CN101235053A - Substituted biphenyl acid phosphate ester amine salt and preparation method thereof - Google Patents
Substituted biphenyl acid phosphate ester amine salt and preparation method thereof Download PDFInfo
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- CN101235053A CN101235053A CNA2008103004691A CN200810300469A CN101235053A CN 101235053 A CN101235053 A CN 101235053A CN A2008103004691 A CNA2008103004691 A CN A2008103004691A CN 200810300469 A CN200810300469 A CN 200810300469A CN 101235053 A CN101235053 A CN 101235053A
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- phosphate ester
- substituted biphenyl
- acid phosphate
- ester amine
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Abstract
The invention discloses a substituted biphenyl acid amine phosphate of formula (I), wherein R1 presents hydrogen or an alkyl group of C1-4, R2 represents hydrogen or an alkyl group of C1-4, and R3 represents hydrogen or an alkyl group of C1-4. The invention further relates a corresponding preparation method, which comprises using compound III as material to be reacted with phosphorus oxytrichloride via esterification reaction to obtain a compound IV, hydrolyzing the compound IV in the presence of organic alkali to obtain a compound V, neutralizing the compound V and compound NH(R3)2 in organic solvent to obtain target product I. The invention keeps alkyl substituted biphenyl structure and changes P element from tervalence to stable pentavalent which is combined with N element via salt formatnion with amine to improve the content of N element to 2.57% around. The molecule structure can improve the storage stability of P-N fire retardant and improve fire-retardancy. The invention optimizes reaction conditions to improve reaction yield.
Description
Technical field
The present invention relates to a kind of substituted biphenyl acid phosphate ester amine salt and preparation method thereof.
Background technology
The P-N flame retardant is the environment friendly flame retardant that enjoys attention at present, because it is not halogen-containing, has the synergistic fire retardation between P, the N element, and therefore good flame retardation effect meets the development trend that current fire retardant low toxicity or nothing poison.Compound shown in the structural formula II is a kind of chief component of P-N flame retardant, uses it in the polymkeric substance, and oxygen index can reach 27 (seeing Aoyama Masaki, Ueki Koji.JP2000160029).Contain alkyl substituted biphenyl base organic phosphorous acid ester structure in this molecule, therefore base material is had the satisfactory stability plastification.
The molecule shortcoming of structural formula II is that the N constituent content is on the low side, only is about 0.96%, and the synergistic fire retardation between the P element is limited, and because the organic phosphorous acid ester structure is oxidized easily rotten, storage stability is relatively poor relatively.Therefore improving the content of middle N element of compound and the stability of compound is exactly the hot issue of current research.
In the prior art, Svara, the German Patent of Juergen etc. (DE3940765) has been reported the synthetic route of said structure formula V, be to be raw material with III and phosphorus oxychloride, with N, dinethylformamide is a catalyzer, and reaction obtains IV under reflux state, handle with a large amount of Glacial acetic acid again and obtain product V, yield 82.4%.This method is owing to the temperature of reaction height, so by product is many, the principal product yield is low, and needs to consume a large amount of Glacial acetic acid, and cost is higher relatively.
Wang Yizhong, Yu Dingsheng etc. are in " the synthetic and application of PP nucleator " [plastics industry, 1999,27 (5): 29? 1] related to synthetic with the similar material of molecular structure described herein in, be to be raw material with alkyl substituted phenol and phosphorus oxychloride, with the triethylamine is catalyzer, at room temperature after the reaction, the product that obtains is obtained the similar product with structure V described herein with a large amount of water treatments.Though this method has reduced side reaction because temperature of reaction is not high, need to consume big water gaging, and hydrolysis is not thorough usually, contains a lot of unhydrolysed muriates in the product, influences product purity.
Summary of the invention
Technical problem to be solved by this invention is, a kind of substituted biphenyl acid phosphate ester amine salt is provided, and it is applied in the improved P-N flame retardant, when this compound has kept alkyl substituted biphenyl based structures, make the P element become more stable pentavalent,, improved the content of N element simultaneously to combine with the N element with the salifiable mode of amine by trivalent, both help to improve the storage stability of P-N flame retardant, helped to strengthen flame retardant resistance again.The present invention also provides the preparation method of this compound in addition, has both reduced the cost of existing partial reaction route, improves product purity again.
In order to address the above problem, the invention provides substituted biphenyl acid phosphate ester amine salt, its structural formula is general formula (I)
Wherein, R
1Represent hydrogen or C
1-4Alkyl, R
2Represent hydrogen or C
1-4Alkyl, R
3Represent hydrogen or C
1-4Alkyl, above-mentioned alkane is meant the alkane of the straight or branched with 1～4 carbon atom.For example: methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, sec-butyl etc., wherein R
1The preferred tertiary butyl, R
2Preferred tertiary butyl or methyl, R
3Preferred ethyl.
The preparation method of substituted biphenyl acid phosphate ester amine salt is a raw material with the following formula compound III, gets compound IV with phosphorus oxychloride through esterification, and compound IV obtains compound V, compound V and compound N H (R through hydrolysis in the presence of organic bases
3)
2Obtain purpose product I through neutralization reaction in organic solvent, this reaction scheme is as follows:
Compound III and phosphorus oxychloride adopt triethylamine in esterification be catalyzer, and temperature of reaction is at 0 ℃～40 ℃, and the reaction times is 5～20 hours, and reaction solvent adopts benzene,toluene,xylene, sherwood oil or hexanaphthene.
In the building-up process of compound V, adopted the improved synthetic method of intermediate, adopting trimeric cyanamide when compound IV and water are hydrolyzed in organic solvent is catalyzer, wherein the mol ratio of compound IV and water is 1: 1～150, temperature of reaction is 50～100 ℃, reaction times is 1～3 hour, and organic solvent adopts benzene,toluene,xylene, sherwood oil or their mixture.
Compound V and compound N H (R
3)
2Mol ratio be 1: 1～10, temperature of reaction is 60～90 ℃, the reaction times is 3～12 hours, solvent adopts benzene,toluene,xylene, sherwood oil or their mixture.
Compared with prior art, when compound of the present invention has kept alkyl substituted biphenyl based structures, the P element becomes more stable pentavalent by trivalent, promptly become and stablize phosphate ester structure by the phosphorous acid ester structure, simultaneously to combine with the N element with the salifiable mode of amine, the N constituent content is brought up to about 2.57%, and this molecular structure had both helped to improve P-N fire retardant storage stability, helped to strengthen flame retardant resistance again.
Preparation method of the present invention possesses following advantage:
(1) reaction is a catalyzer owing to adopted trimeric cyanamide thoroughly, makes hydrolytic process carry out fully.
(2) yield height, because reaction thoroughly, the intermediate product yield improves, and brings up to about 95% by 82.4%.
(3) cost is low, because to have adopted trimeric cyanamide be catalyzer, compares with technology in the past, does not need to consume a large amount of Glacial acetic acid and water, has both saved cost, has reduced pollution again.
Embodiment
Embodiment 1: with 41g2, and 2 '-dihydroxyl-3,3 ', 5,5 '-tetra-tert biphenyl (III) adds in the 1000ml four-hole boiling flask, adds the 700ml sherwood oil and carries out stirring and dissolving, add 33ml phosphorus oxychloride and 30ml triethylamine, at room temperature reacted 18 hours, suction filtration is removed the hydrochloride of triethylamine, and the filtrate distillation concentrates and makes chloro (4,4 ', 6,6 '-tetra-tert-2,2 '-xenyl) phosphoric acid ester (IV), again to wherein adding 2ml distilled water and 11.9g trimeric cyanamide, 50 ℃ of following stirring reactions 3 hours, suction filtration, filtrate is layering in separating funnel, the petroleum ether layer distillation is concentrated, crystallization, dry 37.9g white powder (4,4 ', 6,6 ' tetra-tert-2,2 '-xenyl) phosphate ester acid (V), yield 80.3%.
With 50g (4,4 ', 6,6 '-tetra-tert-2,2 '-xenyl) phosphoric acid ester (V) adds in the 1000ml four-hole boiling flask, adds the 800ml sherwood oil, stirs, and is heated to 60 ℃, after raw material dissolves fully, add the 11ml diethylamine, stirring reaction 12 hours is cooled to envrionment temperature, suction filtration, with a small amount of petroleum ether filter cake, dry 52.2g white powder (4,4 ', 6,6 '-tetra-tert-2,2 '-xenyl) phosphate ester acid diethylamine (I), yield 90.4%, constituent content analysis: C
32H
52NO
4P, measured value (calculated value)/%, C70.11 (70.46), H9.23 (9.54), N2.21 (2.57).
Embodiment 2: with 50g 2, and 2 '-dihydroxyl-3,3 ', 5,5 '-tetra-tert biphenyl (III) adds in the 500ml four-hole boiling flask, adds 300ml dimethylbenzene and carries out stirring and dissolving, add 40ml phosphorus oxychloride and 37ml triethylamine, at room temperature reacted 10 hours, suction filtration is removed the hydrochloride of triethylamine, and the filtrate distillation concentrates and makes chloro (4,4 ', 6,6 '-tetra-tert-2,2 '-xenyl) phosphoric acid ester (IV), again to wherein adding 50ml distilled water and 15.4g trimeric cyanamide, 98 ℃ of following stirring reactions 1 hour, suction filtration, filtrate is layering in separating funnel, the distillation of dimethylbenzene layer concentrated, crystallization, dry 55.2 white powder (4,4 ', 6,6 '-tetra-tert-2,2 '-xenyl) phosphate ester acid (V), yield 95.9%.
With 50g (4,4 ', 6,6 '-tetra-tert-2,2 '-xenyl) phosphate ester acid (V) adds in the 500ml four-hole boiling flask, adds 300 dimethylbenzene, stirs, and is heated to 80 ℃, after raw material dissolves fully, add the 33ml diethylamine, stirring reaction 6 hours is cooled to envrionment temperature, suction filtration, with a small amount of dimethylbenzene washing leaching cake, dry 56.2g white powder (4,4 ', 6,6 '-tetra-tert-2,2 '-xenyl) phosphate ester acid diethylamine (I), yield 97.3%, constituent content analysis: C
32H
52NO
4P, measured value (calculated value)/%, C70.03 (70.46), H9.19 (9.54), N2.22 (2.57).
Embodiment 3: with 50g2,2 '-dihydroxyl-3,3 '-di-t-butyl-5,5 '-dimethyl diphenyl (III) add in the 500ml four-hole boiling flask, add 300ml toluene and carry out stirring and dissolving, add 50ml phosphorus oxychloride and 46.5ml triethylamine, at room temperature reacted 10 hours, suction filtration is removed the hydrochloride of triethylamine, and the filtrate distillation concentrates and makes chloro (4,4 '-dimethyl-6,6 '-di-t-butyl-2,2 '-xenyl) phosphoric acid ester (IV), add 30ml distilled water and 19.4g trimeric cyanamide, 80 ℃ of following stirring reactions 2.5 hours, suction filtration, filtrate is layering in separating funnel, and the toluene layer distillation concentrates, crystallization, dry the 55.0g white powder (4,4 '-dimethyl-6,6 '-di-t-butyl-2,2 '-xenyl) phosphate ester acid (V), yield 92.4%.
With 38.8g (4,4 '-dimethyl-6,6 '-di-t-butyl-2,2 '-xenyl) phosphate ester acid (V) adds in the 500ml four-hole boiling flask, adds 280 toluene, stir, be heated to 90 ℃, after raw material dissolves fully, add the 20ml diethylamine, stirring reaction 3 hours, be cooled to envrionment temperature, suction filtration is used the small amount of toluene washing leaching cake, dry 40.8g white powder (4,4 '-dimethyl-6,6 '-di-t-butyl-2,2 '-xenyl) phosphate ester acid diethylamine (I), yield 88.5%, constituent content analysis: C
26H
40NO
4P, measured value (calculated value)/%, C67.47 (67.69), H8.75 (8.67), N2.87 (3.04).
Claims (10)
1. substituted biphenyl acid phosphate ester amine salt, this structural general formula (I) is:
Wherein R1 represents the alkyl of hydrogen or C1-4, and R2 represents the alkyl of hydrogen or C1-4, and R3 represents the alkyl of hydrogen or C1-4.
2. substituted biphenyl acid phosphate ester amine salt according to claim 1, wherein R1 represents the tertiary butyl.
3. substituted biphenyl acid phosphate ester amine salt according to claim 1, wherein R2 represents the tertiary butyl or methyl.
4. substituted biphenyl acid phosphate ester amine salt according to claim 1, wherein R3 represents ethyl.
5. substituted biphenyl acid phosphate ester amine salt according to claim 1, wherein R1 represents the tertiary butyl, and R2 represents the tertiary butyl or methyl, and R3 represents ethyl.
6. the preparation method of substituted biphenyl acid phosphate ester amine salt as claimed in claim 1, it is characterized in that: with the following formula compound III is raw material, get compound IV with phosphorus oxychloride through esterification, compound IV is in the presence of organic bases, obtain compound V through hydrolysis reaction, compound V and compound N H (R3) 2 obtain purpose product I through neutralization reaction in organic solvent, this reaction scheme is as follows:
7. the preparation method of substituted biphenyl acid phosphate ester amine salt according to claim 6, it is characterized in that: adopting trimeric cyanamide when compound IV and water are hydrolyzed in organic solvent is catalyzer, wherein the mol ratio of compound IV and water is 1: 1～150, temperature of reaction is 50～100 ℃, and the reaction times is 1～3 hour.
8. according to the preparation method of claim 6 or 7 described substituted biphenyl acid phosphate ester amine salts, it is characterized in that: organic solvent adopts benzene,toluene,xylene, sherwood oil or their mixture.
9. the preparation method of substituted biphenyl acid phosphate ester amine salt according to claim 6, it is characterized in that: compound V and compound N H (R3) 2 react in organic solvent, the mol ratio of the two is 1: 1～10, and temperature of reaction is 60～90 ℃, and the reaction times is 3～12 hours.
10. according to the preparation method of claim 6 or 9 described substituted biphenyl acid phosphate ester amine salts, it is characterized in that: organic solvent adopts benzene,toluene,xylene, sherwood oil or their mixture.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370967A (en) * | 2014-10-24 | 2015-02-25 | 沈阳化工大学 | Polymer-type nitrogen-phosphorus-containing flame retardant and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370967A (en) * | 2014-10-24 | 2015-02-25 | 沈阳化工大学 | Polymer-type nitrogen-phosphorus-containing flame retardant and preparation method thereof |
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Effective date of registration: 20100715 Address after: 550003 Weng Fu International Building, No. 57, South City Road, Guizhou, Guiyang Applicant after: Weng Fu (Group) limited liability company Address before: 550025 Huaxi District, Guizhou, Guiyang Applicant before: Guizhou University |
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Correction item: Patentee Correct: Wengfu (Group) Co., Ltd.|550003, International Building, No. 57, South City Road, Guizhou, Guiyang False: Weng Fu (Group) limited liability company|550003 Weng Fu International Building, No. 57, South City Road, Guizhou, Guiyang Number: 34 Volume: 26 |
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