CN104844793A - Preparation method and application of novel flame-retardant polyether glycol - Google Patents
Preparation method and application of novel flame-retardant polyether glycol Download PDFInfo
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Abstract
The invention relates to a preparation method and application of novel flame-retardant polyether glycol. The preparation method comprises the following steps: 1) preparation of nitrogen-containing compounds: reacting cyanuric chloride and ammonia water, substituting at different temperatures to obtain different amines, reacting with ethylenediamine or piperazidine to obtain high-nitrogen-containing compounds, and grinding the compounds to the particle size of 5 mu m or so; and 2) in a high-activity polyether polyalcohol medium, reacting the nitrogen-containing compounds with formaldehyde at 80-95 DEG C for 3-5 hours, thereby obtaining the monomer-dispersed or partially-grafted high-activity flame-retardant polyether glycol. The flame-retardant high-activity polymer polyether glycol has the characteristics of high flame-retardant oxygen index, high tendency to foaming and the like. The oxygen index of the polyurethane high-resilience foam plastic is greater than or equal to 28%, the tobacco density is less than or equal to 60%, and the resilience ratio is greater than or equal to 60%.
Description
Technical field
The invention belongs to chemical industry preparing technical field, be specifically related to a kind of preparation technology simple, be easy to foaming and the preparation method and application of the New Fire Retardant Polyether Polyol of good flame retardation effect.
Background technology
along with the development of world economy, polyurethane material demand in continuous lifting, due to polyurethane foam insulation, sound insulation, ageing-resistant in etc. performance, be widely used in the fields such as automobile, aviation, building.
The fire-retardant approach of current polyurethane material, is roughly divided into two kinds: 1. add non-reactive flame retardant method.As describe in the patent USP4849459 of the U.S. trimeric cyanamide and phosphoric acid ester with the use of, method mainly through adding melamine class nitrogenous compound in polyether polyol with high activity arrives fire-retardant effect, very high to the Particle size requirements of melamine class nitrogenous compound in the process of adding, and can be highly dispersed in polyether glycol, as can not high dispersing, storage period, length was easy to layering, the mutual solubility of adding fire retardant and polyether glycol is very poor, brings a lot of inconveniences in actual production.Add fire retardant be difficult to be applied in actual production.2. reaction-type flame-retarding method mainly flame retarding polyether unit alcohol, nano-size incombustible polyether polyol polymer disclosed in Chinese patent cn01346836A, be external phase with polyether polyol with high activity, the molecular weight 4800-6000 of high activity polyether, its product solid content about 28%.The flame retardant polyether polyol flame retardant properties that existing method obtains is good not, and the oxygen index of the polyurethane foam of preparation is not very high.
Summary of the invention
For the above-mentioned problems in the prior art, an object of the present invention is to provide a kind of preparation method of New Fire Retardant Polyether Polyol, adopt high nitrogenous molecular compound or high nitrogenous Molecularly Imprinted Polymer and formaldehyde to carry out pre-polymerization, high dispersing or local are grafted in polyether polyol with high activity medium.This New Fire Retardant Polyether Polyol has no bibliographical information mistake, lays the first stone for studying New Fire Retardant Polyether Polyol later.
The preparation method of described a kind of New Fire Retardant Polyether Polyol, it is characterized in that taking polyether polyol with high activity as medium, under catalyst action, nitrogenous compound and formaldehyde 3-10 hour at 60-100 DEG C, obtain the High Reactive Flame Retardant Polyether Polyol of monomer dispersion or local grafting, water solvent is sloughed in polycondensation again, vacuum decompression, obtains flame retardant polyether polyol.
The preparation method of described a kind of New Fire Retardant Polyether Polyol, it is characterized in that described nitrogenous compound is that ethylenediamines compound is or/and piperazine compounds, the structural formula of ethylenediamines compound as its structural formula as shown in the formula (I), the structural formula of piperazine compounds is as shown in the formula (II):
The preparation method of described a kind of New Fire Retardant Polyether Polyol, is characterized in that the ethylenediamines compounds process for production thereof shown in formula (I) is as follows:
Take cyanuric chloride as starting raw material, using mineral alkali as acid binding agent, cyanuric chloride dispersion is cooled to-5 ~ 0 DEG C in a solvent, drip ammoniacal liquor, start after dripping off to drip the NaOH aqueous solution, control drip reacting temperature is :-5 ~ 5 DEG C, after reaction terminates, solution reaction temperature is increased to 25 ~ 30 DEG C, then simultaneously, reclaim solution, then drip quadrol after dropping ammoniacal liquor drips NaOH reactant aqueous solution, drip the NaOH aqueous solution simultaneously, after suction filtration, washing, oven dry, namely obtain the ethylenediamines compound shown in formula (I);
Take cyanuric chloride as starting raw material, using mineral alkali as acid binding agent, cyanuric chloride dispersion is cooled to-5 ~ 0 DEG C in a solvent, drip ammoniacal liquor, start after dripping off to drip the NaOH aqueous solution, control drip reacting temperature is :-5 ~ 5 DEG C, after reaction terminates, solution reaction temperature is increased to 25 ~ 30 DEG C, then simultaneously, reclaim solution, then drip piperazine after dropping ammoniacal liquor drips NaOH reactant aqueous solution, drip the NaOH aqueous solution simultaneously, after suction filtration, washing, oven dry, namely obtain the piperazine compounds shown in formula (II).
The preparation method of described a kind of New Fire Retardant Polyether Polyol, is characterized in that catalyzer is dilute hydrochloric acid, sulfuric acid or triethylamine; Described solvent is the mixture of acetone or acetone and water.
The preparation method of described a kind of New Fire Retardant Polyether Polyol, it is characterized in that temperature of reaction is 80-95 DEG C, the reaction times is 3-5 hour.
The preparation method of described a kind of New Fire Retardant Polyether Polyol, it is characterized in that cyanuric chloride temperature of reaction first chlorine substitution reaction temperature setting-5 ~ 5 DEG C, second chlorine substitution reaction temperature is room temperature, and the 3rd chlorine substitution reaction temperature is 95 ~ 100 DEG C.
The preparation method of described a kind of New Fire Retardant Polyether Polyol, it is characterized in that described polyether polyol with high activity is propylene oxide ring-opening polymerization or ethylene oxide-capped formed polyether glycol, its molecular weight is 3000-8000, the functionality of its polyvalent alcohol is between 2-4, hydroxyl value is between 19KOH-36KOH/g, and proportion of primary OH groups is between 65-98%.
The described application of a kind of New Fire Retardant Polyether Polyol in synthesis of polyurethane high resilience foam.
Described New Fire Retardant Polyether Polyol and polyether polyol with high activity, additive compound, synthesis of polyurethane high resilience foam, it is characterized in that each component and parts by weight as follows:
Polyether polyol with high activity 30-70 part
Flame retardant polyether polyol 70-30 part
Silicone oil 0.7-1.2 part
Linking agent 1-2.5 part
Water 1-3 part
Tertiary amine catalyst 0.1-0.5 part
Diisocyanate cpd 100-115 part,
Described tertiary amine catalyst is one in triethylamine, triethylene diamine, Diisopropylamine or a kind of mixture, described diisocyanate cpd comprises tolylene diisocyanate, ditan diphenyl diisocyanate, and described linking agent is one or more the mixture in glycerine, diethanolamine, trolamine.
The preparation method of described high elastic polyurethane porous plastics, it is characterized in that adding respectively in a mixer polyether polyol with high activity, flame retardant polyether polyol, tertiary amine catalyst, water, linking agent, silicone oil foam stabilizer add diisocyanate cpd after mixing, high-speed mixing, after mixing, free foaming obtains high elastic polyurethane porous plastics, and its performance should meet following requirement:
Froth appearance density: 45-70kg/m3
Foam tensile intensity: >=100Kpa
Foam breakdown elongation: >=100%
Foam compression set :≤8%
Oxygen index: >=28%
Smoke density :≤60% rebound degree: >=60%.
By adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows:
1) flame retardant polyether polyol that obtains of the present invention, the objectionable impuritiess such as not phosphorous, halogen, propylene cyanogen, and have preparation technology simple, be easy to the features such as foaming, belong to Green Product;
2) by the flame retarding polyether of the present invention the more resistance combustion polyurethane foam for preparing of alcohol, have a large amount of nitrogenous compounds and the hardness of compound is very high, therefore this resistance combustion polyurethane foam has higher flame retardant resistance (oxygen index can reach 30%) and higher compression elasticity.
3) the present invention carries out polycondensation by adopting new nitrogenous chemical combination, expands the range of application of this compound, produces New Fire Retardant Polyether Polyol.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited in this:
Example 1: the preparation of nitrogenous compound (I)
By acetone/water mixture (119/100, mass ratio) drop in the flask of four mouthfuls of 1000ml, be cooled to-5 ~ 0 DEG C, then cyanuric chloride 92.25g is dropped into, dispersed with stirring 30min, drip ammoniacal liquor 100g (15%), drip the NaOH aqueous solution (NaOH/ water: 20g/50g) simultaneously, control drip reacting temperature is :-5 ~ 5 DEG C, time for adding is about 1.5h, drips off rear solution temperature to be increased to 25 ~ 30 DEG C, then drips ammoniacal liquor 100g (15%), drip the NaOH aqueous solution (NaOH/ water: 20g/50g), reaction terminates rear solution PH for neutral simultaneously.Reclaim acetone, be distilled to 100 DEG C, limit drips quadrol 15g limit and drips the sodium hydroxide solution aqueous solution, drip off rear backflow insulation, cooling room temperature 25 DEG C filtration after reaction, filter cake purified water is washed to neutral, dry filter cake at 110 DEG C, obtain nitrogenous compound (I) 89g, yield: 90%.(calculating with cyanuric chloride).Product is white powder thing, and grinding obtains particle diameter about 5um white powder thing.
Example 2: the preparation of nitrogenous compound (II)
By acetone/water mixture (119/100, mass ratio) drop in the flask of four mouthfuls of 1000ml, be cooled to-5 ~ 0 DEG C, then cyanuric chloride 92.25g is dropped into, dispersed with stirring 30min, drip ammoniacal liquor 100g (15%), drip the NaOH aqueous solution (NaOH/ water: 20g/50g) simultaneously, control drip reacting temperature is :-5 ~ 5 DEG C, time for adding is about 1.5h, drips off rear solution temperature to be increased to 25 ~ 30 DEG C, then drips ammoniacal liquor 100g (15%), drip the NaOH aqueous solution (NaOH/ water: 20g/50g), reaction terminates rear solution PH for neutral simultaneously.23g piperazine and 20g sodium hydroxide join in four-hole bottle, improve temperature of reaction, reflux after 2 hours, and reaction terminates.Filter, wash, at 105 DEG C, dry filter cake, obtain nitrogenous compound (II) 89g, yield: 90%.Product is white powder thing, and grinding obtains particle diameter about 6um white powder thing.
Example 3
Nitrogenous compound (I) 30g obtained by example 1, example 2 nitrogenous compound (II) 30g, formaldehyde 50g (content 37%) add in four-hole boiling flask, PH=8-9 is adjusted with triethylamine, stirring at room temperature 30 minutes, then add polyether glycol 400 g and stir 20 minutes, be warming up to 85-90 DEG C, insulation reaction 4 hours, water is sloughed in the decompression of reaction final vacuum, underpressure distillation was to temperature 100 DEG C insulation 30 minutes, moisture controlled less than 0.1%, obtains flame retardant polyether polyol, outward appearance: oyster white is homogeneous, hydroxyl value: 22mgKOH/g, viscosity 2800mpa.s/25 DEG C.
Example 4
Nitrogenous compound (I) 30g obtained by example 1, example 2 nitrogenous compound (II) 30g, formaldehyde 50g (content 37%) add in four-hole boiling flask, PH=8-9 is adjusted with triethylamine, stirring at room temperature 30 minutes, then add polyether glycol 500 g and stir 20 minutes, be warming up to 85-90 DEG C, insulation reaction 4 hours, water is sloughed in the decompression of reaction final vacuum, and underpressure distillation is incubated 30 minutes to temperature 100 DEG C, moisture controlled less than 0.1%, obtain flame retardant polyether polyol, outward appearance: oyster white is homogeneous, hydroxyl value: 22mgKOH/g, viscosity 2700mpa.s/25 DEG C.
Example 5
Nitrogenous compound (I) 30g obtained by example 1, example 2 nitrogenous compound (II) 30g, formaldehyde 50g (content 37%) add in four-hole boiling flask, PH=8-9 is adjusted with triethylamine, stirring at room temperature 30 minutes, then add polyether glycol 550 g and stir 20 minutes, be warming up to 85-90 DEG C, insulation reaction 4 hours, water is sloughed in the decompression of reaction final vacuum, and underpressure distillation is incubated 30 minutes to temperature 100 DEG C, moisture controlled less than 0.1%, obtain flame retardant polyether polyol, outward appearance: oyster white is homogeneous, hydroxyl value: 22mgKOH/g, viscosity 2000mpa.s/25 DEG C.
Example 6
Nitrogenous compound (I) 30g, the dicyanodiamide 30g that are obtained by example 1, formaldehyde 50g (content 37%) add in four-hole boiling flask, PH=8-9 is adjusted with triethylamine, stirring at room temperature 30 minutes, then add polyether glycol 550 g and stir 20 minutes, be warming up to 85-90 DEG C, insulation reaction 4 hours, water is sloughed in the decompression of reaction final vacuum, and underpressure distillation is incubated 30 minutes to temperature 100 DEG C, moisture controlled less than 0.1%, obtain flame retardant polyether polyol, outward appearance: oyster white is homogeneous, hydroxyl value: 22mgKOH/g, viscosity 2500mpa.s/25 DEG C.
Example 7
Nitrogenous compound (I) 30g, the trimeric cyanamide 30g that are obtained by example 1, formaldehyde 50g (content 37%) add in four-hole boiling flask, PH=8-9 is adjusted with triethylamine, stirring at room temperature 30 minutes, then add polyether glycol 550 g and stir 20 minutes, be warming up to 85-90 DEG C, insulation reaction 4 hours, water is sloughed in the decompression of reaction final vacuum, and underpressure distillation is incubated 30 minutes to temperature 100 DEG C, moisture controlled less than 0.1%, obtain flame retardant polyether polyol, outward appearance: oyster white is homogeneous, hydroxyl value: 22mgKOH/g, viscosity 2300mpa.s/25 DEG C.
Example 8
Nitrogenous compound (II) 30g, the trimeric cyanamide 30g that are obtained by example 2, formaldehyde 50g (content 37%) add in four-hole boiling flask, PH=8-9 is adjusted with triethylamine, stirring at room temperature 30 minutes, then add polyether glycol 550 g and stir 20 minutes, be warming up to 85-90 DEG C, insulation reaction 4 hours, water is sloughed in the decompression of reaction final vacuum, and underpressure distillation is incubated 30 minutes to temperature 100 DEG C, moisture controlled less than 0.1%, obtain flame retardant polyether polyol, outward appearance: oyster white is homogeneous, hydroxyl value: 22mgKOH/g, viscosity 2200mpa.s/25 DEG C.
Example 9 prepares high-rebound polyurethane flame-retardant foam
Be prepared rebound polyurethane flame-retardant foam with the flame retardant polyether polyol that above example 3,4,5,6,7,8 synthesizes respectively, basic recipe is as follows:
Each example flame retardant polyether polyol 40 parts
Polyether polyol with high activity 60 parts
Silicone oil 0.7-1.2 part
Linking agent 1-2.5 part
Water 1-3 part
Sanya ethylene diamine 0.1-0.5 part
TDI or TDI/MDI 100-115 part,
Inject the stainless steel mould of 250*250*150cm through high-speed mixing, foam under room temperature, at 45-50 DEG C after slaking.After the foam demoulding, room temperature places the performance measuring polyurethane foam after a week, and result is as table 1.
Claims (10)
1. the preparation method of a New Fire Retardant Polyether Polyol, it is characterized in that taking polyether polyol with high activity as medium, under catalyst action, nitrogenous compound and formaldehyde 3-10 hour at 60-100 DEG C, obtain the High Reactive Flame Retardant Polyether Polyol of monomer dispersion or local grafting, water solvent is sloughed in polycondensation again, vacuum decompression, obtains flame retardant polyether polyol.
2. the preparation method of a kind of New Fire Retardant Polyether Polyol according to claim 1, it is characterized in that described nitrogenous compound is that ethylenediamines compound is or/and piperazine compounds, the structural formula of ethylenediamines compound as its structural formula as shown in the formula (I), the structural formula of piperazine compounds is as shown in the formula (II):
。
3. the preparation method of a kind of New Fire Retardant Polyether Polyol according to claim 1, is characterized in that the ethylenediamines compounds process for production thereof shown in formula (I) is as follows:
Take cyanuric chloride as starting raw material, using mineral alkali as acid binding agent, cyanuric chloride dispersion is cooled to-5 ~ 0 DEG C in a solvent, drip ammoniacal liquor, start after dripping off to drip the NaOH aqueous solution, control drip reacting temperature is :-5 ~ 5 DEG C, after reaction terminates, solution reaction temperature is increased to 25 ~ 30 DEG C, then simultaneously, reclaim solution, then drip quadrol after dropping ammoniacal liquor drips NaOH reactant aqueous solution, drip the NaOH aqueous solution simultaneously, after suction filtration, washing, oven dry, namely obtain the ethylenediamines compound shown in formula (I);
Take cyanuric chloride as starting raw material, using mineral alkali as acid binding agent, cyanuric chloride dispersion is cooled to-5 ~ 0 DEG C in a solvent, drip ammoniacal liquor, start after dripping off to drip the NaOH aqueous solution, control drip reacting temperature is :-5 ~ 5 DEG C, after reaction terminates, solution reaction temperature is increased to 25 ~ 30 DEG C, then simultaneously, reclaim solution, then drip piperazine after dropping ammoniacal liquor drips NaOH reactant aqueous solution, drip the NaOH aqueous solution simultaneously, after suction filtration, washing, oven dry, namely obtain the piperazine compounds shown in formula (II).
4. the preparation method of a kind of New Fire Retardant Polyether Polyol according to claim 1, is characterized in that catalyzer is dilute hydrochloric acid, sulfuric acid or triethylamine; Described solvent is the mixture of acetone or acetone and water.
5., according to the preparation method of described a kind of New Fire Retardant Polyether Polyol arbitrary in claim 1-3, it is characterized in that temperature of reaction is 80-95 DEG C, the reaction times is 3-5 hour.
6. the preparation method of a kind of New Fire Retardant Polyether Polyol according to claim 3, it is characterized in that cyanuric chloride temperature of reaction first chlorine substitution reaction temperature setting-5 ~ 5 DEG C, second chlorine substitution reaction temperature is room temperature, and the 3rd chlorine substitution reaction temperature is 95 ~ 100 DEG C.
7. the preparation method of a kind of New Fire Retardant Polyether Polyol according to claim 1, it is characterized in that described polyether polyol with high activity is propylene oxide ring-opening polymerization or ethylene oxide-capped formed polyether glycol, its molecular weight is 3000-8000, the functionality of its polyvalent alcohol is between 2-4, hydroxyl value is between 19KOH-36KOH/g, and proportion of primary OH groups is between 65-98%.
8. the application of New Fire Retardant Polyether Polyol in synthesis of polyurethane high resilience foam.
9. New Fire Retardant Polyether Polyol as claimed in claim 1 and polyether polyol with high activity, additive compound, a synthesis of polyurethane high resilience foam, it is characterized in that each component and parts by weight as follows:
Polyether polyol with high activity 30-70 part
Flame retardant polyether polyol 70-30 part
Silicone oil 0.7-1.2 part
Linking agent 1-2.5 part
Water 1-3 part
Tertiary amine catalyst 0.1-0.5 part
Diisocyanate cpd 100-115 part,
Described tertiary amine catalyst is one in triethylamine, triethylene diamine, Diisopropylamine or a kind of mixture, described diisocyanate cpd comprises tolylene diisocyanate, ditan diphenyl diisocyanate, and described linking agent is one or more the mixture in glycerine, diethanolamine, trolamine.
10. the preparation method of a high elastic polyurethane porous plastics as claimed in claim 9, it is characterized in that adding respectively in a mixer polyether polyol with high activity, flame retardant polyether polyol, tertiary amine catalyst, water, linking agent, silicone oil foam stabilizer add diisocyanate cpd after mixing, high-speed mixing, after mixing, free foaming obtains high elastic polyurethane porous plastics, and its performance should meet following requirement:
Froth appearance density: 45-70kg/m3
Foam tensile intensity: >=100Kpa
Foam breakdown elongation: >=100%
Foam compression set :≤8%
Oxygen index: >=28%
Smoke density :≤60% rebound degree: >=60%.
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| CN110591037A (en) * | 2019-11-01 | 2019-12-20 | 上海东大聚氨酯有限公司 | Full-water soft flame-retardant low-density combined polyether, polyurethane foam, bridge-cut-off aluminum and preparation method thereof |
| CN115873203A (en) * | 2022-12-12 | 2023-03-31 | 大连理工大学 | High-wear-resistance single-component water-based polyurethane, and preparation method and application of emulsion or dispersion and coating thereof |
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| CN115873203A (en) * | 2022-12-12 | 2023-03-31 | 大连理工大学 | High-wear-resistance single-component water-based polyurethane, and preparation method and application of emulsion or dispersion and coating thereof |
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