glucose; Nitrogenous compound comprises: Monoethanolamine MEA BASF or diethanolamine or trolamine or quadrol; Dibasic alcohol comprises: water or glycol ether or propylene glycol or dipropylene glycol; Epoxide comprises: propylene oxide and oxyethane; Neutralizing acid comprises: phosphoric acid or oxalic acid or acetate; Pyrophosphate salt comprises: tetra-sodium hydrogen sodium or tetra-sodium hydrogen calcium; Finishing agent comprises: diatomite or atlapulgite or hexa-magnesium silicate; Oxidation inhibitor comprises: 2,6-ditertbutylparacresol.
3, the preparation method of non-freon foaming system use for hard bubble of polyurethane polyether glycol according to claim 1, it is characterized in that: input concentration is 48% potassium hydroxide 8.5g in the 5L reactor, sucrose 585g, diethanolamine 355g, deionized water 146g, after stirring is warmed up to 95 ℃, add continuously propylene oxide 2520g, slaking 1～2 hour is constant to pressure under 115 ℃ of conditions then ,-0.092Mpa, temperature is to outgas 1 hour under 115 ℃ of conditions, the nitrogen vacuum breaker adds oxyethane 388g more continuously, and slaking is constant to pressure, the degassing makes crude polyoxyalkylene polyol;
Crude polyoxyalkylene polyol is cooled to 100 ℃, add deionized water 18g, concentration is 85% phosphoric acid 5.6g, tetra-sodium hydrogen sodium 48g, stirred 0.5 hour down for 105 ℃ in temperature, 115 ℃ were stirred 1 hour down ,-0.092MPa, temperature is to dewater 1.5 hours under 115 ℃ of conditions, vacuum breaker, add hexa-magnesium silicate 0.8g, stirred 0.5 hour down for 110 ℃, add oxidation inhibitor 2,6-ditertbutylparacresol 4g again in temperature, stirred 0.5 hour, be cooled to 80 ℃, filter, make the hard polyether glycol of non-freon system.
4, the preparation method of non-freon foaming system use for hard bubble of polyurethane polyether glycol according to claim 1, it is characterized in that: input concentration is 48% potassium hydroxide 19g in the 5L reactor, sucrose 600g, sorbyl alcohol 200g, glycol ether 400g, stir intensification vacuum hydro-extraction, behind moisture content＜1%, add propylene oxide 2400g continuously, slaking 1～2 hour is constant to pressure under 115 ℃ of conditions then,-0.092MPa, temperature is to outgas 1 hour the nitrogen vacuum breaker under 115 ℃ of conditions, add oxyethane 400g more continuously, slaking is constant to pressure, and the degassing makes crude polyoxyalkylene polyol;
Crude polyoxyalkylene polyol is cooled to 100 ℃, adding concentration is 85% phosphoric acid 6.5g, stirred 0.5 hour down for 105 ℃ in temperature, 115 ℃ were stirred 1 hour down, add hexa-magnesium silicate 0.8g, stirred 0.5 hour down for 110 ℃, be cooled to 80 ℃ in temperature, filter, make the hard polyether glycol of non-freon system.
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| CNB2005100465071A CN1293113C (en) | 2005-05-25 | 2005-05-25 | Method for preparing polyether glycol in use for hard bubble of polyurethane in non-freon foaming system |
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| CNB2005100465071A CN1293113C (en) | 2005-05-25 | 2005-05-25 | Method for preparing polyether glycol in use for hard bubble of polyurethane in non-freon foaming system |
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| CN1293113C true CN1293113C (en) | 2007-01-03 |
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| CN102617848A (en) * | 2012-04-18 | 2012-08-01 | 南宁市化工研究设计院 | Method for preparing sorbitol polyether polyol |
| CN102702473B (en) * | 2012-05-25 | 2013-10-30 | 武汉工程大学 | Epoxy modified polyurethane double-component grouting material for road engineering maintenance and preparation method thereof |
| CN104004178B (en) * | 2014-04-19 | 2016-06-08 | 上海东大化学有限公司 | A kind of Sucrose polyethers polyhydric alcohol and its preparation method and application |
| CN105237760A (en) * | 2015-11-13 | 2016-01-13 | 淄博德信联邦化学工业有限公司 | Preparation method of glucose hard-foam polyether polyol |
| PL440409A1 (en) * | 2022-02-18 | 2023-08-21 | Pcc Rokita Spółka Akcyjna | Process for obtaining polyether polyol of low alkali metal ion content |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57118A (en) * | 1980-06-02 | 1982-01-05 | Mitui Toatsu Chem Inc | Polyether-polyol composition for production of rigid polyurethane foam |
| CN1058025A (en) * | 1991-06-03 | 1992-01-22 | 化学工业部科学技术研究总院 | Low fluorine (Lyons) foamed polyether polyhydric alcohol synthesis technique |
| JPH069773A (en) * | 1992-06-24 | 1994-01-18 | Nippon Steel Chem Co Ltd | Polyhydroxypolyether |
| CN1075528C (en) * | 1997-06-24 | 2001-11-28 | 艾郁声 | Process for preparing polyether polylol |
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2005
- 2005-05-25 CN CNB2005100465071A patent/CN1293113C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57118A (en) * | 1980-06-02 | 1982-01-05 | Mitui Toatsu Chem Inc | Polyether-polyol composition for production of rigid polyurethane foam |
| CN1058025A (en) * | 1991-06-03 | 1992-01-22 | 化学工业部科学技术研究总院 | Low fluorine (Lyons) foamed polyether polyhydric alcohol synthesis technique |
| JPH069773A (en) * | 1992-06-24 | 1994-01-18 | Nippon Steel Chem Co Ltd | Polyhydroxypolyether |
| CN1075528C (en) * | 1997-06-24 | 2001-11-28 | 艾郁声 | Process for preparing polyether polylol |
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