CN103467732B - A kind of synthetic method of phosphor-containing flame-proof polyether glycol - Google Patents
A kind of synthetic method of phosphor-containing flame-proof polyether glycol Download PDFInfo
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Abstract
A synthetic method for phosphor-containing flame-proof polyether glycol, the method mainly comprises the following steps: (1) under nitrogen protection, adopts small molecule alcohol and olefin oxide to be obtained by reacting small molecules polyethers under the effect of catalyzer; (2) under nitrogen protection, mixed by the low molecular polyether that step (1) obtains with P contained compound, heat up, the dehydration of drum nitrogen, to moisture≤0.03%, is lowered the temperature when acid number is less than 0.20mgKOH/g and is obtained initiator; (3) under nitrogen protection, by initiator under the effect of catalyzer, the obtained thick ether of phosphor-containing flame-proof polyether glycol is reacted with olefin oxide; (4) neutralization, refining, purification.Have employed such scheme, obtain a kind of phosphor-containing flame-proof polyether glycol.In the fire-retardant factor, the flame retardant properties of phosphorus is far away higher than halogen, compound nitrogen series, and its final index: hydroxyl value is 28-38mgKOH/g, viscosity is 750-1050mPas/25 DEG C.Adopt P contained compound as ignition-proof element, such as halogen flame retardant element can be avoided to discharge a large amount of toxic gases in combustion, safety non-toxic.
Description
Technical field
The present invention relates to Polyurethane flame-retardant material synthesis field, be specifically related to a kind of synthesis of phosphor-containing flame-proof polyether glycol.
Background technology
Because polyurethane material has good performance, polyurethane industrial is developed rapidly, the urethane foam wherein accounting for urethane output 1/3rd because of ventilative, nontoxic, rebound resilience is good, compression set is little, heat-resisting, moisture-proof, ageing-resistant performance is good, and has oil resistant, the premium propertiess such as organic solvent-resistant, sound insulation, insulation, are widely used in every field.But it is low that it has density, specific surface area is large, very easily the shortcoming such as burning, and therefore the flame retardant properties of urethane foam is the important directions that polyurethane industries among others is studied.
The fire-retardant of current urethane foam mainly contains both direction,
(1) additive flame retardant: additive flame retardant adopts and adds fire retardant, add method that is halogen-containing, nitrogenous, phosphorous, metal-containing compound, the disadvantage of this quadrat method is the performance affecting polyurethane foam, reduce the resilience of porous plastics, compressive strength, can not stable existence in polyurethane foam, easily separate out, affect flame retardant properties.
(2) reaction-type flame-retarding: this flame resistant method is the direction of at present development, main method introduces ignition-proof element in the production of polyethers or isocyanic ester.And the use of halogen ignition-proof element is restricted in the world, because halogen-containing polyurethane foam discharges a large amount of toxic gases when burning, mankind's escape when being unfavorable for catching fire.
Summary of the invention
The present invention is in order to solve the problems of the technologies described above the shortcoming of middle existence, and provide the synthetic method of a kind of safety non-toxic, non-halogen phosphor-containing flame-proof height resilience polyether glycol that flame retardant properties is good, this synthetic method mainly comprises the following steps:
(1) under nitrogen protection, small molecule alcohol and olefin oxide is adopted to be obtained by reacting low molecular polyether under the effect of catalyzer;
(2) under nitrogen protection, mixed by the low molecular polyether that step (1) obtains, be warming up to 100 ~ 150 DEG C with P contained compound, the dehydration of drum nitrogen, to moisture≤0.03%, is cooled to less than 60 DEG C and obtains initiator when acid number is less than 0.20mgKOH/g;
(3) under nitrogen protection, initiator step (2) obtained, under the effect of catalyzer, reacts the thick ether of obtained phosphor-containing flame-proof polyether glycol with olefin oxide.
(4) the thick ether of phosphor-containing flame-proof polyether glycol above-mentioned steps (3) obtained obtains product after neutralizing, refine, dewater, filtering.
Further, described small molecule alcohol is any one or a few mixture of glycerine, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol, N.F,USP MANNITOL, sucrose.
Further, described catalyzer is metal compound as catalyst, comprises any one or a few the mixture in potassium hydroxide, sodium hydroxide.
Further, described P contained compound is Vanadium Pentoxide in FLAKES, phosphoric acid, tetra-sodium, any one or a few mixture in phosphorous acid.
Further, described olefin oxide is the mixture of any one or both in ethylene oxide and propylene oxide.
Further, described ethylene oxide and the weight ratio of propylene oxide are 80 ~ 86:20 ~ 14.
Further, the add-on of described catalyzer be total reaction solution quality 0.1% ?0.5%.
Further, the mol ratio that the small molecules polyethers described in step (2) mixes with P contained compound be 1.0:0.6 ?1.0:1.0.
Further, the thick ether of the phosphor-containing flame-proof polyether glycol of step (4) adopts the neutralization of phosphorus aqueous acid, adopts Magnesium Silicate q-agent finishing agent to refine, vacuum hydro-extraction, filters and obtain product.
Have employed such scheme, obtain a kind of phosphor-containing flame-proof polyether glycol.Organic compound containing halogenide and phosphoric, its fire retardant mechanism mainly catches the free radical that combustion reactions needs.In the fire-retardant factor, the flame retardant properties of phosphorus is far away higher than halogen, compound nitrogen series, and its final index: hydroxyl value is 28-38mgKOH/g, viscosity is 750-1050mPas/25 DEG C.Adopt P contained compound as ignition-proof element, such as halogen flame retardant element can be avoided to discharge a large amount of toxic gases in combustion, so safety non-toxic.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1:
(1) glycerine 150g is put into 2L stainless steel cauldron, add the KOH aqueous solution (alkali content 45% ± 0.5) and remove air with nitrogen, stirring is warming up to 120 DEG C, the dehydration of drum nitrogen is to moisture≤0.03%, close vacuum, add propylene oxide: 850g, to be incubated after 1 hour again vacuum 1 hour, be cooled to 90 DEG C, and neutralize, degassed, dehydration, filter, obtain small molecules polyethers MA-306-1, sampling and testing hydroxyl value 261.45mgKOH/g, moisture 0.02%, acid number: 0.05mgKOH/g, kalium ion and natrium ion: 0.5ppm, colourity (APHA): 40#.
(2) the small molecules polyethers MA-306-1 obtained in above-mentioned steps being taken out 650g joins in 2L stainless steel cauldron, add 190g Vanadium Pentoxide in FLAKES, air is removed with nitrogen, open and stir, be warming up to 100 DEG C, the dehydration of drum nitrogen is to moisture content≤0.03%, and acid number is less than 0.20mgKOH/g, be cooled to less than 60 DEG C, obtain initiator D-1.
(3) the initiator D-1 obtained in above-mentioned steps being taken out 140g joins in 2L stainless steel cauldron, add the KOH aqueous solution (alkali content 45% ± 0.5): 10.5g, stir, vacuum is warming up to 120 DEG C, drum nitrogen vacuum 1 hour, test moisture content≤0.03%, close vacuum, add 855g propylene oxide, keep still internal pressure 0.01MPa-0.4MPa, temperature remains on 80-140 DEG C, aging 2 hours, continue to drip 170g ethylene oxide, to be incubated after 1 hour again vacuum 1 hour, be cooled to 90 DEG C, obtain the thick ether of MA-3034-1, sampling and testing hydroxyl value 36.45mgKOH/g, moisture 0.02%.
(4) get the thick ether of the above-mentioned MA-3034-1 of 1000g and put into 2L stainless steel cauldron, be warming up to 90 DEG C, add the dilute phosphoric acid of 8% ± 0.1: 120g, in and 1 hour, then add finishing agent 1.5 ± 0.1g, vacuum hydro-extraction, moisture content≤0.03%, filter, discharging after clear, and the index of testing MA-3034-1.Hydroxyl value: 33.64mgKOH/g, acid number: 0.04mgKOH/g, moisture content: 0.03%, viscosity: 894mPas/25 DEG C, kalium ion and natrium ion: 0.8ppm, colourity (APHA): 40#.
Example 2:
(1) TriMethylolPropane(TMP) 120g is put into 2L stainless steel cauldron, add the NaOH aqueous solution (alkali content 45% ± 0.5) and remove air with nitrogen, stirring is warming up to 120 DEG C, the dehydration of drum nitrogen is to moisture≤0.03%, close vacuum, add ethylene oxide: 850g, to be incubated after 1 hour again vacuum 1 hour, be cooled to 90 DEG C, and neutralize, degassed, dehydration, filter, obtain small molecules polyethers MA-306-2, sampling and testing hydroxyl value 221.45mgKOH/g, moisture 0.03%, acid number: 0.04mgKOH/g, kalium ion and natrium ion: 0.3ppm, colourity (APHA): 40#.
(2) the small molecules polyethers MA-306-2 obtained in above-mentioned steps being taken out 650g joins in 2L stainless steel cauldron, add 160g tetra-sodium, air is removed with nitrogen, open and stir, be warming up to 120 DEG C, the dehydration of drum nitrogen is to moisture content≤0.03%, and acid number is less than 0.20mgKOH/g, be cooled to less than 60 DEG C, obtain initiator D-2.
(3) the initiator D-2 obtained in above-mentioned steps being taken out 135g joins in 2L stainless steel cauldron, add the KOH aqueous solution (alkali content 45% ± 0.5): 10.5g, stir, vacuum is warming up to 120 DEG C, drum nitrogen vacuum 1 hour, test moisture content≤0.03%, close vacuum, add 855g ethylene oxide, keep still internal pressure 0.01MPa-0.4MPa, temperature remains on 80-140 DEG C, aging 2 hours, continue to drip 170g propylene oxide, to be incubated after 1 hour again vacuum 1 hour, be cooled to 90 DEG C, obtain the thick ether of MA-3034-2, sampling and testing hydroxyl value 36.91mgKOH/g, moisture 0.02%.
(4) get the thick ether of the above-mentioned MA-3034-2 of 1000g and put into 2L stainless steel cauldron, be warming up to 90 DEG C, add the dilute phosphoric acid of 8% ± 0.1: 120g, in and 1 hour, then add finishing agent 1.5 ± 0.1g, vacuum hydro-extraction, moisture content≤0.03%, filter, discharging after clear, and the index of testing MA-3034-2.Hydroxyl value: 34.24mgKOH/g, acid number: 0.03mgKOH/g, moisture content: 0.02%, viscosity: 924mPas/25 DEG C, kalium ion and natrium ion: 1.6ppm, colourity (APHA): 30#.
Example 3:
(1) tetramethylolmethane 60g and sorbyl alcohol 80g is put into 2L stainless steel cauldron, add the KOH aqueous solution (alkali content 45% ± 0.5) and remove air with nitrogen, stirring is warming up to 150 DEG C, the dehydration of drum nitrogen is to moisture≤0.03%, close vacuum, add 400g ethylene oxide and 450g propylene oxide, to be incubated after 1 hour again vacuum 1 hour, be cooled to 90 DEG C, and neutralize, degassed, dehydration, filter, obtain low molecular polyether MA-306-3, sampling and testing hydroxyl value 275.25mgKOH/g, moisture 0.03%, acid number: 0.04mgKOH/g, kalium ion and natrium ion: 0.3ppm, colourity (APHA): 40#.
(2) the low molecular polyether MA-306-3 obtained in above-mentioned steps being taken out 650g joins in 2L stainless steel cauldron, add 80g phosphorous acid and 80g phosphoric acid, air is removed with nitrogen, open and stir, be warming up to 150 DEG C, the dehydration of drum nitrogen is to moisture content≤0.03%, and acid number is less than 0.20mgKOH/g, be cooled to less than 60 DEG C, obtain initiator D-3.
(3) the initiator D-3 obtained in above-mentioned steps being taken out 135g joins in 2L stainless steel cauldron, add the KOH aqueous solution (alkali content 45% ± 0.5): 10.5g, stir, vacuum is warming up to 150 DEG C, drum nitrogen vacuum 1 hour, test moisture content≤0.03%, close vacuum, add 855g ethylene oxide, keep still internal pressure 0.01MPa-0.4MPa, temperature remains on 80-140 DEG C, aging 2 hours, continue to drip 170g ethylene oxide, to be incubated after 1 hour again vacuum 1 hour, be cooled to 90 DEG C, obtain the thick ether of MA-3034-3, sampling and testing hydroxyl value 38.84mgKOH/g, moisture 0.02%.
(4) get the thick ether of the above-mentioned MA-3034-3 of 1000g and put into 2L stainless steel cauldron, be warming up to 90 DEG C, add the dilute phosphoric acid of 8% ± 0.1: 120g, in and 1 hour, then add finishing agent 1.5 ± 0.1g, vacuum hydro-extraction, moisture content≤0.03%, filter, discharging after clear, and the index of testing MA-3034-3.Hydroxyl value: 38.24mgKOH/g, acid number: 0.03mgKOH/g, moisture content: 0.02%, viscosity: 928mPas/25 DEG C, kalium ion and natrium ion: 1.9ppm, colourity (APHA): 30#.
Example 4:
(1) N.F,USP MANNITOL 60g and sucrose 80g is put into 2L stainless steel cauldron, add the KOH aqueous solution (alkali content 45% ± 0.5) and remove air with nitrogen, stirring is warming up to 150 DEG C, the dehydration of drum nitrogen is to moisture≤0.03%, close vacuum, add 400g propylene oxide and 450g ethylene oxide, to be incubated after 1 hour again vacuum 1 hour, be cooled to 90 DEG C, and neutralize, degassed, dehydration, filter, obtain low molecular polyether MA-306-4, sampling and testing hydroxyl value 292.14mgKOH/g, moisture 0.03%, acid number: 0.05mgKOH/g, kalium ion and natrium ion: 0.5ppm, colourity (APHA): 40#.
(2) the small molecules polyethers MA-306-4 obtained in above-mentioned steps being taken out 650g joins in 2L stainless steel cauldron, add 80g phosphorous acid and 80g tetra-sodium, air is removed with nitrogen, open and stir, be warming up to 150 DEG C, the dehydration of drum nitrogen is to moisture content≤0.03%, and acid number is less than 0.20mgKOH/g, be cooled to less than 60 DEG C, obtain initiator D-4.
(3) the initiator D-4 obtained in above-mentioned steps being taken out 135g joins in 2L stainless steel cauldron, add the KOH aqueous solution (alkali content 45% ± 0.5): 10.5g, stir, vacuum is warming up to 150 DEG C, drum nitrogen vacuum 1 hour, test moisture content≤0.03%, close vacuum, add 855g ethylene oxide, keep still internal pressure 0.01MPa-0.4MPa, temperature remains on 80-140 DEG C, aging 2 hours, continue to drip 170g propylene oxide, to be incubated after 1 hour again vacuum 1 hour, be cooled to 90 DEG C, obtain the thick ether of MA-3034-4, sampling and testing hydroxyl value 35.12mgKOH/g, moisture 0.02%.
(4) get the thick ether of the above-mentioned MA-3034-4 of 1000g and put into 2L stainless steel cauldron, be warming up to 90 DEG C, add the dilute phosphoric acid of 8% ± 0.1: 120g, in and 1 hour, then add finishing agent 1.5 ± 0.1g, vacuum hydro-extraction, moisture content≤0.03%, filter, discharging after clear, and the index of testing MA-3034-4.Hydroxyl value: 33.64mgKOH/g, acid number: 0.05mgKOH/g, moisture content: 0.03%, viscosity: 979mPas/25 DEG C, kalium ion and natrium ion: 0.6ppm, colourity (APHA): 50#.
Claims (8)
1. a synthetic method for phosphor-containing flame-proof polyether glycol, is characterized in that, the method mainly comprises the following steps:
(1) under nitrogen protection, small molecule alcohol and olefin oxide is adopted to be obtained by reacting low molecular polyether under the effect of catalyzer;
(2) under nitrogen protection, the low molecular polyether that step (1) obtains is mixed with P contained compound, be warming up to 100 ~ 150 DEG C, the dehydration of drum nitrogen, to moisture≤0.03%, is cooled to less than 60 DEG C and obtains initiator when acid number is less than 0.20mgKOH/g;
(3) under nitrogen protection, initiator step (2) obtained, under the effect of catalyzer, reacts the thick ether of obtained phosphor-containing flame-proof polyether glycol with olefin oxide;
(4) the thick ether of phosphor-containing flame-proof polyether glycol above-mentioned steps (3) obtained is through neutralizing, refining, dewater, filter;
Described catalyzer is metal compound as catalyst, and this metal compound as catalyst is any one or a few the mixture in potassium hydroxide, sodium hydroxide.
2. the synthetic method of a kind of phosphor-containing flame-proof polyether glycol according to claim 1, is characterized in that, described small molecule alcohol is any one or a few mixture of glycerine, TriMethylolPropane(TMP), tetramethylolmethane, sorbyl alcohol, N.F,USP MANNITOL, sucrose.
3. the synthetic method of a kind of phosphor-containing flame-proof polyether glycol according to claim 1, is characterized in that, described P contained compound is Vanadium Pentoxide in FLAKES, phosphoric acid, tetra-sodium, any one or a few mixture in phosphorous acid.
4. the synthetic method of a kind of phosphor-containing flame-proof polyether glycol according to claim 1, is characterized in that, described olefin oxide is the mixture of any one or both in ethylene oxide and propylene oxide.
5. the synthetic method of a kind of phosphor-containing flame-proof polyether glycol according to claim 4, is characterized in that, described ethylene oxide and the weight ratio of propylene oxide are 80 ~ 86:20 ~ 14.
6. the synthetic method of a kind of phosphor-containing flame-proof polyether glycol according to claim 1, is characterized in that, the add-on of described catalyzer be total reaction solution quality 0.1% ?0.5%.
7. the synthetic method of a kind of phosphor-containing flame-proof polyether glycol according to claim 1, is characterized in that, the mol ratio that the low molecular polyether described in step (2) mixes with P contained compound is 1.0 ~ 2.0:1.0 ~ 2.0.
8. the synthetic method of a kind of phosphor-containing flame-proof polyether glycol according to claim 1, it is characterized in that, the phosphor-containing flame-proof polyether glycol of step (4) adopts the neutralization of phosphorus aqueous acid, adopts Magnesium Silicate q-agent finishing agent to refine, vacuum hydro-extraction, filtration obtains.
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| CN104448290A (en) * | 2014-12-09 | 2015-03-25 | 淄博德信联邦化学工业有限公司 | Phosphorus-containing flame-retardant polyether polyol |
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| CN106008950B (en) * | 2016-05-24 | 2018-07-20 | 河北亚东化工集团有限公司 | A kind of polyether polyol and preparation method thereof of the low smoke of high fire-retardance |
| CN106589344B (en) * | 2016-12-01 | 2018-11-02 | 浙江皇马科技股份有限公司 | A kind of preparation method of unsaturated polyether |
| CN108178967A (en) * | 2017-12-29 | 2018-06-19 | 辽宁科技大学 | One kind repairs coating for wooden buildings exterior wall |
| CN109054012B (en) * | 2018-07-17 | 2020-12-01 | 上海邦高化学有限公司 | Synthesis process of polyethylene glycol |
| CN109400837A (en) * | 2018-09-30 | 2019-03-01 | 南通紫琅生物医药科技有限公司 | A kind of Halogen does not migrate flame retardant polyurethane resin and its application without molten drop |
| CN112851925B (en) * | 2021-02-02 | 2023-01-31 | 扬州晨化新材料股份有限公司 | Preparation method of mixed phosphorus-containing polyol flame retardant |
| CN114230752B (en) * | 2021-11-30 | 2023-07-18 | 山东一诺威新材料有限公司 | Intrinsic flame-retardant self-repairing polyurethane and preparation method thereof |
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