CN104004171B - A kind of preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol - Google Patents
A kind of preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol Download PDFInfo
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Abstract
The invention provides a kind of preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol, take DOPO as starting raw material, described DOPO first reacts with diprotic acid or dibasic acid anhydride, generate DOPO complex intermediate, the intermediate generated carries out esterification dehydration reaction with small molecule polyol and diprotic acid or dibasic acid anhydride again at 150-160 DEG C, after dehydration reaction terminates, is again warming up to 200-250 DEG C and carries out transesterification reaction, reaction times is 1-3h, can obtain described polyester polyol like this.The polyester polyol that the present invention prepares, it not conventional polyester polyol, it is the polyester polyol containing 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, make polyester polyol of the present invention be a kind of phosphor-containing halogen-free environmental protection flame retardant polyester polyol.
Description
Technical field
The invention belongs to the preparation method field of Chemicals, relate to a kind of preparation method of polyester polyol, be related specifically 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 widely, and it is mainly for the production of polyurethane product, comprises thermoplastic polyurethane, flexible PU foam, hard polyurethane foam, solvent type polyurethane resin and waterborne polyurethane resin etc.
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 sofa synthetic leather, interior leather for automobiles and building interior decoration leather.
At present, polyurethane flame-proof is main or add fire-retardant method 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, organic concentration over-standard in enclosed space volatility can be caused, easily potential injury is caused to human body.
The permanent fire retardant polyurethane products that market occurs adopt the method synthesis of Halogen polyvalent alcohol being entered molecule segment to realize usually, although this Halogen urethane also has certain flame retardant properties, but this product can produce the irritant gas such as hydracid and hypohalous acid when burning, and produces other injury to human body.
Phosphorus flame retardant is one of fire retardant of environmental protection the most in the market, its mode of mainly later adding for urethane.The phosphorous polyurethane products having no permanent fire retardant come out, relevant research report and Patents also comparatively rare, only China applies for a patent CN103044673A, correlative study has been carried out to halogen-free phosphorus-containing response type polyester polyol, 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, under certain condition, the polyester polyol with flame retardant properties has been synthesized.
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, this invention takes following technical scheme:
A kind of preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol, take DOPO as starting raw material, described DOPO first reacts with diprotic acid or dibasic acid anhydride, generate DOPO complex intermediate, the intermediate generated carries out esterification dehydration reaction with small molecule polyol and diprotic acid or dibasic acid anhydride again at 150-160 DEG C, after dehydration reaction terminates, is again warming up to 200-250 DEG C and carries out transesterification reaction, reaction times is 1-3h, can obtain described polyester polyol like this.DOPO is BACN intermediate.Containing P-H key in its structure, activity is had to alkene, epoxy bond and carbonyl, can react and generate many derivatives.DOPO(9,10-dihydro-9-oxy is mixed-l0-phospho hetero phenanthrene-l0-oxide compound) and derivative due in molecular structure containing cyclohexyl biphenyl and phenanthrene ring structure, particularly phosphorus group in side is introduced in the mode of ring-type O=P-O key, than organophosphate thermostability that is general, non-Cheng Huan and chemical stability high, flame retardant properties is better.DOPO and derivative thereof can be used as response type and additive flame retardant, the fire retardant Halogen of synthesis, smokeless, nontoxic, and do not move, flame retardant properties is lasting.Be incorporated in polyester polyol by DOPO by the mode of synthesis, synthesized polyester polyol can be used for preparing phosphor-containing flame-proof type polyurethane product.
Preferably, when described DOPO and diprotic acid or dibasic acid anhydride react, temperature of reaction is 100-120 DEG C, reaction times 1-3h.
Preferably, when described DOPO and diprotic acid or dibasic acid anhydride react, the mol ratio of described DOPO and diprotic acid or dibasic acid anhydride is 1:1-1:0.9; When described DOPO complex intermediate and small molecule polyol and diprotic acid or dibasic acid anhydride react, the mol ratio of described DOPO complex intermediate and small molecule polyol and diprotic acid or dibasic acid anhydride is 1:(0.4-2.5): (0.4-2.0).
Preferably, described small molecule polyol is the polyvalent alcohol with straight or branched structure that functionality is at least 2.
Further preferably, described small molecule polyol 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.
Preferred further, 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 mentioned in the present invention, toxilic acid, maleic anhydride is
,
,
.
DOPO involved in the present invention introduces the reaction mechanism of polyester construction, for DOPO and toxilic acid:
(DOPO-MA)
DOPO complex intermediate and small molecule polyol and diprotic acid or dibasic acid anhydride react, and for DOPO-MA and hexanodioic acid and ethylene glycol, its reaction mechanism is:
beneficial effect:the present invention of technique scheme is adopted to have the following advantages:
Specifically, compared with prior art, the technical scheme that the present invention takes has following outstanding advantage:
(1) polyester polyol prepared of the present invention, it not conventional polyester polyol, it is the polyester polyol containing P element, there is the reactivity with isocyanic ester, it can be used for the permanent fire retardant modification of polyurethane products, P element is introduced in polyester polyol, polyester polyol of the present invention is made to be 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, the obtained urethane of this kind of flame retardant polyester polyvalent alcohol is used to have good flame retardant properties equally,
(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 prepared of the present invention, its phosphorus content more than 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 illustration of the present invention; can not limit the scope of the invention with this; the equivalence change that every spirit according to the present invention is done or modification, 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, acid number and hydroxyl value is detected every 30min, until acid number and hydroxyl value detect qualified after, be cooled to less than 100 DEG C, discharging is packed.
The theoretical hydroxyl number of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 56mgKOH/g;
The theoretical molecular-weight average (number all) of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 2000;
The theoretical phosphorus content of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 10.65%;
The theoretical yield of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis 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, acid number and hydroxyl value is detected every 30min, until acid number and hydroxyl value detect qualified after, be cooled to less than 100 DEG C, discharging is packed.
The theoretical hydroxyl number of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 224mgKOH/g;
The theoretical molecular-weight average (number all) of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 500;
The theoretical phosphorus content of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 13.2%;
The theoretical yield of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis 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, acid number and hydroxyl value is detected every 30min, until acid number and hydroxyl value detect qualified after, be cooled to less than 100 DEG C, discharging is packed.
The theoretical hydroxyl number of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 11.2mgKOH/g;
The theoretical molecular-weight average (number all) of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 10000;
The theoretical phosphorus content of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 12.9%;
The theoretical yield of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis 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, acid number and hydroxyl value is detected every 30min, until acid number and hydroxyl value detect qualified after, be cooled to less than 100 DEG C, discharging is packed.
The theoretical hydroxyl number of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 112mgKOH/g;
The theoretical molecular-weight average (number all) of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 1000;
The theoretical phosphorus content of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 12.4%;
The theoretical yield of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis 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, acid number and hydroxyl value is detected every 30min, until acid number and hydroxyl value detect qualified after, be cooled to less than 100 DEG C, discharging is packed.
The theoretical hydroxyl number of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 11.4mgKOH/g;
The theoretical molecular-weight average (number all) of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 10000;
The theoretical phosphorus content of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 12.5%;
The theoretical yield of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis 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, acid number and hydroxyl value is detected every 30min, until acid number and hydroxyl value detect qualified after, be cooled to less than 100 DEG C, discharging is packed.
The theoretical hydroxyl number of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 214mgKOH/g;
The theoretical molecular-weight average (number all) of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 600;
The theoretical phosphorus content of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 13.0%;
The theoretical yield of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis 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, acid number and hydroxyl value is detected every 30min, until acid number and hydroxyl value detect qualified after, be cooled to less than 100 DEG C, discharging is packed.
The theoretical hydroxyl number of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 52mgKOH/g;
The theoretical molecular-weight average (number all) of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 2000;
The theoretical phosphorus content of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 10.55%;
The theoretical yield of the phosphorous-containing polyester polyvalent alcohol of the present embodiment synthesis is: 93.4%.
Claims (2)
1. the preparation method of a phosphor-containing halogen-free environmental protection flame retardant polyester polyol, it is characterized in that: take DOPO as starting raw material, described DOPO first reacts with diprotic acid or dibasic acid anhydride, generate DOPO complex intermediate, the intermediate generated carries out esterification dehydration reaction with small molecule polyol and diprotic acid or dibasic acid anhydride again at 150-160 DEG C, after dehydration reaction terminates, again be warming up to 200-250 DEG C and carry out transesterification reaction, reaction times is 1-3h, can obtain described polyester polyol like this;
When described DOPO and diprotic acid or dibasic acid anhydride react, the mol ratio of described DOPO and diprotic acid or dibasic acid anhydride is 1:1-1:0.9; When described DOPO complex intermediate and small molecule polyol and diprotic acid or dibasic acid anhydride react, the mol ratio of described DOPO complex intermediate and small molecule polyol and diprotic acid or dibasic acid anhydride is 1:(0.4-2.5): (0.4-2.0);
Described small molecule polyol is the polyvalent alcohol with straight or branched structure that functionality is at least 2, is one or more in ethylene glycol, BDO, neopentyl glycol, glycerol;
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, described unsaturated dibasic acid is toxilic acid, and described monounsaturated dicarboxylic acid is hexanodioic acid, and described unsaturated dicarboxylic acid anhydride is maleic anhydride.
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 and diprotic acid or dibasic acid anhydride react, temperature of reaction is 100-120 DEG C, reaction times 1-3h.
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| CN111171304B (en) * | 2020-02-12 | 2021-04-06 | 东华大学 | Preparation method and application of phosphorus-containing flame-retardant resin |
| CN111518266B (en) * | 2020-06-16 | 2022-04-12 | 万华化学集团股份有限公司 | Polyester polyol and preparation method and application thereof |
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| CN115093530A (en) * | 2022-07-27 | 2022-09-23 | 旭川化学（苏州）有限公司 | Bio-based flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
| CN115785418A (en) * | 2022-11-03 | 2023-03-14 | 万华化学集团股份有限公司 | Polyester polyol, preparation method thereof and polyurethane soft foam |
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| WO2008119693A1 (en) * | 2007-04-03 | 2008-10-09 | Basf Se | Dopo flame retardant compositions |
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