CN104403094A - Method for preparation of flame retardant polyether polyol based on modified phosphoric acid - Google Patents
Method for preparation of flame retardant polyether polyol based on modified phosphoric acid Download PDFInfo
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- CN104403094A CN104403094A CN201410648168.3A CN201410648168A CN104403094A CN 104403094 A CN104403094 A CN 104403094A CN 201410648168 A CN201410648168 A CN 201410648168A CN 104403094 A CN104403094 A CN 104403094A
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Abstract
The invention discloses a method for preparation of flame retardant polyether polyol based on modified phosphoric acid. Specifically, in a nitrogen environment, a catalyst and modified phosphoric acid, low molecular amine and epoxy propane undergo mixed reaction, wherein the raw material modified phosphate, low molecular amine and epoxy propane are in a mass part ratio of 1:0.5-1.2:2.5-2.5, the dosage of the catalyst accounts for 0.1-2% of the total mass of the materials, the reaction temperature is 90-120DEG C, the reaction pressure is 0.1-0.8MPa, and the reaction time is 2-8h, and the flame retardant polyether polyol product can be obtained. The phosphoric acid flame retardant polyether polyol provided by the invention has excellent intermiscibility with conventional polyether polyol, and the flame retardant composite material prepared from the phosphoric acid polyether polyol has good storage stability. At the same time, during production of polyurethane rigid foams with the flame retardant polyether polyol provided by the invention, no flame retardant is needed additionally, and the oxygen index can reach 22-24.
Description
Technical field
The present invention relates to the production field of flame retardant polyether polyol, particularly relating to a kind of take modified phosphate as the preparation method of the flame retardant polyether polyol of initiator for the production of hard polyurethane foam.
Background technology
Since urethane (PU) rigid foam comes out, rigid urethane foam is one of principal item of polyurethane synthetic material, have lightweight, heat insulation property good, buffering excellent in vibration resistance, specific tenacity is high, processing molding method is simple and flexible and changeable, and with the advantage such as most of material binding is easy, particularly hard polyurethane foams is with the heat-proof quality of its brilliance, be considered to building field and substitute one of ideal material of conventional inorganic lagging material, but because it is flammable and discharge toxic gas in combustion, limits it and further promote.
At present the conventional method dosing fire retardant is to improve the flame retardant properties of hard polyaminoester on the market, and most fire retardant is the compound containing halogen, and it burns and slow down flame transmission speed reach fire-retardant object by restraining.The most frequently used fire retardant has the compounds such as halogen system, phosphorus system, nitrogen system, but often can discharge the smog with corrodibility, toxicity due to Halogen additive, to environment and etching apparatus, is even detrimental to health.Meanwhile, phosphonic acid ester and nitrogen based flame retardant flame retardant effect not obvious, and use fire retardant in premixed systems after, the package stability of its premixed systems is poor, and in premixed systems, has better package stability to halogen-free phosphorus-containing fire retardant polyether glycol.Like this, high flame resistance is used and the synthesis of the little halogen-free flameproof polyether glycol of environmental pollution just seems very important.
Patent 201310559390.1 discloses a kind of Polyurethane hard foam flame-retardant polyether polyol and preparation method thereof, and its raw material comprises (parts by weight): water 20-50 part, starch 25-30 part, phosphoric acid 8-10 part, PHT4 20-40 part, vitriol oil 0.5-1.5 part, propylene oxide 30-80 part.The preparation method of open file: water, the vitriol oil, starch and PHT4 are mixed post-heating reaction to transparent, add phosphoric acid again, under 120-150 DEG C of condition, slowly propylene oxide is added after abundant mixing, under 100-120 DEG C of condition, vacuumize 20-40min after having reacted, namely obtain Polyurethane hard foam flame-retardant polyether polyol; But because the PHT4 that adopts in this law and the vitriol oil are as the raw materials for production of product, this Contents In Polyether Polyol in use can discharge the smog with corrodibility, toxicity at the polyurethane hard foam of synthesis, to environment, practical function is poor.
Summary of the invention
For above-mentioned Problems existing, the invention provides and a kind ofly can reach the flame retardant polyether polyol of about 23 for having better package stability, the simultaneously oxygen index of institute's hair products in premixed systems.
In order to achieve the above object, the technical solution used in the present invention is as follows: a kind of method preparing flame retardant polyether polyol based on modified phosphate, described preparation method is: in a nitrogen environment, by the phosphoric acid of catalyzer and modification, low molecule amine and propylene oxide carry out hybrid reaction, wherein the ratio of quality and the number of copies of raw material dosage is: the phosphoric acid of modification: low molecule amine: propylene oxide=1:0.5 ~ 1.2:2.5 ~ 2.5, described catalyst levels is 0.1 ~ 2% of above-mentioned material total mass, temperature of reaction is 90 ~ 120 DEG C, reaction pressure is 0.1 ~ 0.8MPa, reaction times is 2 ~ 8 hours, obtain flame retardant polyether polyol product.
The phosphoric acid of modification of the present invention refers to: after phosphoric acid and propylene oxide react in presence of an acid catalyst, the phosphoric acid that the acid number obtained is less than 300.The described preparation method changing phosphoric acid is: in pressure reaction still, add phosphoric acid and propylene oxide that ratio of quality and the number of copies is 1.5 ~ 2.5:1, reactor rotating speed is 85 revs/min, then adds the acid catalyst of 0.1g, temperature of reaction controls at 100 ~ 180 DEG C, Depressor response 2 ~ 4h; In reaction process, sample at regular intervals, measure the acid number of sample according to standard method, when the acid number of analytical reaction product is less than 300, stopped reaction; Intermediate product modified phosphate is obtained after cooling, overvoltage.
Described low molecule amine refers to the one in unit molecule aminated compounds.Specifically comprise amine water, trolamine, triethylamine, tri-isopropanolamine, diethanolamine etc.
Catalyzer of the present invention is amines catalyst, and described catalyzer is the mixture of amines catalyst simple substance or multiple simple substance.Dimethylamine, Trimethylamine 99 etc.Amines catalyst process characteristic is that initial reaction stage speed is fast, and along with polyethers relative molecular mass increases, speed of response slows down gradually.This technique has need not Removal of catalyst, and material consumption energy consumption is lower, can add less or not add the advantages such as amine catalyst in PU foaming formulation.
Acid catalyst of the present invention is Lewis acid: boron trifluoride.Select its major cause of this catalyzer to be that the catalytic activity of this catalyzer itself is higher, the speed of response of catalyze propylene oxide ring-opening polymerization is fast, and reaction just can be carried out at quite low temperatures, is suitable for the polyether glycol of preparation intermediate molecular weight.
The invention has the advantages that: phosphoric acid flame retardant polyether polyol of the present invention and conventional polyether polyvalent alcohol have splendid intermiscibility, and have better package stability with the flame retardant combination material prepared by phosphoric acid polyether glycol of the present invention, when using flame retardant polyether polyol of the present invention and ZS-4110 polyether glycol 1:1 to foam simultaneously, do not need additional fire retardant, oxygen index can reach 22-24.Because this product is not containing halogens, therefore this product is in the use procedure of synthesis of polyurethane rigid foam, does not produce obnoxious flavour, the smog of corrodibility, toxicity can not be produced, can not to environment, health environment-friendly, substantially increases the range of application of this polyurethane hard foam.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
embodiment 1:the preparation of modified phosphate: in a 1L pressure reaction still, adds phosphoric acid 297g, and then adds propylene oxide 138g, catalyzer 0.1g, reacts 2 ~ 4h under control temperature 120-160 DEG C reduced pressure.In reaction process, sample at regular intervals, according to standard method, measure the acid number of sample.When the acid number of analytical reaction product is less than 300, namely stopped reaction obtains product.Obtain modified phosphate performance perameter as follows:
Product appearance: colourless to amber transparent liquid;
Moisture: 0.5%;
Acid number (%): 298;
Viscosity (cSt): 600,25 DEG C.
embodiment 2:modified phosphate 300g, ammoniacal liquor 50g and trolamine 120g is dropped in 1L reactor, after reactor being replaced with nitrogen, vacuumize dehydration, suck dimethylamine 5g, be warmed up to 110 DEG C of final vacuums and carry gas 2 hours, pass into propylene oxide 300 g again, control temperature of reaction at 100 ~ 140 DEG C, pressure 0.1 ~ 0.6MPa, after having led to PO, react aging 1.5hr, through in control qualified after, with leaf filter filter get product.Obtain end properties parameter as follows:
Product appearance: colourless transparent liquid;
Hydroxyl value (mgKOH/g): 435;
Moisture: 0.12%;
Acid number (mgKOH/g): 3.95;
Viscosity (cSt): 14500,25 DEG C;
Density (gm/cc): 1.0208,25 DEG C.
embodiment 3:modified phosphate 280g, triethylamine 80g and diethanolamine 100g is dropped in 1L reactor, after reactor being replaced with nitrogen, vacuumize dehydration, suck dimethylamine 5g, be warmed up to 110 DEG C of final vacuums and carry gas 2 hours, pass into PO propylene oxide 350g again, control temperature of reaction at 90 ~ 140 DEG C, pressure 0.1 ~ 0.6MPa, after having led to PO, react aging 1.5hr, through in control qualified after, with leaf filter filter get product.Obtain end properties parameter as follows:
Product appearance: colourless transparent liquid;
Hydroxyl value (mgKOH/g): 430;
Moisture: 0.15%;
Acid number (mgKOH/g): 4.25;
Viscosity (cSt): 18500,25 DEG C;
Density (gm/cc): 1.0218,25 DEG C.
embodiment 4:modified phosphate 265g, amine water 40g and tri-isopropanolamine 150g is dropped in 1L reactor, after reactor being replaced with nitrogen, vacuumize dehydration, suck Trimethylamine 99 5g, be warmed up to 110 DEG C of final vacuums and carry gas 2 hours, pass into PO propylene oxide 320 g again, control temperature of reaction at 100 ~ 140 DEG C, pressure 0.1 ~ 0.6MPa, after having led to PO, react aging 1.5hr, through in control qualified after, with leaf filter filter get product.Obtain end properties parameter as follows:
Product appearance: colourless transparent liquid;
Hydroxyl value (mgKOH/g): 435;
Moisture: 0.11%;
Acid number (mgKOH/g): 4.55;
Viscosity (cSt): 19500,25 DEG C;
Density (gm/cc): 1.0188,25 DEG C.
embodiment 5:by embodiment 2,3 and 4 middle fingers flame retardant polyether polyol and identical raw material: polyethers ZS-4110 carries out synthesis of polyurethane rigid foam, and the particular product performance parameters finally obtained is as shown in the table: wherein polyether glycol ZS-4110 is buied by Jiangsu Zhongshang Chemical Co., Ltd. of Jin Pu group;
The synthesizing formula (each component concentration is mass parts) that table 1 is each batch of hard polyurethane foam:
After all reaction raw materials that wherein compound package stability refers to except isocyanic ester mix, place one week 40 DEG C time after, with before placement whether this compound be consistent with isocyanate reaction characteristic with isocyanate reaction characteristic again; Isocyanate index refers to the degree that in polyurethane formulations, isocyanic ester is excessive; Can show that the stable phase of the flame retardant polyether polyol of production of the present invention is better thus, there is better package stability.
Table 2 is the performance perameter of each batch of hard polyurethane foam:
Oxygen index of the present invention refers under defined terms, and polyurethane foam carries out the minimum oxygen concn needed for flaming combustion in oxygen-nitrogen mixture stream.Represent with the numerical value of the percent by volume shared by oxygen.As known from Table 2, oxygen index is the important indicator detecting flame-retardant foam, and the oxygen index of conventional polyurethanes foam sample is 19, the oxygen index 22-24 of obvious low resistance combustion polyurethane foam of the present invention, and when burning, resistance combustion polyurethane foam of the present invention is starkly lower than the amount of being fuming of polyurethane foam samples, and conventional polyurethanes foam sample contains halogen, producing along with poisonous smog when burning, affecting environment.
Other performances of the present invention are simultaneously identical with the performance of the hard polyurethane foam that conventional sample is produced or close, range of application for original hard polyurethane foam all can drop into application, but the present invention is in the use procedure of synthesis of polyurethane rigid foam, do not produce obnoxious flavour, the smog of corrodibility, toxicity can not be produced, can not to environment, health environment-friendly, saves the production of enterprise and the processing cost of waste.
It should be noted that, above-mentioned is only preferred embodiment of the present invention, is not used for limiting protection scope of the present invention, and equivalents done on the basis of above-described embodiment all belongs to protection scope of the present invention.
Claims (6)
1. prepare the method for flame retardant polyether polyol based on modified phosphate for one kind, it is characterized in that, described preparation method is: in a nitrogen environment, by the phosphoric acid of catalyzer and modification, low molecule amine and propylene oxide carry out hybrid reaction, wherein the ratio of quality and the number of copies of raw material dosage is: the phosphoric acid of modification: low molecule amine: propylene oxide=1:0.5 ~ 1.2:2.5 ~ 2.5, described catalyst levels is 0.1 ~ 2% of above-mentioned material total mass, temperature of reaction is 90 ~ 120 DEG C, reaction pressure is 0.1 ~ 0.8MPa, reaction times is 2 ~ 8 hours, obtain flame retardant polyether polyol product.
2. the method preparing flame retardant polyether polyol based on modified phosphate according to claim 1, is characterized in that, the phosphoric acid of described modification refers to: after phosphoric acid and propylene oxide react in presence of an acid catalyst, the phosphoric acid that the acid number obtained is less than 300.
3. the method preparing flame retardant polyether polyol based on modified phosphate according to claim 2, it is characterized in that, the described preparation method changing phosphoric acid is: in pressure reaction still, add phosphoric acid and propylene oxide that ratio of quality and the number of copies is 1.5 ~ 2.5:1, reactor rotating speed is 85 revs/min, then add the acid catalyst of 0.1g, temperature of reaction controls at 100 ~ 180 DEG C, Depressor response 2 ~ 4h; In reaction process, sample at regular intervals, measure the acid number of sample according to standard method, when the acid number of analytical reaction product is less than 300, stopped reaction; Intermediate product modified phosphate is obtained after cooling, overvoltage.
4. the method preparing flame retardant polyether polyol based on modified phosphate according to claim 1, is characterized in that, described low molecule amine refers to the one in unit molecule aminated compounds.
5. the method preparing flame retardant polyether polyol based on modified phosphate according to claim 1, is characterized in that, described catalyzer is amines catalyst, and described catalyzer is the mixture of amines catalyst simple substance or multiple simple substance.
6. the method preparing flame retardant polyether polyol based on modified phosphate according to claim 3, is characterized in that, described acid catalyst is Lewis acid: boron trifluoride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085897A (en) * | 2015-08-03 | 2015-11-25 | 黄河三角洲京博化工研究院有限公司 | Synthesis method of phosphorus based-starch flame-retardant polyester polyol |
| CN111070809A (en) * | 2019-12-23 | 2020-04-28 | 江苏吉润住宅科技有限公司 | Composite board |
Citations (4)
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| US5414103A (en) * | 1992-01-10 | 1995-05-09 | Oceanfloor Limited | Polyether phosphate esters |
| CN101747371A (en) * | 2009-12-09 | 2010-06-23 | 湖北福瑞斯化工科技有限公司 | Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and preparation method thereof |
| CN102086262A (en) * | 2010-11-10 | 2011-06-08 | 张家港卡邦新材料有限公司 | Epoxy resin flexibilizer as well as preparation method and application thereof |
| CN103483575A (en) * | 2013-08-22 | 2014-01-01 | 常州市中亚化工有限公司 | Preparation method of polyether glycol applied to flame-retardant slow rebound polyurethane foam plastic |
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2014
- 2014-11-17 CN CN201410648168.3A patent/CN104403094A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| US5414103A (en) * | 1992-01-10 | 1995-05-09 | Oceanfloor Limited | Polyether phosphate esters |
| CN101747371A (en) * | 2009-12-09 | 2010-06-23 | 湖北福瑞斯化工科技有限公司 | Non-halogen flame retardant hydrolysis resistant phosphorus-containing polyether/polyester polyol and preparation method thereof |
| CN102086262A (en) * | 2010-11-10 | 2011-06-08 | 张家港卡邦新材料有限公司 | Epoxy resin flexibilizer as well as preparation method and application thereof |
| CN103483575A (en) * | 2013-08-22 | 2014-01-01 | 常州市中亚化工有限公司 | Preparation method of polyether glycol applied to flame-retardant slow rebound polyurethane foam plastic |
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| 刘益军: "《聚氨酯原料及助剂手册》", 30 April 2005 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085897A (en) * | 2015-08-03 | 2015-11-25 | 黄河三角洲京博化工研究院有限公司 | Synthesis method of phosphorus based-starch flame-retardant polyester polyol |
| CN111070809A (en) * | 2019-12-23 | 2020-04-28 | 江苏吉润住宅科技有限公司 | Composite board |
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Application publication date: 20150311 |