CN104004171A - Preparation method of phosphorus-containing halogen-free environmentally-friendly flame-retardant polyester polyol - Google Patents
Preparation method of phosphorus-containing halogen-free environmentally-friendly flame-retardant polyester polyol Download PDFInfo
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- CN104004171A CN104004171A CN201410266542.3A CN201410266542A CN104004171A CN 104004171 A CN104004171 A CN 104004171A CN 201410266542 A CN201410266542 A CN 201410266542A CN 104004171 A CN104004171 A CN 104004171A
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Abstract
The invention provides a preparation method of phosphorus-containing halogen-free environmentally-friendly flame-retardant polyester polyol. The method comprises the steps that with DOPO being starting material, firstly, the DOPO reacts with dibasic acid or dibasic acid anhydride to generate a DOPO complex intermediate; secondly, esterification dehydration reaction is performed on the generated intermediate, small-molecules polyol and dibasic acid or dibasic acid anhydride at 150 DEG C-160 DEG C; after the dehydration reaction is over, the temperature is raised to 200 DEG C-250 DEG C for transesterification, wherein the reaction time is 1 h-3 h, and in this way, the polyester polyol is obtained. The prepared polyester polyol is not conventional polyester polyol but the polyester polyol containing the phosphorus element, has the reactivity with isocyanate and can be used for permanent flame retardant modification of polyurethane products. As the phosphorus element is introduced to the polyester polyol, the polyester polyol contains phosphorus and is free of halogen, environmentally friendly and capable of inflaming retarding.
Description
Technical field
The invention belongs to the preparation method field of Chemicals, relate to a kind of preparation method of polyester polyol, specially refer to a kind of preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol.
Background technology
Polyester polyol is a purposes class chemical intermediate very widely, and it comprises thermoplastic polyurethane, flexible PU foam, hard polyurethane foam, solvent type polyurethane resin and waterborne polyurethane resin etc. mainly for the production of polyurethane product.
In the product for civilian use of a lot of urethane, need certain flame retardant properties, as: for the hard polyurethane foam of exterior-wall heat insulation, for the flexible PU foam of sofa and automotive seat liner, for the production of the urethane resin of synthetic leather, interior leather for automobiles and building interior decoration leather for sofa.
At present, polyurethane flame-proof is main or the fire-retardant method of interpolation realizes later, the flame retardant properties that this mode reaches can reduce gradually along with the prolongation of time, in addition, because rear interpolation fire retardant is generally small molecules liquid substance, for automotive trim and building interior material, can cause organic concentration over-standard in enclosed space volatility, easily human body is caused to potential injury.
The permanent fire retardant polyurethane products that occur on market conventionally adopt the synthetic method that enters molecule segment of Halogen polyvalent alcohol are realized, although this Halogen urethane also has certain flame retardant properties, but this product can produce the irritant gas such as hydracid and hypohalous acid in the time of burning, and human body is produced to other injury.
Phosphorus flame retardant is one of fire retardant of environmental protection the most in the market, the mode of adding after it is main for urethane.The phosphorous polyurethane products that have no permanent fire retardant come out, relevant research report and Patents are also comparatively rare, only China applies for a patent CN 103044673 A, halogen-free phosphorus-containing response type polyester polyol has been carried out to correlative study, it adopts one or more mixtures in diprotic acid, dibasic alcohol and hydroxymethyl phenyl Hypophosporous Acid, 50, hydroxyethyl phenyl Hypophosporous Acid, 50, hydroxypropyl phenyl Hypophosporous Acid, 50, carboxyethyl phenyl phosphinic acid, synthesize the polyester polyol with flame retardant properties under certain condition.
Summary of the invention
goal of the invention:in order to overcome above-mentioned defect, the object of this invention is to provide a kind of preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol.
technical scheme:for achieving the above object, the present invention has taked following technical scheme:
A kind of preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol, taking DOPO as starting raw material, described DOPO first reacts with diprotic acid or dibasic acid anhydride, generate DOPO complex compound intermediate, the intermediate generating carries out esterification dehydration reaction with small molecules polyvalent alcohol and diprotic acid or dibasic acid anhydride again at 150-160 DEG C, after dehydration reaction finishes, is again warming up to 200-250 DEG C and carries out transesterification reaction, reaction times is 1-3h, can obtain so described polyester polyol.DOPO is BACN intermediate.In its structure, contain P-H key, alkene, epoxy bond and carbonyl are had to activity, can react and generate many derivatives.DOPO(9,10-dihydro-9-oxy is assorted-l0-phospho hetero phenanthrene-l0-oxide compound) and derivative owing to containing cyclohexyl biphenyl and phenanthrene ring structure in molecular structure, particularly side phosphorus group is introduced in the mode of ring-type O=P-O key, than general, organophosphate thermostability and the chemical stability of Cheng Huan are not high, flame retardant properties is better.DOPO and derivative thereof can be used as response type and additive flame retardant, and synthetic fire retardant Halogen, smokeless, nontoxic, does not move, and flame retardant properties is lasting.DOPO is incorporated in polyester polyol by synthetic mode, and the polyester polyol of synthesized can be used for preparing phosphor-containing flame-proof type polyurethane product.
Preferably, when described DOPO reacts with diprotic acid or dibasic acid anhydride, temperature of reaction is 100-120 DEG C, reaction times 1-3h.
Preferably, when described DOPO reacts with diprotic acid or dibasic acid anhydride, the mol ratio of described DOPO and diprotic acid or dibasic acid anhydride is 1:1-1:0.9; When described DOPO complex compound intermediate and small molecules polyvalent alcohol and diprotic acid or dibasic acid anhydride react, the mol ratio of described DOPO complex compound intermediate and small molecules polyvalent alcohol and diprotic acid or dibasic acid anhydride is 1:(0.4-2.5): (0.4-2.0).
Preferably, described small molecules polyvalent alcohol is that functionality is at least 2 the polyvalent alcohol with straight or branched structure.
Further preferred, described small molecules polyvalent alcohol is one or more in ethylene glycol, BDO, neopentyl glycol, glycerol.
Preferably, described diprotic acid comprises monounsaturated dicarboxylic acid and unsaturated dibasic acid, and described dibasic acid anhydride comprises monounsaturated dicarboxylic acid acid anhydride and unsaturated dicarboxylic acid anhydride.
Further preferred, described unsaturated dibasic acid is toxilic acid, and described monounsaturated dicarboxylic acid is hexanodioic acid, and described unsaturated dicarboxylic acid anhydride is maleic anhydride.
The chemical structural formula of the DOPO that mentions in the present invention, toxilic acid, maleic anhydride is
,
,
.
DOPO involved in the present invention introduces the reaction mechanism of polyester construction, taking DOPO and toxilic acid as example:
(DOPO-MA)
DOPO complex compound intermediate and small molecules polyvalent alcohol and diprotic acid or dibasic acid anhydride react, and taking DOPO-MA and hexanodioic acid and ethylene glycol as example, its reaction mechanism is:
beneficial effect:adopt the present invention of technique scheme to have the following advantages:
Particularly, compared with prior art, the technical scheme that the present invention takes has following outstanding advantage:
(1) polyester polyol that the present invention prepares, it not conventional polyester polyol, it is the polyester polyol that contains P element, there is the reactivity with isocyanic ester, it can be used for the permanent fire retardant modification of polyurethane products, in polyester polyol, introduce P element, making polyester polyol of the present invention is a kind of phosphor-containing halogen-free environmental protection flame retardant polyester polyol, polyester polyol of the present invention can be used for producing polyurethane products, comprise: soft bubble urethane resin, hard-foam polyurethane resin, solvent type polyurethane resin, solvent-free polyurethane resin and waterborne polyurethane resin, use the urethane that this kind of flame retardant polyester polyvalent alcohol makes to there is equally good flame retardant properties,
(2) reaction involved in the present invention belongs to bulk reaction, operation is simple, raw material is easy to get, in production process, by product is less, and contaminative is little, and reactions steps is few, it is a kind of environment friendly and pollution-free production method, can carry out suitability for industrialized production, productive rate is higher simultaneously, and productive rate remains essentially in more than 90%;
(3) the polyester polyol phosphor-containing halogen-free that the present invention prepares, its phosphorus content exceedes 10%, in 10.65-13.2%(mass content); Its hydroxyl value is at 11.2 ~ 224mgKOH/g; Its molecular weight (number all) is 500 ~ 10000.
Embodiment
Below by specific embodiment, the present invention is further elaborated; but it should be noted that concrete material proportion, processing condition and result thereof described in embodiments of the invention is only for illustrating the present invention; can not limit the scope of the invention with this; the equivalence that every spirit according to the present invention is done changes or modifies, and all should be encompassed in protection scope of the present invention.
embodiment 1
Agitator is being housed, in the 500ml reaction flask of nitrogen protection and condensation reflux unit, add 174.36g, 0.81moLDOPO and 93.6g, 0.81moL toxilic acid, be warming up to and be slowly warming up to 100-105 DEG C, open and stir and nitrogen, after reaction 180min, add 117.95, 0.81moL hexanodioic acid and 113.83g, 1.83moL ethylene glycol, after melting completely, slowly be warming up to 150-155 DEG C, carry out esterification dehydration reaction, after end to be drained off, be warming up to 200-210 DEG C, carry out transesterification reaction, after reaction 180min, detect acid number and hydroxyl value every 30min, until acid number and hydroxyl value detect qualified after, be cooled to below 100 DEG C, discharging packaging.
The theoretical hydroxyl value of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 56mgKOH/g;
The theoretical molecular-weight average (number all) of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 2000;
The theoretical phosphorus content of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 10.65%;
The theoretical yield of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 93.8%.
embodiment 2
Agitator is being housed, in the 500ml reaction flask of nitrogen protection and condensation reflux unit, add 134.3g, 0.62moLDOPO and 72.12g, 0.62moL toxilic acid, be warming up to and be slowly warming up to 105-110 DEG C, open and stir and nitrogen, after reaction 100min, add 155g, 1.06moL hexanodioic acid and 38.6g, 0.43moL1, 4-butyleneglycol, after melting completely, slowly be warming up to 155-160 DEG C, carry out esterification dehydration reaction, after end to be drained off, be warming up to 210-220 DEG C, carry out transesterification reaction, after reaction 150min, detect acid number and hydroxyl value every 30min, until acid number and hydroxyl value detect qualified after, be cooled to below 100 DEG C, discharging packaging.
The theoretical hydroxyl value of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 224mgKOH/g;
The theoretical molecular-weight average (number all) of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 500;
The theoretical phosphorus content of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 13.2%;
The theoretical yield of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 92.9%.
embodiment 3
Agitator is being housed, in the 500ml reaction flask of nitrogen protection and condensation reflux unit, add 202.3g, 0.94moLDOPO and 108.7g, 0.94moL toxilic acid, be warming up to and be slowly warming up to 110-115 DEG C, open and stir and nitrogen, after reaction 130min, add 87.17g0.60moL hexanodioic acid and 43.17g, 0.48moL1, 4-butyleneglycol, after melting completely, slowly be warming up to 155-160 DEG C, carry out esterification dehydration reaction, after end to be drained off, be warming up to 225-235 DEG C, carry out transesterification reaction, after reaction 120min, detect acid number and hydroxyl value every 30min, until acid number and hydroxyl value detect qualified after, be cooled to below 100 DEG C, discharging packaging.
The theoretical hydroxyl value of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 11.2mgKOH/g;
The theoretical molecular-weight average (number all) of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 10000;
The theoretical phosphorus content of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 12.9%;
The theoretical yield of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 90.36%.
embodiment 4
Agitator is being housed, in the 500ml reaction flask of nitrogen protection and condensation reflux unit, add 195.7g, 0.91moLDOPO and 105.11g, 0.91moL toxilic acid, be warming up to and be slowly warming up to 115-120 DEG C, open and stir and nitrogen, after reaction 120min, add 56.7g, 0.39moL hexanodioic acid, 110g, 1.22moL1, 4-butyleneglycol and 32.2g, 0.35moL glycerol, after melting completely, slowly be warming up to 150-155 DEG C, carry out esterification dehydration reaction, after end to be drained off, be warming up to 240-250 DEG C, carry out transesterification reaction, after reaction 90min, detect acid number and hydroxyl value every 30min, until acid number and hydroxyl value detect qualified after, be cooled to below 100 DEG C, discharging packaging.
The theoretical hydroxyl value of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 112mgKOH/g;
The theoretical molecular-weight average (number all) of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 1000;
The theoretical phosphorus content of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 12.4%;
The theoretical yield of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 90.68%.
embodiment 5
Agitator is being housed, in the 500ml reaction flask of nitrogen protection and condensation reflux unit, add 196.6g, 0.91moLDOPO and 88.2g, 0.90moL maleic anhydride, be warming up to and be slowly warming up to 110-115 DEG C, open and stir and nitrogen, after reaction 130min, add 80.3g, 0.55moL hexanodioic acid and 45.06g, 0.50moL1, 4-butyleneglycol, after melting completely, slowly be warming up to 155-160 DEG C, carry out esterification dehydration reaction, after end to be drained off, be warming up to 225-235 DEG C, carry out transesterification reaction, after reaction 120min, detect acid number and hydroxyl value every 30min, until acid number and hydroxyl value detect qualified after, be cooled to below 100 DEG C, discharging packaging.
The theoretical hydroxyl value of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 11.4mgKOH/g;
The theoretical molecular-weight average (number all) of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 10000;
The theoretical phosphorus content of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 12.5%;
The theoretical yield of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 90.26%.
embodiment 6
Agitator is being housed, in the 500ml reaction flask of nitrogen protection and condensation reflux unit, add 129.6g, 0.60moLDOPO and 58.8g, 0.60moL maleic anhydride, be warming up to and be slowly warming up to 105-110 DEG C, open and stir and nitrogen, after reaction 100min, add 146.14g, 1.0moL hexanodioic acid and 43.74g, 0.42moL neopentyl glycol, after melting completely, slowly be warming up to 155-160 DEG C, carry out esterification dehydration reaction, after end to be drained off, be warming up to 210-220 DEG C, carry out transesterification reaction, after reaction 150min, detect acid number and hydroxyl value every 30min, until acid number and hydroxyl value detect qualified after, be cooled to below 100 DEG C, discharging packaging.
The theoretical hydroxyl value of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 214mgKOH/g;
The theoretical molecular-weight average (number all) of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 600;
The theoretical phosphorus content of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 13.0%;
The theoretical yield of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 91.9%.
embodiment 7
Agitator is being housed, in the 500ml reaction flask of nitrogen protection and condensation reflux unit, add 170.64g, 0.79moLDOPO and 77.47g, 0.79moL maleic anhydride, be warming up to and be slowly warming up to 100-105 DEG C, open and stir and nitrogen, after reaction 180min, add 117.95, 0.81moL hexanodioic acid and 164.84g, 1.79moL glycerol, after melting completely, slowly be warming up to 150-155 DEG C, carry out esterification dehydration reaction, after end to be drained off, be warming up to 200-210 DEG C, carry out transesterification reaction, after reaction 180min, detect acid number and hydroxyl value every 30min, until acid number and hydroxyl value detect qualified after, be cooled to below 100 DEG C, discharging packaging.
The theoretical hydroxyl value of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 52mgKOH/g;
The theoretical molecular-weight average (number all) of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 2000;
The theoretical phosphorus content of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 10.55%;
The theoretical yield of the synthetic phosphorous-containing polyester polyvalent alcohol of the present embodiment is: 93.4%.
Claims (7)
1. the preparation method of a phosphor-containing halogen-free environmental protection flame retardant polyester polyol, it is characterized in that: taking DOPO as starting raw material, described DOPO first reacts with diprotic acid or dibasic acid anhydride, generate DOPO complex compound intermediate, the intermediate generating carries out esterification dehydration reaction with small molecules polyvalent alcohol and diprotic acid or dibasic acid anhydride again at 150-160 DEG C, after dehydration reaction finishes, again be warming up to 200-250 DEG C and carry out transesterification reaction, reaction times is 1-3h, can obtain so described polyester polyol.
2. the preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol according to claim 1, is characterized in that: when described DOPO reacts with diprotic acid or dibasic acid anhydride, temperature of reaction is 100-120 DEG C, reaction times 1-3h.
3. the preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol according to claim 1, is characterized in that: when described DOPO reacts with diprotic acid or dibasic acid anhydride, the mol ratio of described DOPO and diprotic acid or dibasic acid anhydride is 1:1-1:0.9; When described DOPO complex compound intermediate and small molecules polyvalent alcohol and diprotic acid or dibasic acid anhydride react, the mol ratio of described DOPO complex compound intermediate and small molecules polyvalent alcohol and diprotic acid or dibasic acid anhydride is 1:(0.4-2.5): (0.4-2.0).
4. the preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol according to claim 1, is characterized in that: described small molecules polyvalent alcohol is that functionality is at least 2 the polyvalent alcohol with straight or branched structure.
5. the preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol according to claim 4, is characterized in that: described small molecules polyvalent alcohol is one or more in ethylene glycol, BDO, neopentyl glycol, glycerol.
6. the preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol according to claim 1, is characterized in that: described diprotic acid comprises monounsaturated dicarboxylic acid and unsaturated dibasic acid, described dibasic acid anhydride comprises monounsaturated dicarboxylic acid acid anhydride and unsaturated dicarboxylic acid anhydride.
7. the preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol according to claim 6, is characterized in that: described unsaturated dibasic acid is toxilic acid, and described monounsaturated dicarboxylic acid is hexanodioic acid, and described unsaturated dicarboxylic acid anhydride is maleic anhydride.
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| CN104211900A (en) * | 2014-09-02 | 2014-12-17 | 北京理工大学 | Polyurethane containing DOPO groups and preparation method thereof |
| CN104448202A (en) * | 2014-12-23 | 2015-03-25 | 兰州理工大学 | Preparation method of phosphorus-containing flame-retardant thermoplastic polyurethane elastomer |
| CN104448229A (en) * | 2014-12-23 | 2015-03-25 | 兰州理工大学 | Phosphorus-containing water-based polyurethane resin and preparation method thereof |
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| CN104927038A (en) * | 2015-06-18 | 2015-09-23 | 福建师范大学泉港石化研究院 | Method for preparing DOPO-base flame-retarding polyester polyol in solvent-free mode |
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