CN102432859B - Synthesis method of flexible-foam flame-retardant polyether polyol - Google Patents
Synthesis method of flexible-foam flame-retardant polyether polyol Download PDFInfo
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- CN102432859B CN102432859B CN 201110243875 CN201110243875A CN102432859B CN 102432859 B CN102432859 B CN 102432859B CN 201110243875 CN201110243875 CN 201110243875 CN 201110243875 A CN201110243875 A CN 201110243875A CN 102432859 B CN102432859 B CN 102432859B
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Abstract
The invention relates to a synthesis method of flexible-foam flame-retardant polyether polyol, aiming at providing the synthesis method of the flexible-foam flame-retardant polyether polyol with good flame retardance, safety, no toxicity and low cost. The synthesis method comprises the following steps of: adopting a melamine-formaldehyde condensation compound and a polyol compound as a mixed initiator; firstly under the action of amine, carrying out polymerization with olefin oxide and obtaining high-hydroxyl-value polyether; and then under the action of alkali metal catalyst, adding the olefin oxide again for further polymerization and obtaining the flexible-foam flame-retardant polyether polyol. In the synthesis method, the preparation process is simple, the cost is low and the influence on the physical and mechanical performances is less. The flexible-foam flame-retardant polyether polyol prepared by the method is light in color and low in viscosity and can be widely used for preparing the flame-retardant flexible polyurethane foam. A prepared flame-retardant flexible polyurethane foam plastic product has the advantages of high oxygen index, good flame-retardant effect, high heat resistance, good size stability and high strength.
Description
Technical field
The present invention relates to a kind of synthetic method of soft bubble flame retardant polyether polyol, this soft bubble flame retardant polyether polyol can be used for the preparation of flame retardant type flexible urethane foam.
Background technology
In recent years, because of the premium properties that polyurethane material has, China's polyurethane industrial has obtained fast development.Account for wherein that urethane output flex foam greatly is soft because of light weight, insulation, ventilative, nontoxic, rebound resilience is good, compression set is little, moisture-proof, ageing-resistant performance are good, and have multiple good characteristics such as oil resistant, organic solvent-resistant, sound insulation, insulation, be widely used in every field, purposes is extremely extensive.But simultaneously, flex foam is also because density is little, specific surface area is large, very easily lighted and burns, and combustion problem is outstanding, so be important research direction of urethane industry with flame-retardant polyurethane foam plastic.
Fire-retardant the mainly containing of polyurethane foam added fire retardant method and two kinds of methods of reactive flame retardant method at present.
Add the fire retardant method and tend to cause foam collapse bubble, cracking, efflorescence or the physical and mechanical properties such as its resilience is significantly descended, lost the performance advantage that itself has, and these fire retardants when adding separately flame retardant effect not remarkable.
The reactive flame retardant method is at the main raw material of producing polyurethane soft foamed plastics---introduces ignition-proof element in polyether glycol, the isocyanate molecule, makes in the polyurethane soft foamed plastics molecule that makes and contain ignition-proof element, thereby obtain flame retardant properties.Introduce the polyether glycol of the halogen series elements such as ignition-proof element chlorine, bromine because the product acid number is too high and to shortcomings such as equipment corrosion are large, eliminated gradually.Introduce high, the low bearing capacity of the prepared polyurethane foam cost of polyether glycol of ignition-proof element phosphorus, also out-of-date.So need that a kind of flame retardant properties is good, the synthetic method of safety non-toxic, fire-retardant polyether polyol for soft PU foam that cost is low.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of flame retardant properties is good, the synthetic method of safety non-toxic, fire-retardant polyether polyol for soft PU foam that cost is low.
Technical scheme of the present invention is: a kind of synthetic method of soft bubble flame retardant polyether polyol, take carbamide condenses and multicomponent alcoholics compound as mixing initiator, under the amines catalyst effect, carry out polymerization with olefin oxide and obtain high hydroxyl value polyethers first, its hydroxyl value is 400～600; High hydroxyl value polyethers under the base metal catalysts effect, is added the further polymerization of olefin oxide and is obtained soft bubble flame retardant polyether polyol again, and its hydroxyl value is 40～70.
Described carbamide condenses be trimeric cyanamide and formaldehyde with the mol ratio of 1:3, make in 60～100 ℃ of lower reactions of temperature.
The mass ratio of described carbamide condenses and multicomponent alcoholics compound is 1:100～100:1, preferred 100:30.
Described carbamide condenses and multicomponent alcoholics compound quality sum are 5%～80% of whole reaction system quality, preferred 20%～50%.Described reaction system is carbamide condenses, multicomponent alcoholics compound, amines catalyst, olefin oxide and base metal catalysts.
The quality consumption of described amines catalyst is 0.5%～5%, preferred 1%～3% of carbamide condenses and multicomponent alcoholics compound quality sum.
The quality consumption of described olefin oxide is carbamide condenses and multicomponent alcoholics compound quality sum 3 times～20 times, preferred 5 times～10 times.
The quality consumption of described base metal catalysts is 0.5%～5%, preferred 1%～3% of carbamide condenses and multicomponent alcoholics compound quality sum.
Described multicomponent alcoholics compound is selected from the mixture of one or more compositions 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.
Described amines catalyst is selected from the mixture of one or more compositions in dimethylamine, diethylamine, diethanolamine, triethylamine, trolamine, the tertiary amine.
Described olefin oxide is the mixture of one or more compositions in oxyethane, propylene oxide, the epoxy chloropropane.
Described base metal catalysts is selected from the mixture of one or more compositions in sodium methylate, sodium ethylate, sodium hydroxide, the potassium hydroxide.
Method of the present invention is to introduce ignition-proof element nitrogen in polyether glycol, thereby obtains flame retardant properties.This method have the flame retardant properties persistence good, on advantages such as physical and mechanical properties impact are less.
Beneficial effect of the present invention is:
1, the synthetic method of soft bubble flame retardant polyether polyol provided by the invention, preparation technology is simple, and cost is low, and is less on the physical and mechanical properties impact.
2, the soft bubble flame retardant polyether polyol that utilizes method provided by the invention to make, lighter color, viscosity are low, good stability, easily foaming, and the hazardous and noxious substances such as not phosphorous, halogen, vinylbenzene, vinyl cyanide can be widely used in the preparation of the soft bubble of flame-retardant polyurethane.
3, the flame retardant type flexible urethane foam goods that the soft bubble flame retardant polyether polyol that utilizes the present invention to make makes have the oxygen index height, good flame retardation effect, thermotolerance height, good stability of the dimension, intensity high.
Embodiment
Following examples are used for further specifying the present invention, but do not limit the present invention.
Embodiment 1:
Add trimeric cyanamide 126g in the 5L stainless steel cauldron, massfraction is 37% formaldehyde solution 244g, and suction diethanolamine 5g at 70 ℃ of reaction 3h, makes carbamide condenses 216g; Add ethylene glycol 62g, after continuing to react 1h, 70 ℃ of lower decompression dehydrations are to water ratio 5% again.Be warming up to 80 ℃, begin to add propylene oxide, keep still internal pressure 0.1～0.4MPa, 80～100 ℃ of temperature add the 716g propylene oxide continuously, after propylene oxide feed finishes, interior pressure reaction 3h, unreacted propylene oxide and water are sloughed in decompression, get the high hydroxyl value polyethers of water ratio≤0.01%, and its hydroxyl value is 426mgKOH/g.
In reactor, add 5.2gKOH, be warming up to 110 ℃, begin to add propylene oxide, add continuously the 1570g propylene oxide, react and to get thick polyethers, through refining the soft bubble flame retardant polyether polyol that neutralizes.Soft bubble flame retardant polyether polyol analysis indexes is as follows: hydroxyl value is 51.8mgKOH/g, viscosity 840mPa.s/25 ℃.
Embodiment 2:
Add trimeric cyanamide 126g in the 5L stainless steel cauldron, massfraction is 37% formaldehyde solution 244g, and suction tertiary amine 5g at 70 ℃ of reaction 3h, makes carbamide condenses 216g; Add dipropylene glycol 134g, after continuing to react 1h, 70 ℃ of lower decompression dehydrations are to water ratio 5% again.Be warming up to 80 ℃, begin to add oxyethane, keep still internal pressure 0.1～0.4MPa, 80～100 ℃ of temperature add 396g oxyethane continuously, after the oxyethane charging finishes, interior pressure reaction 3h, unreacted oxyethane and water are sloughed in decompression, get the high hydroxyl value polyethers of water ratio≤0.01%, and its hydroxyl value is 492mgKOH/g.
In reactor, add 4.8gNaOH, be warming up to 110 ℃, begin to add oxyethane, add continuously 1210g oxyethane, react and to get thick polyethers, through refining the soft bubble flame retardant polyether polyol that neutralizes.Soft bubble flame retardant polyether polyol analysis indexes is as follows: hydroxyl value is 63.5mgKOH/g, viscosity 630mPa.s/25 ℃.
Embodiment 3:
Add trimeric cyanamide 126g in the 5L stainless steel cauldron, massfraction is 37% formaldehyde solution 244g, and suction triethylamine 5g at 70 ℃ of reaction 3h, makes carbamide condenses 216g; Add glycerine 92g, after continuing to react 1h, 70 ℃ of lower decompression dehydrations are to water ratio 5% again.Be warming up to 80 ℃, begin to add propylene oxide, keep still internal pressure 0.1～0.4MPa, 80～100 ℃ of temperature add the 522g propylene oxide continuously, after propylene oxide feed finishes, interior pressure reaction 3h, unreacted propylene oxide and water are sloughed in decompression, get the high hydroxyl value polyethers of water ratio≤0.01%, and its hydroxyl value is 558mgKOH/g.
In reactor, add 4.2gCH
3ONa is warming up to 110 ℃, begins to add propylene oxide, adds continuously the 1680g propylene oxide, reacts to get thick polyethers, through refining the soft bubble flame retardant polyether polyol that neutralizes.Soft bubble flame retardant polyether polyol analysis indexes is as follows: hydroxyl value is 49.6mgKOH/g, viscosity 700mPa.s/25 ℃.
Embodiment 4:
Add trimeric cyanamide 126g in the 5L stainless steel cauldron, massfraction is 37% formaldehyde solution 244g, and suction tertiary amine 5g at 70 ℃ of reaction 3h, makes carbamide condenses 216g; Add tetramethylolmethane 136g, after continuing to react 1h, 70 ℃ of lower decompression dehydrations are to water ratio 5% again.Be warming up to 80 ℃, begin to add oxyethane, keep still internal pressure 0.1～0.4MPa, 80～100 ℃ of temperature add 440g oxyethane continuously, after the oxyethane charging finishes, interior pressure reaction 3h, unreacted oxyethane and water are sloughed in decompression, get the high hydroxyl value polyethers of water ratio≤0.01%, and its hydroxyl value is 510mgKOH/g.
In reactor, add 4gCH
3CH
2ONa is warming up to 110 ℃, begins to add oxyethane, adds continuously 1325g oxyethane, reacts to get thick polyethers, through refining the soft bubble flame retardant polyether polyol that neutralizes.Soft bubble flame retardant polyether polyol analysis indexes is as follows: hydroxyl value is 60.7mgKOH/g, viscosity 670mPa.s/25 ℃.
Embodiment 5:
Add trimeric cyanamide 126g in the 5L stainless steel cauldron, massfraction is 37% formaldehyde solution 244g, and suction triethylamine 5g at 70 ℃ of reaction 3h, makes carbamide condenses 216g; Add sorbyl alcohol 182g, after continuing to react 1h, 70 ℃ of lower decompression dehydrations are to water ratio 5% again.Be warming up to 80 ℃, begin to add propylene oxide, keep still internal pressure 0.1～0.4MPa, 80～100 ℃ of temperature add the 630g propylene oxide continuously, after propylene oxide feed finishes, interior pressure reaction 3h, unreacted propylene oxide and water are sloughed in decompression, get the high hydroxyl value polyethers of water ratio≤0.01%, and its hydroxyl value is 397mgKOH/g.
In reactor, add 4.8gKOH, be warming up to 110 ℃, begin to add propylene oxide, add continuously the 1435g propylene oxide, react and to get thick polyethers, through refining the soft bubble flame retardant polyether polyol that neutralizes.Soft bubble flame retardant polyether polyol analysis indexes is as follows: hydroxyl value is 55.5mgKOH/g, viscosity 820mPa.s/25 ℃.
The performance index of the flame retarded polyurethane-foam that the performance index of the soft bubble flame retardant polyether polyol that table 1 makes for embodiment 1-5, table 2 make for the soft bubble flame retardant polyether polyol foaming that utilizes embodiment 1-5 to make.
The performance index of the soft bubble flame retardant polyether polyol of table 1
Can find out by table 1: low, the good stability of soft bubble flame retardant polyether polyol viscosity that method of the present invention makes.
The performance index of table 2 flame retarded polyurethane-foam
| Performance index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Oxygen index/(OI) | 30 | 30.5 | 30 | 30.5 | 30 |
| Rebound degree/% | 60 | 61 | 61 | 59 | 60 |
| Tensile strength/KPa | 123 | 125 | 124 | 125 | 126 |
| Smoke density/% | 57 | 57 | 58 | 58 | 57 |
Can find out that by table 2 the soft bubble flame retardant polyether polyol that utilizes method provided by the invention to make utilizes the flame retarded polyurethane-foam goods oxygen index of its foaming preparation high, good flame retardation effect, thermotolerance height, good stability of the dimension, intensity height.
Claims (8)
1. the synthetic method of a soft bubble flame retardant polyether polyol, it is characterized in that, take carbamide condenses and multicomponent alcoholics compound as mixing initiator, first under the amines catalyst effect, carry out polymerization with olefin oxide and obtain high hydroxyl value polyethers, high hydroxyl value polyethers under the base metal catalysts effect, is added the further polymerization of olefin oxide and is obtained again;
The mass ratio of described carbamide condenses and multicomponent alcoholics compound is 1:100～100:1;
The quality consumption of described olefin oxide is carbamide condenses and multicomponent alcoholics compound quality sum 3 times～20 times;
Described high hydroxyl value polyethers hydroxyl value is 400～600mgKOH/g;
Described multicomponent alcoholics compound is selected from the mixture of one or more compositions 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;
Described olefin oxide is the mixture of one or more compositions in oxyethane, propylene oxide, the epoxy chloropropane.
2. the synthetic method of soft bubble flame retardant polyether polyol according to claim 1 is characterized in that, described carbamide condenses be trimeric cyanamide and formaldehyde with the mol ratio of 1:3, make in 60～100 ℃ of lower reactions of temperature.
3. the synthetic method of soft bubble flame retardant polyether polyol according to claim 1 is characterized in that, described soft bubble flame retardant polyether polyol hydroxyl value is 40～70mgKOH/g.
4. the synthetic method of soft bubble flame retardant polyether polyol according to claim 1 is characterized in that, described carbamide condenses and multicomponent alcoholics compound quality sum are 5%～80% of whole reaction system quality; Described reaction system is carbamide condenses, multicomponent alcoholics compound, amines catalyst, olefin oxide and base metal catalysts.
5. the synthetic method of soft bubble flame retardant polyether polyol according to claim 1 is characterized in that, the quality consumption of described amines catalyst is 0.5%～5% of carbamide condenses and multicomponent alcoholics compound quality sum.
6. the synthetic method of soft bubble flame retardant polyether polyol according to claim 1 is characterized in that, the consumption of described base metal catalysts is 0.5%～5% of carbamide condenses and multicomponent alcoholics compound quality sum.
7. the synthetic method of soft bubble flame retardant polyether polyol according to claim 1 is characterized in that, described amines catalyst is selected from the mixture of one or more compositions in dimethylamine, diethylamine, diethanolamine, the tertiary amine.
8. the synthetic method of soft bubble flame retardant polyether polyol according to claim 1 is characterized in that, described base metal catalysts is selected from the mixture of one or more compositions in sodium methylate, sodium ethylate, sodium hydroxide, the potassium hydroxide.
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| CN103467732A (en) * | 2013-08-22 | 2013-12-25 | 常州市中亚化工有限公司 | Phosphorus-containing antiflaming polyether polyol synthetic method |
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| CN114957641B (en) * | 2022-01-24 | 2023-12-22 | 佳化化学科技发展（上海）有限公司 | Flame-retardant polyether polyol and single-component polyurethane foam joint mixture using same as raw material |
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| CN1130409C (en) * | 2001-11-06 | 2003-12-10 | 朱吕民 | Nano-size incombustible polyether polyol polymer and its preparing process and application |
| EP2094757B1 (en) * | 2006-11-14 | 2021-01-13 | Basf Se | Method for the production of rigid polyurethane foams |
| CN101775131A (en) * | 2010-02-03 | 2010-07-14 | 山东蓝星东大化工有限责任公司 | Method for synthesis of novel flame-retardant rigid-foam polyether polyol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103467732A (en) * | 2013-08-22 | 2013-12-25 | 常州市中亚化工有限公司 | Phosphorus-containing antiflaming polyether polyol synthetic method |
| CN103467732B (en) * | 2013-08-22 | 2015-12-23 | 常州市盛发灯泡厂 | A kind of synthetic method of phosphor-containing flame-proof polyether glycol |
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