CN105111429A - Preparation method and application of brominated flame-retardant polyether glycol - Google Patents
Preparation method and application of brominated flame-retardant polyether glycol Download PDFInfo
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Abstract
The invention discloses a preparation method and application of brominated flame-retardant polyether glycol. The method mainly comprises the following steps: ring-opening polymerization reaction of dibasic alcohol/phenolic compound and epoxy chloropropane, bromination reaction, cyclization dechlorination reaction, and ring-opening hydrolysis reaction. The brominated flame-retardant polyether glycol can be used for preparing a polyurethane rigid foam material with the flame-retardant grade of B1 when being combined with an additive phosphorus flame retardant, and endows the polyurethane rigid foam material with excellent mechanical properties on the premise of enhancing the flame retardancy of the polyurethane rigid foam.
Description
Technical field
The present invention relates to a kind of preparation method that can be used for the fire-retardant bromopolyether polyvalent alcohol of hard polyurethane foam material, more specifically relate to a kind of preparation method and purposes of brominated flame retardant polyether glycol.Belong to organic synthesis field.
Background technology
Rigid polyurethane foam heat-insulating property is excellent, and light weight, good stability of the dimension, convenient formation, is widely used in the fields such as building heat preservation, refrigeration, transport and chemical industry usually used as lagging material.But its inflammableness is the greatest problem of restriction rigid polyurethane foam range of application.Current, addressing this problem main path is by adding fire retardant to realize in material preparation process.The fire retardant being applicable to rigid polyurethane foam can be divided into addition type and the large class of response type two.Wherein, additive flame retardant is containing ignition-proof elements such as certain chlorine, bromine, phosphorus or nitrogen but not containing any compound with reaction active groups; Reactive flame retardant then comprises ignition-proof element and reaction active groups simultaneously, and it directly as the raw material of hard polyurethane material, can participate in the chemical reaction of urethane.Additive flame retardant mostly is micromolecular compound, and the weathering process with material can be moved out problem, and has certain plasticization effect to material itself; And reactive flame retardant is fixed in material this subject with chemical bond form, there is lasting flame retardant effect, and add number more time, can't have much impact to the mechanical property of foam materials, because of but high performance polyurethane lagging material fill a prescription in requisite composition.
US Patent No. 5985965 reports a kind of reaction-type flame-retarding polyether glycol of halogen-free phosphorus-containing, adding this fire retardant of 6-12 part in every 100 formulas can by German DIN4102B level test, but there is facile hydrolysis in this based flame retardant, the problem bad with other polyether polyatomic alcohol component consistencies.US Patent No. 5049697 reports a kind of brominated reaction-type flame-retarding polyethers, this flame retarding polyether is reacted by PHT4 and glycol ether and propylene glycol and prepares, its feature is that bromine content is high, stable in properties, with polyvalent alcohol and whipping agent, there is good consistency, current Albemarle company has corresponding commercially produced product SaytexRB-79, but the typical problem of this based flame retardant to be viscosity excessive, need during use with other non-reactive low viscosity fire retardant with the use of.Chinese Patent Application No. be 20101029581.6 patent describes a kind of reaction-type flame-retarding polyether glycol prepared by polyvalent alcohol, epoxy compounds and tribromophenol, and be applied to the preparation of hard polyurethane foam material, because molecular weight of product is comparatively large and viscosity is too high, exist during practical application and mix difficult problem with whipping agent; Chinese Patent Application No. 201110249069.4 discloses a kind of method that phosphorous Halogen flame retardant polyester polyvalent alcohol is prepared in reaction by phosphoryl chloride and brominated dibasic alcohol, the flame retardant properties of polyurethane material significantly can be improved after adding a certain amount of this polyester, but expensive acid binding agent is used in a large number in its preparation process, preparation cost is excessive, and due to polyester itself, to have viscosity large, the problem that functionality is low, the addition in hard polyurethane foam formula is limited.
Summary of the invention
Technical problem to be solved by this invention is the preparation method providing a kind of brominated flame retardant polyether glycol for above-mentioned prior art, and solve current flame retarding polyether ubiquitous on the high side, viscosity is excessive, the problem that functionality is on the low side.The method utilizes cheap dibasic alcohol (phenol) to be initiator, and after being first polymerized with epoxy chloropropane, then through bromination, epoxidation, the process be finally hydrolyzed, has prepared the low viscosity halopolyether polyvalent alcohol with polyfunctionality (3 ~ 4).The method raw material is cheap and easy to get, and reaction is simple, has great industrial prospect.
The present invention's adopted technical scheme that solves the problem is: a kind of preparation method of brominated flame retardant polyether glycol, comprises the following steps:
(1) with dibasic alcohol/phenol for initiator causes the ring-opening polymerization of epoxy chloropropane under catalyst action, prepare the Hydrin of difunctionality, temperature of reaction is 60 ~ 120
oc, the reaction times is 3 ~ 10 hours;
(2) bromine be added dropwise in the difunctionality Hydrin that step (1) obtains and react, dropping temperature is-20
oc ~ 20
oc, time for adding is 3 ~ 10 hours.
(3) Hydrin of bromination step (2) obtained and strong base solution react to be sloughed part chlorine atom and obtains epoxy terminated compound, and temperature of reaction is 0 ~ 90
oc, the reaction times is 2 ~ 6 hours;
(4) under an acidic catalyst effect, under water and organic solvent, be hydrolyzed the epoxy terminated compound that step (3) obtains reaction, and obtain polyfunctionality Halogen flame retardant polyether polyol solution, hydrolysis temperature is 45 ~ 95
oc, hydrolysis time is 2 ~ 8 hours;
(5) the polyether polyols alcoholic solution obtained in step (4) is carried out underpressure distillation, obtain product Halogen flame retardant polyether polyol;
Wherein:
Dibasic alcohol/phenol described in step (1) is the combination of one or more (containing two kinds) in BDO, neopentyl glycol, dinitrobenzene propylene glycol, 1,6-hexylene glycol, Isosorbide-5-Nitrae-butylene glycol, dihydroxyphenyl propane, bisphenol S;
Described in step (1), catalyzer is Lewis acid, protonic acid or trialkyloxonium salt, is preferably protonic acid, more preferably oleum and/or perchloric acid; The add-on of catalyzer is 0.05 ~ 0.5wt% of initiator dibasic alcohol/phenol, preferably 0.08 ~ 0.12wt%.
Described in step (1), the mol ratio of initiator dibasic alcohol/phenol and epoxy chloropropane is 1:4 ~ 10, preferred 1:5 ~ 6; Temperature of reaction is 60 ~ 120
oc, preferably 110 ~ 120
oc; Reaction times is 3 ~ 10 hours, is preferably 4 ~ 6 hours.
In step (2), the mol ratio of the Hydrin that bromine used and step (1) obtain is 1 ~ 4:1, preferably 2 ~ 3:1; Temperature of reaction is-20 ~ 20
oc, preferred-20 ~ 0
oc; Reaction times is 3 ~ 10 hours, preferably 7 ~ 9 hours.
Described in step (3), highly basic is sodium hydroxide, potassium hydroxide, calcium hydroxide or lithium hydroxide aqueous solution, preferred sodium hydroxide or potassium hydroxide aqueous solution; Sodium hydroxide or potassium hydroxide aqueous solution concentration are 30 ~ 80wt%, preferably 40 ~ 50wt%; The mol ratio of the bromination Hydrin that sodium hydroxide used or potassium hydroxide and step (2) obtain is 1 ~ 6:1, preferably 2 ~ 3:1; Temperature of reaction is 0 ~ 90
oc, preferably 50 ~ 60
oc; Reaction times is 2 ~ 6 hours, preferably 3 ~ 4 hours.
In step of the present invention (4), an acidic catalyst used is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, tosic acid or perchloric acid, preferred hydrochloric acid (38wt%) or nitric acid (68wt%); The add-on of an acidic catalyst is 0.1 ~ 1wt% of the epoxy terminated compound that step (3) obtains, preferably 0.5 ~ 0.8wt%.
In step of the present invention (4), organic solvent used is one in tetrahydrofuran (THF), dimethyl formamide, dioxane, acetone, methyl alcohol, ethanol or acetonitrile or its mixture, and preferred acetone is or/and tetrahydrofuran (THF); The mass ratio of the epoxy terminated compound obtained in organic solvent used, water and step (3) is 1 ~ 5:1 ~ 5:1, preferably 2 ~ 2.5:1 ~ 1.5:1; Hydrolysis temperature is 45 ~ 95
oc, preferably 50 ~ 60
oc.Hydrolysis time is 2 ~ 8 hours, preferably 4 ~ 5 hours.
In step of the present invention (5), vacuum distillation temperature is 60 ~ 120
oc, preferably 80 ~ 90
oc.
Preferably, described in step (1), catalyzer is oleum and/or perchloric acid, and the add-on of catalyzer is initiator dibasic alcohol/dihydric phenol 0.08 ~ 0.12wt%.
Preferably, in step (1), the mol ratio of initiator dibasic alcohol/dihydric phenol and epoxy chloropropane is 1:5 ~ 6, and temperature of reaction is 110 ~ 120
oc, the reaction times is 4 ~ 6 hours.
Preferably, in step (2), the mol ratio of the Hydrin that bromine used and step (1) obtain is 2 ~ 3:1, and temperature of reaction is-20 ~ 0
oc, the reaction times is 7 ~ 9 hours.
Preferably, step (3) sodium hydroxide or potassium hydroxide aqueous solution concentration are 40 ~ 50wt%, and the mol ratio of the bromination Hydrin that sodium hydroxide used or potassium hydroxide and step (2) obtain is 2 ~ 3:1, and temperature of reaction is 50 ~ 60
oc, the reaction times is 3 ~ 4 hours.
Preferably, in step (4), an acidic catalyst used is the hydrochloric acid of 38wt% or the nitric acid of 68wt%, and the add-on of an acidic catalyst is 0.5 ~ 0.8wt% of the epoxy terminated compound that step (3) obtains.
Preferably, in step (4) organic solvent used be acetonitrile or/and tetrahydrofuran (THF), the mass ratio of the epoxy terminated compound obtained in organic solvent used, water and step (3) is 1:1.2 ~ 1.4:3.3 ~ 3.4, and hydrolysis temperature is 50 ~ 60
oc, hydrolysis time is 4 ~ 5 hours.
Preferably, in step (5), vacuum distillation temperature is 80 ~ 90
oc.
Another object of the present invention utilizes the brominated flame retardant polyether glycol prepared, in conjunction with the phosphorus flame retardant of addition type, strengthened the flame retardant effect of flame retardant polyether polyol by phosphorus halogen synergy, while raising hard polyurethane foam flame retardant resistance, give the mechanical property of its excellence.Brominated flame retardant polyether glycol the present invention prepared is used for the preparation of flame retardant polyurethane material as reactive flame retardant, described flame retardant polyurethane material includes but not limited to the materials such as polyurethane foam, polyurethane elastomer, polyurethane adhesive, polyurethane sealant and polyurethane coating, optimization polyurethane foam materials, further optimization polyurethane hard foam.
Compared with prior art, the invention has the advantages that:
1, in the present invention, dibasic alcohol used (phenol) raw material is cheap and easy to get, and react simply controlled, reaction yield reaches more than 95%.
2, the present invention utilizes the hydrolysis of epoxy terminated compound to obtain the polyether glycol of polyfunctionality (3 ~ 4), this raw material is adopted to add in the formula of hard polyurethane foam as reactive flame retardant, even if during large usage quantity, also obviously impact can not be produced on the mechanical property of foam materials.
3, the response type brominated flame retardant polyether glycol modest viscosity prepared of the present invention, with whipping agent and other auxiliary agent consistency good, with the premixed systems homogeneous transparent of its configuration, mobility is good, good stability.Add a small amount of this flame retardant polyether polyol, coordinate phosphorus flame retardant, can prepare there is excellent mechanical performance, B1 level lagging material that oxygen index is greater than 30.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
1, take neopentyl glycol 104g, join in the 1L four-hole boiling flask with mechanical stirring, thermometer, dropping funnel and prolong, take 462g epoxy chloropropane simultaneously and add dropping funnel solid material is heated to 120
oc, after its complete melting, adds 0.09g oleum, keeps 110
oc starts to drip epoxy chloropropane, dropwises follow-up continuation of insurance temperature 4 hours, obtains the Hydrin of difunctionality, reaction yield 99%.
2, the product that the 1st step is obtained by reacting is cooled to-20
oc, then keeps stream temperature-20
odrip bromine 320g under C condition, time for adding is 7 hours.After dropwising, at room temperature underpressure distillation removes unreacted bromine, reaction yield 98%.
3, by product heats to 45 that the 2nd step is obtained by reacting
oc, adds 50wt% aqueous sodium hydroxide solution 160g, 45
ostir under C after 3 hours and leave standstill separatory, after lower floor's dark brown liquid is separated, 90
ocarry out underpressure distillation under C and remove a small amount of moisture, finally filtering residual chloride sodium obtains the epoxy terminated compound of bromination excessively.Reaction yield 96%.
4, take the product 100g that the 3rd step is obtained by reacting, join in the 1L there-necked flask with mechanical stirring, thermometer, prolong, then add acetone 200g, water 100g, nitric acid (68wt%) 0.5g, 50
ostirring reaction 4 hours under C condition, reaction yield 99%.
5, the reaction solution the 4th step reacted is 90
ocarry out underpressure distillation removing reaction solvent under C condition, obtain brown color reaction-type flame-retarding polyether polyol product.Total yield of products 94%.
Embodiment 2
1. take BDO 90g, join in the 1L four-hole boiling flask with mechanical stirring, thermometer, dropping funnel and prolong, take 555g epoxy chloropropane simultaneously and add dropping funnel, solid material is heated to 120
oc, after its complete melting, adds 0.1g oleum, keeps 120
oc starts to drip epoxy chloropropane, dropwises follow-up continuation of insurance temperature 6 hours, obtains the Hydrin of difunctionality, reaction yield 99%.
2. the product that the 1st step is obtained by reacting is cooled to 0
oc, then keeps stream temperature 0
odrip bromine 480g under C condition, time for adding is 9 hours, and after dropwising, at room temperature underpressure distillation removes unreacted bromine, reaction yield 98%.
3. by product heats to 60 that the 2nd step is obtained by reacting
oc, adds 50wt% aqueous sodium hydroxide solution 240g, 60
ostir under C after 4 hours and leave standstill separatory, after lower floor's dark brown liquid is separated, 90
ocarry out underpressure distillation under C and remove a small amount of moisture, finally filtering residual chloride sodium obtains the epoxy terminated compound of bromination, reaction yield 98% excessively.
4. take the product 100g that the 3rd step is obtained by reacting, join in the 1L there-necked flask with mechanical stirring, thermometer, prolong, then add dioxane 250g, water 150g, hydrochloric acid (38wt%) 0.8g, 60
ostirring reaction 5 hours under C condition, reaction yield 99%.
5. the reaction solution the 4th step reacted is 80
ocarry out underpressure distillation removing reaction solvent under C condition, obtain brown color reaction-type flame-retarding polyether polyol product.Total yield of products 96%.
Embodiment 3
1, take dihydroxyphenyl propane 228g, epoxy chloropropane 162g, join in the 2L four-hole boiling flask with mechanical stirring, thermometer, dropping funnel and prolong, take 763g epoxy chloropropane simultaneously and add dropping funnel, solid material is heated to 60
oc, after its complete melting, adds 1.1g perchloric acid, keeps 60
oc starts to drip epoxy chloropropane, dropwises follow-up continuation of insurance temperature 10 hours, obtains the Hydrin of difunctionality, reaction yield 99%.
2, the product that the 1st step is obtained by reacting is cooled to 20
oc, then keeps stream temperature 20
odrip bromine 160g under C condition, time for adding is 3 hours, and after dropwising, at room temperature underpressure distillation removes unreacted bromine, reaction yield 98%.
3, the product that the 2nd step is obtained by reacting is cooled to 0
oc, adds 50wt% potassium hydroxide aqueous solution 112g, 0
ostir under C after 2 hours and leave standstill separatory, after lower floor's dark brown liquid is separated, 90
ocarry out underpressure distillation under C and remove a small amount of moisture, finally filtering residual chloride sodium obtains the epoxy terminated compound of bromination excessively.Reaction yield 96%.
4, take the product 100g that the 3rd step is obtained by reacting, join in the 1L there-necked flask with mechanical stirring, thermometer, prolong, then add tetrahydrofuran (THF) 100g, water 100g, hydrochloric acid (38wt%) 1g, 45
ostirring reaction 2 hours under C condition, reaction yield 99%.
5, the reaction solution the 4th step reacted is 120
ocarry out underpressure distillation removing reaction solvent under C condition, obtain brown color reaction-type flame-retarding polyether polyol product.Total yield of products 94%.
Embodiment 4
1, claim 1,6-hexylene glycol 59g, butylene glycol 44g, joins in the 1L four-hole boiling flask with mechanical stirring, thermometer, dropping funnel and prolong, takes 370g epoxy chloropropane simultaneously and adds dropping funnel, solid material is heated to 80
oc, after its complete melting, adds 0.08g magnesium chloride, keeps 80
oc starts to drip epoxy chloropropane, dropwises follow-up continuation of insurance temperature 3 hours, obtains the Hydrin of difunctionality, reaction yield 99%.
2, the product that the 1st step is obtained by reacting is cooled to-5
oc, then keeps stream temperature-5
odrip bromine 640g under C condition, time for adding is 10 hours, and after dropwising, at room temperature underpressure distillation removes unreacted bromine, reaction yield 98%.
3, by product heats to 90 that the 2nd step is obtained by reacting
oc, adds 80wt% potassium hydroxide aqueous solution 420g, 90
ostir under C after 6 hours and leave standstill separatory, after lower floor's dark brown liquid is separated, 90
ocarry out underpressure distillation under C and remove a small amount of moisture, finally filtering residual chloride sodium obtains the epoxy terminated compound of bromination excessively.Reaction yield 94%.
4, take the product 100g that the 3rd step is obtained by reacting, join in the 1L there-necked flask with mechanical stirring, thermometer, prolong, then add dimethyl formamide 500g, water 100g, sulfuric acid (98wt%) 0.1g, 95
ostirring reaction 1 hour under C condition, reaction yield 99%.
5, the reaction solution the 4th step reacted is 120
ocarry out underpressure distillation removing reaction solvent under C condition, obtain brown color response type Halogen flame retardant polyether polyol product.Total yield of products 92%.
Embodiment 5
1, take neopentyl glycol 52g, bisphenol S 125g, epoxy chloropropane 100g, join in the 1L four-hole boiling flask with mechanical stirring, thermometer, dropping funnel and prolong, take 548g epoxy chloropropane simultaneously and add dropping funnel, solid material is heated to 90
oc, after its complete melting, adds 0.8g triphenyl phosphorus, keeps 90
oc starts to drip epoxy chloropropane, dropwises follow-up continuation of insurance temperature 4 hours, obtains the Hydrin of difunctionality, reaction yield 99%.
2, the product that the 1st step is obtained by reacting is cooled to 10
oc, then keeps stream temperature 10
odrip bromine 300g under C condition, time for adding is 6 hours, and after dropwising, at room temperature underpressure distillation removes unreacted bromine, reaction yield 98%.
3, the product that the 2nd step is obtained by reacting is cooled to 40
oc, adds 40wt% lithium hydroxide aqueous solution 300g, 40
ostir under C after 2 hours and leave standstill separatory, after lower floor's dark brown liquid is separated, 90
ocarry out underpressure distillation under C and remove a small amount of moisture, finally filtering residual chloride sodium obtains the epoxy terminated compound of bromination excessively.Reaction yield 95%.
4, take the product 100g that the 3rd step is obtained by reacting, join in the 1L there-necked flask with mechanical stirring, thermometer, prolong, then add acetonitrile 100g, tetrahydrofuran (THF) 50g, water 100g, perchloric acid 0.5g, 70
ostirring reaction 3 hours under C condition, reaction yield 99%.
5, the reaction solution the 4th step reacted is 100
ocarry out underpressure distillation removing reaction solvent under C condition, obtain brown color reaction-type flame-retarding polyether polyol product.Total yield of products 92%.
Embodiment 6
1, take ethylene glycol 31g, bis-phenol a114g, epoxy chloropropane 240g, join in the 1L four-hole boiling flask with mechanical stirring, thermometer, dropping funnel and prolong, take 500g epoxy chloropropane simultaneously and add dropping funnel, solid material is heated to 100
oc, after its complete melting, adds 0.13g perchloric acid, keeps 100
oc starts to drip epoxy chloropropane, dropwises follow-up continuation of insurance temperature 5 hours, obtains the Hydrin of difunctionality, reaction yield 99%.
2, the product that the 1st step is obtained by reacting is cooled to 5
oc, then keeps stream temperature 5
odrip bromine 450g under C condition, time for adding is 8 hours, and after dropwising, at room temperature underpressure distillation removes unreacted bromine, reaction yield 98%.
3, the product that the 2nd step is obtained by reacting is cooled to 10
oc, adds 30wt% potassium hydroxide aqueous solution 280g, 10
ostir under C after 5 hours and leave standstill separatory, after lower floor's dark brown liquid is separated, 90
ocarry out underpressure distillation under C and remove a small amount of moisture, finally filtering residual chloride sodium obtains the epoxy terminated compound of bromination excessively.Reaction yield 96%.
4, take the product 100g that the 3rd step is obtained by reacting, join in the 1L there-necked flask with mechanical stirring, thermometer, prolong, acetone 100g, tetrahydrofuran (THF) 90g, then add water 138g, tosic acid 0.3g, 90
ostirring reaction 4 hours under C condition, reaction yield 99%.
5, the reaction solution the 4th step reacted is 80
ocarry out underpressure distillation removing reaction solvent under C condition, obtain brown color reaction-type flame-retarding polyether polyol product.Total yield of products 94%.
Embodiment 7
1, take glycol ether 53g, Isosorbide-5-Nitrae-butylene glycol 44g, join in the 1L four-hole boiling flask with mechanical stirring, thermometer, dropping funnel and prolong, take 418g epoxy chloropropane simultaneously and add dropping funnel, solid material is heated to 70
oc, after its complete melting, adds 0.45g oleum, keeps 70
oc starts to drip epoxy chloropropane, dropwises follow-up continuation of insurance temperature 5 hours, obtains the Hydrin of difunctionality, reaction yield 99%.
2, the product that the 1st step is obtained by reacting is cooled to 0
oc, then keeps stream temperature 0
odrip bromine 188g under C condition, time for adding is 5 hours, and after dropwising, at room temperature underpressure distillation removes unreacted bromine, reaction yield 98%.
3, by product heats to 30 that the 2nd step is obtained by reacting
oc, adds 40wt% aqueous sodium hydroxide solution 250g, 30
ostir under C after 4 hours and leave standstill separatory, after lower floor's dark brown liquid is separated, 90
ocarry out underpressure distillation under C and remove a small amount of moisture, finally filtering residual chloride sodium obtains the epoxy terminated compound of bromination excessively.Reaction yield 96%.
4, take the product 100g that the 3rd step is obtained by reacting, join in the 1L there-necked flask with mechanical stirring, thermometer, prolong, dimethyl formamide 200g, methyl alcohol 80g, then add water 200g, tosic acid 0.2g, 70
ostirring reaction 6 hours under C condition, reaction yield 99%.
5, the reaction solution the 4th step reacted is 110
ocarry out underpressure distillation removing reaction solvent under C condition, obtain brown color reaction-type flame-retarding polyether polyol product.Total yield of products 94%.
By embodiment of the present invention 2(flame retarding polyether 1) and embodiment 6(flame retarding polyether 5) based on the brominated flame retardant polyether glycol prepared, conveniently formula prepares combined polyether, then with polymeric MDI high-speed mixing after carry out foaming experiment.
Correlation analysis test result is in table 1
The formula of hard polyurethane foam prepared by the brominated flame retardant polyether glycol that table 1 adopts common polyether and the present invention to prepare and the performance test results.
Test result shows: in the formula of hard polyurethane foam, add 40 parts of response type brominated flame retardant polyether glycols of the present invention, the hard polyurethane foam material that flame retardant rating is B1 level can be obtained, and, other performances added for foam of response type Halogen flame retardant polyether polyol do not affect substantially, therefore, response type Halogen flame retardant polyether polyol provided by the invention is preparing polyurethane material, particularly has the preparation in the hard polyurethane foam material of high flame retardant requirement may have great application prospect.
Claims (9)
1. a preparation method for brominated flame retardant polyether glycol, is characterized in that: said method comprising the steps of:
(1) with dibasic alcohol/dihydric phenol for initiator causes the ring-opening polymerization of epoxy chloropropane under catalyst action, prepare difunctionality Hydrin, temperature of reaction is 60 ~ 120
oc, the reaction times is 3 ~ 10 hours;
(2) bromine be added dropwise in the difunctionality Hydrin that step (1) obtains and react, dropping temperature is-20 ~ 20
oc, time for adding is 3 ~ 10 hours;
(3) Hydrin and the strong base solution of bromination step (2) obtained are obtained by reacting end rings oxycompound, and temperature of reaction is 0 ~ 90
oc, the reaction times is 2 ~ 6 hours;
(4) the epoxy terminated compound that step (3) obtains is added water, organic solvent and catalyzer, be hydrolyzed reaction, and obtain polyfunctionality brominated flame retardant polyether polyols alcoholic solution, hydrolysis temperature is 45 ~ 95
oc, hydrolysis time is 2 ~ 8 hours;
(5) the polyether polyols alcoholic solution obtained in step (4) is carried out underpressure distillation, obtain product brominated flame retardant polyether polyol;
Wherein:
Dibasic alcohol/dihydric phenol described in step (1) is the combination of one or more (containing two kinds) in ethylene glycol, glycol ether, BDO, neopentyl glycol, dinitrobenzene propylene glycol, 1,6-hexylene glycol, Isosorbide-5-Nitrae-butylene glycol, dihydroxyphenyl propane, bisphenol S; Catalyzer is Lewis acid or protonic acid, and the add-on of catalyzer is 0.05 ~ 0.5wt% of initiator dibasic alcohol/dihydric phenol; The mol ratio of initiator dibasic alcohol/dihydric phenol and epoxy chloropropane is 1:4 ~ 10;
In step (2), the mol ratio of the Hydrin that bromine used and step (1) obtain is 1 ~ 4:1;
Highly basic described in step (3) is the aqueous solution of sodium hydroxide, potassium hydroxide, calcium hydroxide or lithium hydroxide; The mol ratio of the bromination Hydrin that highly basic used and step (2) obtain is 1 ~ 6:1;
In step (4), an acidic catalyst used is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, tosic acid or perchloric acid, and the add-on of an acidic catalyst is 0.1 ~ 1wt% of the epoxy terminated compound that step (3) obtains; Organic solvent used is one in tetrahydrofuran (THF), dimethyl formamide, dioxane, acetone, methyl alcohol, ethanol or acetonitrile or its mixture; The mass ratio of the epoxy terminated compound obtained in organic solvent used, water and step (3) is 1 ~ 10:1 ~ 10:1;
In step (5), vacuum distillation temperature is 60 ~ 120
oc.
2. the preparation method of a kind of brominated flame retardant polyether glycol according to claim 1, is characterized in that described in step (1), catalyzer is oleum and/or perchloric acid, and the add-on of catalyzer is initiator dibasic alcohol/dihydric phenol 0.08 ~ 0.12wt%.
3. the preparation method of a kind of brominated flame retardant polyether glycol according to claim 1, it is characterized in that the mol ratio of initiator dibasic alcohol/dihydric phenol and epoxy chloropropane in step (1) is 1:5 ~ 6, temperature of reaction is 110 ~ 120
oc, the reaction times is 4 ~ 6 hours.
4. the preparation method of a kind of brominated flame retardant polyether glycol according to claim 1, it is characterized in that the mol ratio of the Hydrin that bromine used and step (1) obtain in step (2) is 2 ~ 3:1, temperature of reaction is-20 ~ 0
oc, the reaction times is 7 ~ 9 hours.
5. the preparation method of a kind of brominated flame retardant polyether glycol according to claim 1, it is characterized in that step (3) sodium hydroxide or potassium hydroxide aqueous solution concentration are 40 ~ 50wt%, the mol ratio of the bromination Hydrin that sodium hydroxide used or potassium hydroxide and step (2) obtain is 2 ~ 3:1, and temperature of reaction is 50 ~ 60
oc, the reaction times is 3 ~ 4 hours.
6. the preparation method of a kind of brominated flame retardant polyether glycol according to claim 1, it is characterized in that in step (4), an acidic catalyst used is the hydrochloric acid of 38wt% or the nitric acid of 68wt%, the add-on of an acidic catalyst is 0.5 ~ 0.8wt% of the epoxy terminated compound that step (3) obtains.
7. the preparation method of a kind of brominated flame retardant polyether glycol according to claim 1, it is characterized in that in step (4), organic solvent used is that acetonitrile is or/and tetrahydrofuran (THF), the mass ratio of the epoxy terminated compound obtained in organic solvent used, water and step (3) is 1:1.2 ~ 1.4:3.3 ~ 3.4, and hydrolysis temperature is 50 ~ 60
oc, hydrolysis time is 4 ~ 5 hours.
8. the preparation method of a kind of brominated flame retardant polyether glycol according to claim 1, is characterized in that in step (5), vacuum distillation temperature is 80 ~ 90
oc.
9. the application of brominated flame retardant polyether glycol in flame retardant polyurethane hard foam prepared of method according to any one of claim 1-8.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106084198A (en) * | 2016-08-04 | 2016-11-09 | 潍坊鑫洋化工有限公司 | A kind of synthesis technique of halogenated polyether polyhydric alcohol |
| CN106117536A (en) * | 2016-07-22 | 2016-11-16 | 山东润科化工股份有限公司 | A kind of synthetic method of flame retardant polyether polyol |
| CN108148191A (en) * | 2016-12-06 | 2018-06-12 | 上海东大化学有限公司 | A kind of branched polyether, intermediate and preparation method thereof |
| CN110295025A (en) * | 2019-06-20 | 2019-10-01 | 福建华夏蓝新材料科技有限公司 | A kind of antibacterial aqueous polyurethane adhesive and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3645962A (en) * | 1970-02-26 | 1972-02-29 | Hercules Inc | Flame retardant polyester compositions |
| US3988302A (en) * | 1974-05-24 | 1976-10-26 | Texaco Development Corporation | Polyurethanes prepared by reaction of organic polyisocyanate with brominated ester-containing polyols |
| CN101497691A (en) * | 2008-12-31 | 2009-08-05 | 青岛科技大学 | High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation thereof |
| CN103497322A (en) * | 2013-09-09 | 2014-01-08 | 江苏雅克科技股份有限公司 | Preparation method and application for reaction-type halogen-containing flame-retardant polyether polyol |
| CN104292448A (en) * | 2014-09-29 | 2015-01-21 | 句容宁武新材料发展有限公司 | Preparation method and application of flame-retardant polyether containing N and Br |
-
2015
- 2015-09-06 CN CN201510559320.5A patent/CN105111429A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3645962A (en) * | 1970-02-26 | 1972-02-29 | Hercules Inc | Flame retardant polyester compositions |
| US3988302A (en) * | 1974-05-24 | 1976-10-26 | Texaco Development Corporation | Polyurethanes prepared by reaction of organic polyisocyanate with brominated ester-containing polyols |
| CN101497691A (en) * | 2008-12-31 | 2009-08-05 | 青岛科技大学 | High activityhydroxyl-terminated polyepichlorohydrin polyatomic alcohol and preparation thereof |
| CN103497322A (en) * | 2013-09-09 | 2014-01-08 | 江苏雅克科技股份有限公司 | Preparation method and application for reaction-type halogen-containing flame-retardant polyether polyol |
| CN104292448A (en) * | 2014-09-29 | 2015-01-21 | 句容宁武新材料发展有限公司 | Preparation method and application of flame-retardant polyether containing N and Br |
Non-Patent Citations (1)
| Title |
|---|
| 周红欣等: ""含溴阻燃聚醚多元醇的合成及在聚氨酯硬泡中的应用研究"", 《新型建筑材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117536A (en) * | 2016-07-22 | 2016-11-16 | 山东润科化工股份有限公司 | A kind of synthetic method of flame retardant polyether polyol |
| CN106084198A (en) * | 2016-08-04 | 2016-11-09 | 潍坊鑫洋化工有限公司 | A kind of synthesis technique of halogenated polyether polyhydric alcohol |
| CN108148191A (en) * | 2016-12-06 | 2018-06-12 | 上海东大化学有限公司 | A kind of branched polyether, intermediate and preparation method thereof |
| CN110295025A (en) * | 2019-06-20 | 2019-10-01 | 福建华夏蓝新材料科技有限公司 | A kind of antibacterial aqueous polyurethane adhesive and preparation method thereof |
| CN110295025B (en) * | 2019-06-20 | 2021-04-23 | 福建华夏蓝新材料科技有限公司 | Antibacterial water-based polyurethane adhesive and preparation method thereof |
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