CN103739626A - Method for synthesis of hydroxy-containing reactive type phosphonate ester flame retardant agent without catalyst and through one-pot method - Google Patents
Method for synthesis of hydroxy-containing reactive type phosphonate ester flame retardant agent without catalyst and through one-pot method Download PDFInfo
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- CN103739626A CN103739626A CN201310488425.7A CN201310488425A CN103739626A CN 103739626 A CN103739626 A CN 103739626A CN 201310488425 A CN201310488425 A CN 201310488425A CN 103739626 A CN103739626 A CN 103739626A
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Abstract
The invention discloses a preparation method of a reactive type phosphonate ester flame retardant agent having the structure general formula as described in the specification, wherein R is represented by the formula (1), the formula (2), the formula (3), the formula (4), the formula (5), the formula (6), or the formula (7). The preparation method comprises the steps: firstly, carrying out a reaction of phosphorus trichloride with neopentyl glycol according to a certain proportion in an organic solvent to obtain a chlorinated phosphite ester intermediate, then dropwise adding anhydrous formic acid, oxidizing the chlorinated phosphite ester intermediate into cyclic phosphonate ester containing active P-H bonds, then carrying out a reaction of cyclic phosphonate ester with a carbonyl compound, and synthesizing the hydroxyl-containing reactive type phosphonate ester flame retardant agent. The above reaction intermediates are directly used in the next step reaction without separation and purification, that is to say, the reaction is the so-called 'one-pot method' reaction. The synthesis method is simple, and is easy to operate, high in yield and low in cost; and the synthesized phosphorus-containing flame retardant agent has stable chemical properties, and has broad application prospects by being used as the reactive type flame retardant agent.
Description
Technical field
The present invention relates to response type phosphonic acid ester fire retardant and the technology of preparing thereof of a class hydroxyl, relate in particular to a kind of method that does not need " one kettle way " building-up reactions type phosphonate fire retardant that adds catalyzer.
Background technology
At present fire retardant development field presents the trend of non-halogen, high efficiency, LSZH.Phosphonic acid ester (phosphoric acid ester) based flame retardant is one of phosphorus flame retardant developing rapidly in recent years, and it is the halogen-free flame retardants that a class is important, have broad prospect of application.In polymer materials, add this small amount of based flame retardant, just can reach good flame retardant effect.
Phosphonium flame retardant can be divided into addition type and response type.Additive flame retardant is to add in by the last handling process of ignition resistant substrate (being generally superpolymer); there is not chemical reaction with other components in base material and base material; just with physics mode, be scattered in base material and give its flame retardant resistance; this based flame retardant addition is larger; often can destroy by the mechanical property of fire-retardant matrix, affect the quality of material.Reactive flame retardant is to add in by ignition resistant substrate manufacturing processed, they or as the monomer of superpolymer, or as linking agent, participate in chemical reaction, finally become the structural unit of superpolymer and give its permanent fire retardant, and less to the Effect on Mechanical Properties of base material.
Response type phosphonium flame retardant is normally grafted in polymer architecture with covalent linkage forms such as P-O or P-C, chemistry bond energy is large, can be present in more stably and lastingly in polymkeric substance, the more general chain phosphoric acid ester of cyclic phosphonate compound of alcoholic hydroxy and P-C key has more thermostability, hydrolytic resistance.Due to the hydroxy functional group of this compounds, can react with the high polymer monomer that contains the groups such as carboxyl, epoxy group(ing), isocyanic ester, therefore when the synthetic macromolecular compound that comprises this type of monomer, if flame-retardant monomer is added as reaction raw materials, fire-retardant unit will access in polymer segment the mode such as to embed, crosslinked, thereby give, it is permanent fire-retardant.As can reacting with urethane (PU) monomeric diisocyanate, the phosphonate compound of hydroxyl generates carbamate groups, therefore, if in polyurethane foam process, set it as flame-retardant monomer and isocyanic ester blend foaming, this fire-retardant unit will be connected in polymer chain, can realize permanent fire-retardant to urethane, will be the reactive flame retardant that a class has application prospect.
Summary of the invention
The method that the object of the present invention is to provide the response type phosphonate fire retardant of the synthetic hydroxyl of one " one kettle way ", step is simple, easy handling, productive rate is higher.
Another object of the present invention is that this based flame retardant is mixed with urethane monomer or performed polymer, as reactive flame retardant, realizes permanent fire-retardant to urethane.
The general structure of response type phosphonate fire retardant provided by the invention is:
Wherein R is:
The synthetic of phosphonate fire retardant provided by the invention is achieved through the following technical solutions.
Preparation method's reaction expression is as follows:
Comprise the steps: that 1. join toluene by neopentyl glycol, benzene, methylene dichloride, chloroform, 1,2-ethylene dichloride, any in Isosorbide-5-Nitrae-dioxane, forms homogeneous phase solution.
2. step (1) gained solution is placed in to frozen water, keeps solution at 5 ~ 10 ℃, stir the lower phosphorus trichloride that slowly drips, within approximately 0.5 ~ 1.5 hour, drip and finish, preferably 1 hour; Keep 40 ℃ of solution temperatures to continue reaction 1 ~ 3 hour, preferably 2 hours.
3. in step (2) gained solution, add ketone or aldehyde compound, then control temperature and at 20 ~ 30 ℃, slowly drip anhydrous formic acid, drip and finish, continue at 40 ~ 55 ℃ of reactions 1 hour, underpressure distillation, except desolventizing, obtains corresponding hydroxyethylidene diphosphonic acid ester cpds.
Owing to having adopted above-mentioned technique and condition, the present invention has following outstanding effect.
1. synthesis technique is simple, easy to operate: neopentyl glycol is reacted products therefrom with phosphorus trichloride do not need separation and purification, directly with reaction solution form, is used for next step reaction.Gained target product purity is higher, very easily purifies.
2. reaction does not need catalyzer, with low cost: in whole preparation process, without using required organic bases or the metal salt catalyst of additive method, reduced cost, simplified post-processing step, reduced the pollution to environment.
3. yield is high, and industrialization prospect is good: the target product of preparing by " one kettle way ", overall yield, more than 60%, adds that cheap raw material and simple technique make cost lower, therefore have good industrialization prospect.
4. response type phosphonate fire retardant provided by the invention, because it has hydroxyl and ring texture simultaneously, not only can give the macromolecular materials such as urethane desirable permanent fire retardant performance, simultaneously on its mechanical property almost without impact.
Accompanying drawing explanation
Fig. 1 is the fire retardant prepared of example 1 of the present invention
1h NMR spectrogram (CDCl
3).
Fig. 2 is the fire retardant prepared of example 1 of the present invention
31p NMR spectrogram (CDCl
3).
Fig. 3 is the infrared spectrum of the fire retardant prepared of example 1 of the present invention.
Fig. 4 is the fire retardant prepared of example 2 of the present invention
1h NMR spectrogram (CDCl
3).
Fig. 5 is the fire retardant prepared of example 2 of the present invention
31p NMR spectrogram (CDCl
3).
Fig. 6 is the infrared spectrum of the fire retardant prepared of example 2 of the present invention.
Fig. 7 is the fire retardant prepared of example 3 of the present invention
1h NMR spectrogram (CDCl
3).
Fig. 8 is the fire retardant prepared of example 3 of the present invention
31p NMR spectrogram (CDCl
3).
Fig. 9 is the infrared spectrum of the fire retardant prepared of example 3 of the present invention.
Figure 10 is the phosphonium flame retardant prepared of example 4 of the present invention
1h NMR spectrogram (CDCl
3).
Figure 11 is the phosphonium flame retardant prepared of example 4 of the present invention
31p NMR collection of illustrative plates (CDCl
3).
Figure 12 is the infared spectrum of the phosphonium flame retardant prepared of example 4 of the present invention.
Figure 13 is the phosphonium flame retardant prepared of example 5 of the present invention
1h NMR collection of illustrative plates (DMSO).
Figure 14 is the phosphonium flame retardant prepared of example 5 of the present invention
31p NMR collection of illustrative plates (DMSO).
Figure 15 is the infared spectrum of the phosphonium flame retardant prepared of example 5 of the present invention.
Figure 16 is the phosphonium flame retardant prepared of example 6 of the present invention
1h NMR spectrogram (CDCl
3).
Figure 17 is the phosphonium flame retardant prepared of example 6 of the present invention
31p NMR spectrogram (CDCl
3).
Figure 18 is the infrared spectrum of the phosphonium flame retardant prepared of example 6 of the present invention.
Figure 19 is the phosphonium flame retardant prepared of example 7 of the present invention
1h NMR spectrogram (CDCl
3).
Figure 20 is the phosphonium flame retardant prepared of example 7 of the present invention
31p NMR spectrogram (CDCl
3).
Figure 21 is the infrared spectrum of the phosphonium flame retardant prepared of example 7 of the present invention.
Claims (5)
1. the method for " one kettle way " building-up reactions type phosphonate fire retardant, is characterized in that: neopentyl glycol is joined to toluene, and benzene, methylene dichloride, chloroform, 1,2-ethylene dichloride, in any organic solvent in Isosorbide-5-Nitrae-dioxane, forms homogeneous phase solution.
2. the method for " one kettle way " building-up reactions type phosphonate fire retardant, is characterized in that: claim 1 gained homogeneous phase solution is placed in to frozen water, keeps solution at 5 ~ 10 ℃, then slowly drip phosphorus trichloride, within approximately 0.5 ~ 1.5 hour, drip and finish, preferably 1 hour; Keep solution temperature to continue reaction 1 ~ 3 hour, preferably 2 hours in 40 ℃.
3. the method for " one kettle way " building-up reactions type phosphonate fire retardant, it is characterized in that: in claim 2 gained solution, add ketone or aldehyde compound, then control temperature and at 20 ~ 30 ℃, slowly drip anhydrous formic acid, drip and finish, continue at 40 ~ 55 ℃ of reactions 1 hour, solvent is removed, obtained target compound.
4. the class response type phosphonate fire retardant described in, is characterized in that, this based flame retardant is the phosphorous heterocylic compound that contains active hydroxyl, and its general structure is as follows
Wherein R is:
。
5.. a preparation method for the response type phosphonate fire retardant as described in claim 1 ~ 4, is characterized in that, described preparation method's reaction expression is as follows:
。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108586704A (en) * | 2018-04-26 | 2018-09-28 | 汤广金 | Insulation aluminium section bar and preparation method thereof |
| CN112480688A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Silicon rubber composition and preparation method and application thereof |
| CN112646122A (en) * | 2020-12-21 | 2021-04-13 | 安徽嘉明新材料科技有限公司 | Preparation method and application of reactive flame-retardant TPU (thermoplastic polyurethane) |
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| US2899455A (en) * | 1959-08-11 | O oxch | ||
| WO1996024626A1 (en) * | 1995-02-10 | 1996-08-15 | Akzo Nobel Nv | Neopentylene phosphonate compounds |
| CN100577670C (en) * | 2004-11-02 | 2010-01-06 | 大八化学工业株式会社 | Method for producing phosphorus compound having phosphate-phosphonate bond |
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2013
- 2013-10-18 CN CN201310488425.7A patent/CN103739626A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2899455A (en) * | 1959-08-11 | O oxch | ||
| WO1996024626A1 (en) * | 1995-02-10 | 1996-08-15 | Akzo Nobel Nv | Neopentylene phosphonate compounds |
| CN100577670C (en) * | 2004-11-02 | 2010-01-06 | 大八化学工业株式会社 | Method for producing phosphorus compound having phosphate-phosphonate bond |
Non-Patent Citations (5)
| Title |
|---|
| K.C.KUMARA SWAMY ET AL.: "Synthesis of New α-Hydroxy-,α-Halogeno- and Vinylphosphates Derived from 5,5-Dimethyl-1,3,2-dioxaphosphinan-2-one", 《SYNTHESIS》 * |
| K.C.KUMARA SWAMY ET AL.: "Synthesis of New α-Hydroxy-,α-Halogeno- and Vinylphosphates Derived from 5,5-Dimethyl-1,3,2-dioxaphosphinan-2-one", 《SYNTHESIS》, 31 December 1997 (1997-12-31), pages 207 - 1 * |
| RUI-LAN FAN ET AL.: "Solubilities of 1,3,2-Dioxaphosphorinane-2-methanol-α,α-5,5-tetramethyl 2-oxide in Selected Solvents at 273.15 K to 343.15 K", 《J. CHEM. ENG. DATA》 * |
| RUI-LAN FAN ET AL.: "Solubilities of 1,3,2-Dioxaphosphorinane-2-methanol-α,α-5,5-tetramethyl 2-oxide in Selected Solvents at 273.15 K to 343.15 K", 《J. CHEM. ENG. DATA》, vol. 58, 10 June 2013 (2013-06-10), pages 2267 - 1 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108586704A (en) * | 2018-04-26 | 2018-09-28 | 汤广金 | Insulation aluminium section bar and preparation method thereof |
| CN108586704B (en) * | 2018-04-26 | 2021-05-07 | 广东金华海铝业有限公司 | Heat-preservation and heat-insulation aluminum profile and preparation method thereof |
| CN112480688A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Silicon rubber composition and preparation method and application thereof |
| CN112646122A (en) * | 2020-12-21 | 2021-04-13 | 安徽嘉明新材料科技有限公司 | Preparation method and application of reactive flame-retardant TPU (thermoplastic polyurethane) |
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Application publication date: 20140423 |