CN105085575A - Flame-retardant polyol containing phosphorus linked pendant groups and preparation method of polyol - Google Patents
Flame-retardant polyol containing phosphorus linked pendant groups and preparation method of polyol Download PDFInfo
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- CN105085575A CN105085575A CN201510554927.4A CN201510554927A CN105085575A CN 105085575 A CN105085575 A CN 105085575A CN 201510554927 A CN201510554927 A CN 201510554927A CN 105085575 A CN105085575 A CN 105085575A
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Abstract
The invention discloses a flame-retardant polyol containing phosphorus linked pendant groups and a preparation method of the polyol. The method specifically comprises steps as follows: 1) a solvent and neopentyl glycol are arranged in a reaction kettle, phosphorus oxychloride is dropwise added, and an intermediate, namely, neopentyl glycol phosphorus oxychloride, is prepared; 2) a solvent and micro-molecular trihydric alcohol or tetrahydric alcohol are arranged in the reaction kettle, an acid-binding agent is added, the intermediate dissolved in the solvent is dropwise added, a reflux reaction is performed, and the flame-retardant polyol containing the phosphorus linked pendant groups is obtained through cooling, filtration and washing. The flame-retardant polyol containing the phosphorus linked pendant groups contains no halogen and is environment-friendly and non-toxic, raw materials are cheap and easy to obtain, the technology is simple and controllable, two or three contained activated terminal hydroxyl groups can react with isocyanate, an intrinsically flame-retardant polyurethane material containing the phosphorus linked pendant groups can be prepared, so that defects that additional flame retardants are poor in compatibility in water-based polyurethane systems, migrate and separate out easily and the like are overcome, and the problem of reduction of physical and chemical properties of the material due to breakage of the polyurethane main chain structure due to the fact that phosphate ester bonds of traditional polyols containing phosphorus linked main chains are not resistant to hydrolysis is also solved.
Description
Technical field
The invention belongs to fire-retardant FRW technical field, be specifically related to a kind of side base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof.
Background technology
Waterbased urethane (WPU) has been widely used in the industries such as leather finish, synthetic leather manufacture, fabric coating, material of construction, tackiness agent, printing, ink and papermaking as multifunctional environment friendly material.But waterbased urethane limiting oxygen index(LOI) (LOI) is only 17% ~ 18%, belongs to inflammable material, and produce the toxic gases such as a large amount of smog and HCN, CO during burning, this greatly hinders it and applies further.At present, improve the flame retardant properties of waterbased urethane and realize mainly through outer interpolation fire retardant, but outer addition type exists that amount of flame-retardant agent is large, compatibleness is poor, easy migration precipitation and affect the defects such as large to material mechanical performance.Thus, preparing inherent flame retardant waterbased urethane by the polyvalent alcohol of the ignition-proof element such as chloride, bromine, phosphorus, nitrogen or isocyanic ester block to waterbased urethane structure, is the development trend of flame-retardant water based polyurethanes.This reactive phosphorus flame retardant wherein becomes the ideal chose of flame-retardant water based polyurethanes owing to not producing the advantages such as corrosive gases when having high, the fire-retardant lasting stability of flame retarding efficiency, burning.But traditional reactive phosphorus flame retardant is positioned at main chain due to ignition-proof element, there is phosphoric acid ester facile hydrolysis thus cause the shortcoming that polyurethane backbone ruptures and then causes material mechanical performance to decline.Therefore, provide the development of a kind of side base phosphor-containing flame-proof polyvalent alcohol to waterbased urethane fire retardant material significant.
Chinese invention patent CN201210103713.1 provides a kind of preparation method of phosphorus halogen cooperative flame retardant polyether glycol, and be applied to the preparation of flame retardant polyurethane, gained polyurethane material has good flame retardant properties (LOI is 30.8%), thermostability and mechanical property, but because this flame retardant polyether polyol contains halogen, the environmental protection theory that this and the world today advocate runs in the opposite direction, and is difficult to meet market demands.
Chinese invention patent CN201010227072.1 describes a kind of preparation method of oligomerization phosphate polyalcohol, synthesis can Some substitute polyether glycol or polyester polyol containing terminal hydroxy group oligomerization phosphate polyalcohol, prepare flame retardant polyurethane with isocyanate reaction.Chinese invention patent CN201210581748.6 discloses a kind of preparation method of phosphorus-containing polyol, this phosphorus-containing polyol linearly structure, the molecular weight of the polyether/polyester macromolecular polyol in original with urethane is close, can give the mechanical property that prepared flame retardant polyurethane is good.Chinese invention patent CN201310309684.9 provides a kind of halogen-free organophosphorous ester flame-proof agent and preparation method thereof, the phosphate flame retardant containing hydrophobic side chains of preparation is embedded in polyurethane structural, can obtain the flame retardant polyurethane foam material of uniform foam cell densification.
Although several patent solves halogen-containing problem above, and in disclosed response type phosphonium flame retardant block to polyurethane structural, improve the flame retardant properties of polyurethane material all to a certain extent, but because fire-retardant phosphoric is all arranged in polyol backbone structure, and there is the defect (M.Sato of facile hydrolysis in phosphate ester flame retardants
j.Appl.Polym.Sci., 2000,5:1134; S.Lu,
prog.Polym.Sci., 2002,8:1661), cause polyurethane backbone to rupture in hydrolytic process and then cause the decline of material physicochemical property.
Summary of the invention
The object of the invention is for above-mentioned the deficiencies in the prior art, a kind of side base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof is provided, the method raw material is cheap to be easy to get, preparation technology is simple, has broad application prospects in manufacture fields such as flame retardant polyurethane rigid foam, flame-retardant polyurethane flexible foam and flame-retardant water based polyurethanes materials.
To achieve these goals, a kind of side provided by the invention base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof, is characterized in that having following structural formula:
，
Wherein, R
1, R
2and R
3represent H or C
1~ C
8alkyl in any one, R
1, R
2and R
3can be the same or different, R
4represent H, – CH
3, – C
2h
5, – NO
2huo – CH
2any one in OH.
A kind of side provided by the invention base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof, it is characterized in that the concrete technology step of the method and condition as follows:
(1) neopentyl glycol of organic solvent dissolution is placed in reactor, phosphorus oxychloride is dripped under nitrogen atmosphere protection, time for adding is 1 ~ 2h, wait to dropwise, slowly be warming up to 45 ~ 65 DEG C of back flow reaction 4 ~ 6h, obtain white solid, cool, filter, with deionized water wash, at 70 ~ 80 DEG C, after vacuum-drying, obtain white powder intermediate neopentyl glycol phosphoryl chloride;
(2) by small molecules trivalent alcohol or tetravalent alcohol and organic solvent
be placed in reactor, add acid binding agent, drip organic solvent
the intermediate neopentyl glycol phosphoryl chloride dissolved, time for adding is 1 ~ 2h, after dropwising, is warming up to 75 ~ 95 DEG C of back flow reaction 4 ~ 6h, and cooling, filtration, use organic solvent
washing, namely obtains the side base phosphor-containing flame-proof polyvalent alcohol of white powder or thick liquid nano in 70 ~ 80 DEG C of vacuum-dryings.
The concrete reaction equation of above-mentioned steps is:
。
In above-mentioned steps (1), the mol ratio of phosphorus oxychloride used and neopentyl glycol is 1:1 ~ 1.2:1.
Organic solvent used in above-mentioned steps (1) is any one in methylene dichloride or chloroform.
Small molecules trivalent alcohol used in above-mentioned steps (2) or tetravalent alcohol be glycerol,
1,2,4-trihydroxybutane,
1,2,5-penta triol,
1,2,6-hexanetriol,
1,2,7-heptan triol,
1,2,8-Xin triol,
1,2,9-the ninth of the ten Heavenly Stems triol,
1,2,10-the last of the ten Heavenly stems triol, trimethylolethane, TriMethylolPropane(TMP), any one in trishydroxymethylnitromethane or tetramethylolmethane.
The mol ratio of small molecules trivalent alcohol used in above-mentioned steps (2) or tetravalent alcohol and intermediate neopentyl glycol phosphoryl chloride is 1:1 ~ 1.2:1.
Acid binding agent used in above-mentioned steps (2) is any one in pyridine or triethylamine.
In above-mentioned steps (2), the mol ratio of acid binding agent used and small molecules trivalent alcohol or tetravalent alcohol is 1:1 ~ 1.5:1.
Organic solvent used in above-mentioned steps (2)
for acetonitrile,
n,N-dimethyl formamide or
n,Nany one in-N,N-DIMETHYLACETAMIDE.
Organic solvent used in above-mentioned steps (2)
for any one in acetone, butanone, ethanol or tetrahydrofuran (THF) or isopyknic any two.
Side base phosphor-containing flame-proof polyvalent alcohol prepared by above-mentioned steps can be applicable to the materials such as flame retardant polyurethane rigid foam, flame-retardant polyurethane flexible foam and flame-retardant water based polyurethanes, preferred flame-retardant water based polyurethanes material.
The present invention compared with prior art, has following positively effect:
1. side provided by the invention base phosphor-containing flame-proof polyol starting material is cheap and easy to get, not halogen-containing, environment-protecting asepsis, and technique is simple and easy to control;
2. side provided by the invention base phosphor-containing flame-proof polyvalent alcohol contains 2 or 3 reactive hydroxyl end group, belongs to reactive flame retardant.It partly or entirely can substitute small molecule polyol chainextender, prepares inherent flame retardant waterbased urethane material with isocyanate reaction, overcomes the defects such as poor, the easy migration precipitation of outer additive flame retardant compatibleness in waterbased urethane system;
3. side provided by the invention base phosphor-containing flame-proof polyvalent alcohol when preparing extinguishing waterborn polyurethane by fire-retardant phosphoric " suspension " on the side chain of urethane segment, efficiently solve traditional response type main chain phosphorus-containing polyol due to not hydrolysis and the problem causing polyurethane backbone structural break and then cause material physicochemical property to decline;
4. when waterbased urethane prepared by side provided by the invention base phosphor-containing flame-proof polyvalent alcohol, technique is easy to control, performance is easy to regulate, and prepared flame-retardant water based polyurethanes is widely used in the industries such as leather finish, synthetic leather manufacture, fabric coating, material of construction, tackiness agent, printing, ink and papermaking.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of prepared intermediate neopentyl glycol phosphoryl chloride.
In the infrared spectrum of the neopentyl glycol of intermediate shown in Fig. 1 phosphoryl chloride, used test instrument is NicoletIS10 type Fourier infrared spectrograph, the sample preparation of KBr pressed disc method.2981cm
-1and 2896cm
-1chu Wei – CH
3he – CH
2stretching vibration absorption peak, 1303cm
-1place is the stretching vibration peak of P=O key, 1052cm
-1and 1005cm
-1place is the stretching vibration peak of P – O – C key, 550cm
-1place is the stretching vibration peak of P – Cl key, and the appearance of these charateristic avsorption bands shows the successful preparation of neopentyl glycol phosphoryl chloride.
The infrared spectrogram of the side base phosphor-containing flame-proof polyvalent alcohol of Fig. 2 synthesized by embodiment 3.
Figure 2 shows that the infrared spectrum of side base phosphor-containing flame-proof polyvalent alcohol, used test instrument is NicoletIS10 type Fourier infrared spectrograph, the sample preparation of KBr pressed disc method.3421cm
-1the stretching vibration absorption peak of Chu Wei – OH, 2976cm
-1and 2939cm
-1chu Shi – CH
3he – CH
2stretching vibration absorption peak, the stretching vibration absorption peak of 1289cm-1 place P=O key, 1036cm
-1and 1010cm
-1place is the stretching vibration absorption peak of P – O – C key, and appears at 550cm
-1the stretching vibration peak completely dissolve of place P – Cl, this illustrates that the hydroxyl of P – Cl key and small molecules trivalent alcohol there occurs reaction, successfully prepares side base phosphor-containing flame-proof polyvalent alcohol.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that following examples are just for being further detailed the present invention; limiting the scope of the invention can not be interpreted as; the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above, still belongs to protection scope of the present invention.
Embodiment 1
(1) in the 500ml four-hole boiling flask that mechanical stirrer, constant pressure dropping funnel, thermometer, nitrogen condensing reflux pipe are housed, add 200ml methylene dichloride and 104.2g(1.0mol) neopentyl glycol, stir, dissolve, 184.0g(1.2mol is dripped by constant pressure funnel) phosphorus oxychloride, time for adding 2h.Wait to dropwise, oil bath is heated, and is slowly warming up to 45 DEG C of back flow reaction 6h, obtains white solid, cools, filters, with deionized water wash, obtains white powder intermediate neopentyl glycol phosphoryl chloride at 70 DEG C after vacuum-drying;
(2) in the 500ml four-hole boiling flask that mechanical stirrer, constant pressure funnel, thermometer, condensing reflux pipe are housed, add 50ml acetonitrile and 55.3g(0.6mol) glycerol, stir, dissolve, add triethylamine 60.7g(0.6mol), the 92.2g(0.5mol of 150ml acetonitrile dissolving is dripped by constant pressure funnel) intermediate neopentyl glycol phosphoryl chloride, time for adding 2h.After dropwising, oil bath is heated, and is warming up to 75 DEG C of back flow reaction 6h, and cooling, filtration, with washing with acetone, namely obtain thick liquid shape side base phosphor-containing flame-proof polyvalent alcohol in 70 DEG C of vacuum-dryings.
Embodiment 2
(1) in the 500ml four-hole boiling flask that mechanical stirrer, constant pressure dropping funnel, thermometer, nitrogen condensing reflux pipe are housed, add 150ml chloroform and 104.2g(1.0mol) neopentyl glycol, stir, dissolve, 153.3g(1.0mol is dripped by constant pressure funnel) phosphorus oxychloride, time for adding 1h.Wait to dropwise, oil bath is heated, and is slowly warming up to 65 DEG C of back flow reaction 4h, obtains white solid, cools, filters, with deionized water wash, obtains white powder intermediate neopentyl glycol phosphoryl chloride at 80 DEG C after vacuum-drying;
(2) in the 500ml four-hole boiling flask that mechanical stirrer, constant pressure funnel, thermometer, condensing reflux pipe are housed, 50ml is added
n,N-dimethyl formamide and 67.1g(0.5mol)
1,2,6-hexanetriol, stirs, and dissolves, adds pyridine 59.3g(0.75mol), drip 100ml by constant pressure funnel
n,Nthe 92.2g(0.5mol that-dimethyl formamide dissolves) intermediate neopentyl glycol phosphoryl chloride, time for adding 1h.After dropwising, oil bath is heated, and is warming up to 95 DEG C of back flow reaction 4h, and cooling, filtration, by butanone and the washing with alcohol of equal proportion, namely obtain thick liquid shape side base phosphor-containing flame-proof polyvalent alcohol in 80 DEG C of vacuum-dryings.
Embodiment 3
(1) in the 500ml four-hole boiling flask that mechanical stirrer, constant pressure dropping funnel, thermometer, nitrogen condensing reflux pipe are housed, add 200ml chloroform and 104.2g(1.0mol) neopentyl glycol, stir, dissolve, 168.7g(1.1mol is dripped by constant pressure funnel) phosphorus oxychloride, time for adding 1.5h.Wait to dropwise, oil bath is heated, and is slowly warming up to 60 DEG C of back flow reaction 5h, obtains white solid, cools, filters, with deionized water wash, obtains white powder intermediate neopentyl glycol phosphoryl chloride at 75 DEG C after vacuum-drying;
(2) in the 500ml four-hole boiling flask that mechanical stirrer, constant pressure funnel, thermometer, condensing reflux pipe are housed, 80ml is added
n,N-N,N-DIMETHYLACETAMIDE and 66.1g(0.55mol) trimethylolethane, stir, dissolve, add pyridine 48.3g(0.66mol), drip 100ml by constant pressure funnel
n,Nthe 92.2g(0.5mol of-dimethylacetamide amine solvent) intermediate neopentyl glycol phosphoryl chloride, time for adding 1.5h.After dropwising, oil bath is heated, and is warming up to 85 DEG C of back flow reaction 5h, cooling, filtration, with tetrahydrofuran (THF) washing, namely obtains white powder side base phosphor-containing flame-proof polyvalent alcohol in 75 DEG C of vacuum-dryings.
Embodiment 4
(1) in the 500ml four-hole boiling flask that mechanical stirrer, constant pressure dropping funnel, thermometer, nitrogen condensing reflux pipe are housed, add 200ml methylene dichloride and 104.2g(1.0mol) neopentyl glycol, stir, dissolve, 168.7g(1.1mol is dripped by constant pressure funnel) phosphorus oxychloride, time for adding 1h.Wait to dropwise, oil bath is heated, and is slowly warming up to 50 DEG C of back flow reaction 6h, obtains white solid, cools, filters, with deionized water wash, obtains white powder intermediate neopentyl glycol phosphoryl chloride at 80 DEG C after vacuum-drying;
(2) in the 500ml four-hole boiling flask that mechanical stirrer, constant pressure funnel, thermometer, condensing reflux pipe are housed, add 150ml acetonitrile and 136.2g(0.6mol) tetramethylolmethane, stir, dissolve, add triethylamine 91.1g(0.9mol), the 92.2g(0.5mol of 150ml acetonitrile dissolving is dripped by constant pressure funnel) intermediate neopentyl glycol phosphoryl chloride, time for adding 2h.After dropwising, oil bath is heated, and is warming up to 90 DEG C of back flow reaction 6h, cooling, filtration, with acetone and the butanone washing of equal proportion, namely obtains white powder side base phosphor-containing flame-proof polyvalent alcohol in 70 DEG C of vacuum-dryings.
Claims (10)
1. side base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof, is characterized in that having following structural formula:
，
Wherein, R
1, R
2and R
3represent H or C
1~ C
8alkyl in any one, R
1, R
2and R
3can be the same or different, R
4represent H, – CH
3, – C
2h
5, – NO
2huo – CH
2any one in OH.
2. side according to claim 1 base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof, it is characterized in that the concrete technology step of the method and condition as follows:
(1) neopentyl glycol of organic solvent dissolution is placed in reactor, phosphorus oxychloride is dripped under nitrogen atmosphere protection, time for adding is 1 ~ 2h, wait to dropwise, slowly be warming up to 45 ~ 65 DEG C of back flow reaction 4 ~ 6h, obtain white solid, cool, filter, with deionized water wash, at 70 ~ 80 DEG C, after vacuum-drying, obtain white powder intermediate neopentyl glycol phosphoryl chloride;
(2) by small molecules trivalent alcohol or tetravalent alcohol and organic solvent
be placed in reactor, add acid binding agent, drip organic solvent
the intermediate neopentyl glycol phosphoryl chloride dissolved, time for adding is 1 ~ 2h, after dropwising, is warming up to 75 ~ 95 DEG C of back flow reaction 4 ~ 6h, and cooling, filtration, use organic solvent
washing, namely obtains the side base phosphor-containing flame-proof polyvalent alcohol of white powder or thick liquid nano in 70 ~ 80 DEG C of vacuum-dryings.
3. side according to claim 2 base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof, is characterized in that the mol ratio of phosphorus oxychloride used in the method and neopentyl glycol is 1:1 ~ 1.2:1.
4. side base phosphor-containing flame-proof polyvalent alcohol according to Claims 2 or 3 and preparation method thereof, is characterized in that organic solvent used in the method is any one in methylene dichloride or chloroform.
5. side according to claim 2 base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof, it is characterized in that small molecules trivalent alcohol used in the method or tetravalent alcohol be glycerol,
1,2,4-trihydroxybutane,
1,2,5-penta triol,
1,2,6-hexanetriol,
1,2,7-heptan triol,
1,2,8-Xin triol,
1,2,9-the ninth of the ten Heavenly Stems triol,
1,2,10-the last of the ten Heavenly stems triol, trimethylolethane, TriMethylolPropane(TMP), any one in trishydroxymethylnitromethane or tetramethylolmethane.
6. side base phosphor-containing flame-proof polyvalent alcohol according to claim 2 or 5 and preparation method thereof, is characterized in that the mol ratio of small molecules trivalent alcohol used in the method or tetravalent alcohol and intermediate neopentyl glycol phosphoryl chloride is 1:1 ~ 1.2:1.
7. side base phosphor-containing flame-proof polyvalent alcohol according to claim 2 or 6 and preparation method thereof, is characterized in that acid binding agent used in the method is any one in pyridine or triethylamine.
8. side according to claim 7 base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof, is characterized in that the mol ratio of acid binding agent used in the method and small molecules trivalent alcohol or tetravalent alcohol is 1:1 ~ 1.5:1.
9. side according to claim 2 base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof, is characterized in that organic solvent used in the method
for acetonitrile,
n,N-dimethyl formamide or
n,Nany one in-N,N-DIMETHYLACETAMIDE.
10. side according to claim 2 base phosphor-containing flame-proof polyvalent alcohol and preparation method thereof, is characterized in that organic solvent used in the method
for any one in acetone, butanone, ethanol or tetrahydrofuran (THF) or isopyknic any two.
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| CN107602847A (en) * | 2017-09-30 | 2018-01-19 | 中国科学院福建物质结构研究所 | Phosphorus-nitrogen containing PPG and its preparation method and application |
| CN108329519A (en) * | 2018-01-31 | 2018-07-27 | 福建师范大学 | A kind of polyhydroxy phosphate flame retardants and the preparation method and application thereof |
| CN109320684A (en) * | 2018-09-29 | 2019-02-12 | 南京工业大学 | A kind of polyurethane polyol and its preparation method and application |
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| CN106977689A (en) * | 2017-04-20 | 2017-07-25 | 福建清源科技有限公司 | A kind of preparation method and application of aqueous polyurethane |
| CN106977689B (en) * | 2017-04-20 | 2019-09-13 | 福建清源科技有限公司 | A kind of preparation method and application of aqueous polyurethane |
| CN107602847A (en) * | 2017-09-30 | 2018-01-19 | 中国科学院福建物质结构研究所 | Phosphorus-nitrogen containing PPG and its preparation method and application |
| CN107602847B (en) * | 2017-09-30 | 2020-02-21 | 中国科学院福建物质结构研究所 | Polyether polyol containing phosphorus and nitrogen, and preparation method and application thereof |
| CN108329519A (en) * | 2018-01-31 | 2018-07-27 | 福建师范大学 | A kind of polyhydroxy phosphate flame retardants and the preparation method and application thereof |
| CN109320684A (en) * | 2018-09-29 | 2019-02-12 | 南京工业大学 | A kind of polyurethane polyol and its preparation method and application |
| CN109320684B (en) * | 2018-09-29 | 2020-09-04 | 南京工业大学 | Polyurethane polyol and preparation method and application thereof |
| CN109585916A (en) * | 2018-11-13 | 2019-04-05 | 吉林师范大学 | A kind of flame-retardant polymer solid electrolyte material and its dielectric film and application |
| CN114316239A (en) * | 2021-12-28 | 2022-04-12 | 万华化学集团股份有限公司 | Polycarbonate polyol with phosphorus-containing side chain, and preparation method and application thereof |
| CN114316239B (en) * | 2021-12-28 | 2023-08-11 | 万华化学集团股份有限公司 | Polycarbonate polyol with side chain containing phosphorus as well as preparation method and application thereof |
| CN115521750A (en) * | 2022-10-08 | 2022-12-27 | 上海嘉均瑞科技有限公司 | Polyurethane-based pouring sealant and preparation method thereof |
| CN115521750B (en) * | 2022-10-08 | 2023-09-22 | 江苏穿越光电科技有限公司 | Polyurethane-based pouring sealant and preparation method thereof |
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Application publication date: 20151125 |