CN1459453A - Phosphate type liquid alicyclic olefin compound and its preparation method - Google Patents
Phosphate type liquid alicyclic olefin compound and its preparation method Download PDFInfo
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- CN1459453A CN1459453A CN 02119743 CN02119743A CN1459453A CN 1459453 A CN1459453 A CN 1459453A CN 02119743 CN02119743 CN 02119743 CN 02119743 A CN02119743 A CN 02119743A CN 1459453 A CN1459453 A CN 1459453A
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- alicyclic olefin
- type liquid
- phosphate type
- olefin compound
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Abstract
A phosphate-type alicyclic olefine compound in the form of liquid is prepared through proportioning alicyclic olefine alkoxide, phosphorus trioxyhalide and alamine, preparing the organic solution of alicyclic olefine alkoxide and alamine, dropping the phosphorus trioxyhalide to the said organic solution, heating to 50-80 deg.c, reaction for 0.5-2, and purifying.
Description
Technical field:
The present invention relates to a kind of alicyclic olefin compound and preparation method thereof, particularly a kind of phosphate type alicyclic olefin compound and preparation method thereof.
Background technology:
Alicyclic olefin is to study and use all a compounds very widely.Alicyclic olefin can be used as monomer carries out cyclopolymerization and the ring copolymerization, obtain fused ring polymers system (J.Polym.Sci.:Part A-1,1967,5,1827-1844); Also can be used as intermediate and carry out alkene prepared in reaction olefin resin (U.S.Pat.4849532 and JP Patent 05032647A).Can also generate alicyclic epoxide compound with the peroxy acid oxidation.Synthetic method can be raw material synthetic (GE.Pat.1099733 and U.S.Pat.2848426) with phenol or Resorcinol, can be starting raw material also with divinyl and propenal or crotonaldehyde, through reactions such as diene additions, obtain the ester or the etherate (U.S.Pat.2750395 and U.S.Pat.2745847) of alicyclic ring diolefine.The compound of alicyclic olefin is similar to fatty compounds, owing to have low C/H ratio, and intramolecularly do not have the conjugation rock steady structure, possesses fire retardancy hardly, reaches the practical application purpose for making it, must carry out fire-retardant finish to it.
At present, flame resistant method mainly contains two kinds:
A kind of method of carrying out fire-retardant finish comprises inorganic combustion inhibitor, as aluminium hydroxide, magnesium hydroxide, ammonium polyphosphate, simple substance red phosphorus, borate family for adding fire retardant; Halogen containing flame-retardant such as bromide fire retardant, chlorine-based flame retardant; Phosphonium flame retardant such as phosphoric acid ester, phosphonic acid ester.In order to reach the ideal flame retardant effect, the add-on of fire retardant is generally all bigger, can affect greatly Mechanical Properties of Materials, electrical property, viscosity etc., and the compatibility problem of existence and material.
Another kind of flame resistant method is the flame-retardant system that adopts response type, and promptly material molecule itself has the group of tool fire retardancy.The fire-retardant group of more introducing so far is a halogen atom.This class material also has the total meeting generation hydrogen halide that is heated of halogenated flame retardant, the big shortcoming of being fuming when burning produces Dioxins, burning, and disabled in Europe at present, developed countries such as the Japanese U.S. also reduce the use of halide-containing gradually.
For requirement on environmental protection, present countries in the world are developed country especially, is seeking not halogen-containing flame-retardant system.Normally adopt physical method, in base material, dose a large amount of phosphorated fire retardants.As JP2000-154234, CN1257075 and CN1147517 disclose the manufacture method of 3 kinds of phosphate flame retardants respectively.Fire retardant and base material are dosed calorifics and the bigger decline of mechanical property that fire retardant must cause material in a large number owing to there is the problem of dispersed and interface compatibility.And phosphorus is incorporated in the phosphate type compound molecule with covalent, can when possessing fire retardancy, not reduce the physical and mechanical properties of material, be the new direction of flame-retarded technology development.
Summary of the invention:
The structural formula of a kind of phosphate type liquid alicyclic olefin compound of the present invention is as follows:
M is 0 to 10 positive integer; R is a hydrogen, C
1-C
5Alkyl (CH
3～-C
5H
11), phenyl, or benzyl; N is the positive integer of 0-5, for example specifically comprises following compound:
Work as R=H, m=0, during n=0, the structural formula of gained compound is
Work as R=H, m=1, during n=0, the structural formula of gained compound is
Work as R=H, m=2, during n=0, the gained structural formula of compound is
Work as R=H, m=1, during n=1, the gained structural formula of compound is
The preparation method of a kind of phosphate type liquid alicyclic olefin compound of the present invention, specifically carry out according to the following step:
1. the alicyclic olefin phosphoric acid ester is synthetic:
Alicyclic olefin alcoholate and three oxyhalogen phosphorus, tertiary amine are according to 3.0: 0.8-1.2: the 3.0-6.0 (ratio preferred 3.0 of alicyclic olefin alcoholate and phosphorus oxychloride: 0.9-1.1; The ratio preferred 3 of alicyclic olefin alcoholate and tertiary amine: 3.1-4.0.) mol ratio-10 ℃-20 ℃ (preferred-5 ℃-5 ℃) three oxyhalogen phosphorus are added drop-wise in the organic solvent of alicyclic olefin alcoholate, tertiary amine, every mole of alicyclic olefin alcoholate of solvent load: 75-250ml/, preferred every mole of alicyclic olefin alcoholate of 100-150ml/.Be warming up to 50～80 ℃ after waiting to dropwise, and, make the phosphoric acid ester of alicyclic olefin alcoholate this thermotonus 0.5～2 hour.Selected solvent can be one or more mixed solvents such as benzene,toluene,xylene, tetrahydrofuran (THF), sherwood oil, methylene dichloride, chloroform, tetracol phenixin, acetone, benzene, ethyl acetate, preferred benzene; Selected three oxyhalogen phosphorus are phosphorus oxychloride, tribromo oxygen phosphorus, from cost consideration, and preferred phosphorus oxychloride; Used tertiary amine is triethylamine, Tri-n-Propylamine, tri-isopropyl amine, triallylamine, pyridine, N, accelerine, N, N-dimethyl benzylamine, N, N-Diethyl Aniline, N, one or more mixture such as N-diethyl benzylamine, preferred triethylamine, N, accelerine.
The structural formula of described alicyclic olefin alcoholate is as follows:
M is 0 to 10 positive integer; R is a hydrogen, C
1-C
5Alkyl (CH
3～-C
5H
11), phenyl, or benzyl; N is the positive integer of 0-5.
2. the purifying of alicyclic olefin phosphoric acid ester
With the carboxylate of top gained,, extremely neutral with deionized water wash again with the sodium hydroxide solution washing to not showing acid, add siccative, siccative is anhydrous sodium sulphate, anhydrous magnesium sulfate, Calcium Chloride Powder Anhydrous, anhydrous calciumsulphate, preferred anhydrous magnesium sulfate.Remove by filter siccative, slough solvent, underpressure distillation or separate with column chromatography can get pure product.
Liquid alicyclic olefin compound of the present invention is through infrared spectra, and elemental analysis method detects, and has confirmed that its structure is the alicyclic olefin compound that contains phosphoric acid ester bond and two keys.See embodiment.
Compound of the present invention can be used as the monomer of cyclopolymerization reaction and the intermediate of synthesis of alicyclic epoxy resin.
Embodiment
Embodiment 1
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 3-cyclohexenol 29.4g (0.30mol), 31.8g (0.315mol) triethylamine, and 32ml benzene, mechanical stirring is bathed with cryosel simultaneously and is cooled to-4 ℃; Drip phosphorus oxychloride, the control rate of addition rises temperature of reaction system and is not higher than 5 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 80 ℃, be incubated 2 hours.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 2% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous magnesium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 3-cyclohexenol phosphoric acid ester.Column chromatography is separated, and gets product 19.3 grams.Yield 57%.
IR(KBr)：1018cm
-1(P-O)；1260(P＝O)；3012cm
-1(H-C＝C-H)；1645cm
-1(H-C＝C-H)
Anal.calcd.For?C，63.91％，H，7.99％.Found：C，63.97％，H，7.93％
Embodiment 2
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 3-cyclopentenol 25.2g (0.30mol), 31.8g (0.315mol) triethylamine, and 32ml benzene, mechanical stirring is bathed with cryosel simultaneously and is cooled to-6 ℃; Drip phosphorus oxychloride, the control rate of addition rises temperature of reaction system and is not higher than 5 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 80 ℃, be incubated 2 hours.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous magnesium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 3-cyclopentenol phosphoric acid ester.Column chromatography is separated, and gets product 16.6 grams.Yield 56%.
IR(KBr)：1021cm
-1(P-O)；1258(P＝O)；3010cm
-1(H-C＝C-H)；1638cm
-1(H-C＝C-H)
Anal.calcd.For?C，60.81％，H，7.09％.Found：C，60.85％，H，7.16％
Embodiment 3
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 2-cyclopentenol 25.2g (0.30mol), 31.8g (0.315mol) triethylamine, and 32m toluene, mechanical stirring is bathed with cryosel simultaneously and is cooled to-5 ℃; Drip phosphorus oxychloride, the control rate of addition rises temperature of reaction system and is not higher than 5 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 70 ℃, be incubated 1.5 hours.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous sodium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 3-cyclopentenol phosphoric acid ester.Column chromatography is separated.Get product 15.9 grams.Yield 54%.
IR(KBr)：1012cm
-1(P-O)；1258(P＝O)；3010cm
-1(H-C＝C-H)；1638cm
-1(H-C＝C-H)
Anal.calcd.For C, 60.81%, H, 7.09%.Found:C, 60.76%, H, 7.15% embodiment 4
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 3-cyclohexenol 29.4g (0.30mol), 31.8g (0.315mol) triethylamine, and 32ml benzene, mechanical stirring is bathed with cryosel simultaneously and is cooled to-4 ℃; Drip phosphorus oxychloride, the control rate of addition rises temperature of reaction system and is not higher than 5 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 65 ℃, be incubated 1 hour.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous sodium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 3-cyclohexenol phosphoric acid ester.Column chromatography is separated.Get product 18.8 grams.Yield 55%.
IR(KBr)：1015cm
-1(P-O)；1254(P＝O)；3014cm
-1(H-C＝C-H)；1641cm
-1(H-C＝C-H)
Anal.calcd.For?C，63.91％，H，7.99％.Found：C，63.82％，H，8.04％
Embodiment 5
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 2,3-cyclohexenyl methyl alcohol 33.6g (0.30mol), 38.1g (0.315mol) N, N-dimethyl benzylamine, 40ml benzene, mechanical stirring are bathed with cryosel simultaneously and are cooled to-7 ℃; Drip phosphorus oxychloride, the control rate of addition rises temperature of reaction system and is not higher than 10 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 60 ℃, be incubated 1 hour.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous sodium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 2,3-cyclohexenyl methyl alcohol phosphoric acid ester.Column chromatography is separated.Get product 19.8 grams.Yield 52%.
IR(KBr)：1014cm
-1(P-O)；1257(P＝O)；3010cm
-1(H-C＝C-H)；1651cm
-1(H-C＝C-H)
Anal.calcd.For?C，66.31％，H，8.68％.Found：C，66.27％，H，8.64％
Embodiment 6
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 3,4-cyclohexenyl methyl alcohol 33.6g (0.30mol), 45.7g (0.315mol) N, N-diethyl benzylamine, 50ml benzene, mechanical stirring are bathed with cryosel simultaneously and are cooled to-6 ℃; Drip phosphorus oxychloride, the control rate of addition rises temperature of reaction system and is not higher than 10 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 60 ℃, be incubated 1 hour.Reduce to room temperature, add deionized water 30ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous sodium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 2,3-cyclohexenyl methyl alcohol phosphoric acid ester.Column chromatography is separated.Get product 19.4 grams.Yield 51%.
IR(KBr)：1021cm
-1(P-O)；1265(P＝O)；3019cm
-1(H-C＝C-H)；1645cm
-1(H-C＝C-H)
Anal.calcd.For?C，66.31％，H，8.68％.Found：C，66.37％，H，8.59％
Embodiment 7
250 milliliters of four-hole boiling flasks are loaded onto thermometer, mechanical stirring, dropping funnel, and nitrogen conduit adds 2-suberene alcohol 33.6g (0.30mol), 31.8g (0.315mol) triethylamine, and 45ml dimethylbenzene, mechanical stirring is bathed with cryosel simultaneously and is cooled to-5 ℃; Drip phosphorus oxychloride, the control rate of addition rises temperature of reaction system and is not higher than 10 ℃; Dropwise, dropping funnel is taken off, change reflux condensing tube, slowly be warming up to 55 ℃, be incubated 1.5 hours.Reduce to room temperature, add deionized water 25ml; Move into separating funnel, leave standstill, divide the phase of anhydrating; Sodium hydroxide solution 25ml washing with 5% 2 times; With the deionized water wash secondary, divide the phase of anhydrating again; With anhydrous sodium sulfate drying; Solvent is sloughed in decompression, gets colourless transparent liquid 2-suberene alcohol phosphoric acid ester.Column chromatography is separated.Get product 17.5 grams.Yield 46%.
IR(KBr)：1025cm
-1(P-O)；1257(P＝O)；3014cm
-1(H-C＝C-H)；1643cm
-1(H-C＝C-H)
Anal.calcd.For?C，66.31％，H，8.68％.Found：C，66.38％，H，8.61％
Claims (9)
1. phosphate type liquid alicyclic olefin compound, its structural formula is as follows:
M is 0 to 10 positive integer; R is a hydrogen, C
1-C
5Alkyl (CH
3～-C
5H
11), phenyl, or benzyl; N is the positive integer of 0-5.
2. according to a kind of phosphate type liquid alicyclic olefin compound of claim 1, it is characterized in that R=H, m=0, n=0.
3. according to a kind of phosphate type liquid alicyclic olefin compound of claim 1, it is characterized in that R=H, m=1, n=0.
4. according to a kind of phosphate type liquid alicyclic olefin compound of claim 1, it is characterized in that R=H, m=2, n=0.
5. according to a kind of phosphate type liquid alicyclic olefin compound of claim 1, it is characterized in that R=H, m=1, n=1.
6. the preparation method of a phosphate type liquid alicyclic olefin compound, carry out according to the following step:
(1) the alicyclic olefin phosphoric acid ester is synthetic:
Alicyclic olefin alcoholate and three oxyhalogen phosphorus, tertiary amine are according to 3.0: the mol ratio of 0.8-1.2: 3.0-6.0 is added drop-wise to three oxyhalogen phosphorus in the organic solution of alicyclic olefin alcoholate, tertiary amine at-10 ℃-20 ℃, every mole of alicyclic olefin alcoholate of solvent load: 75-250ml/; Be warming up to 50～80 ℃ after waiting to dropwise, and, make the phosphoric acid ester of alicyclic olefin alcoholate this thermotonus 0.5～2 hour;
Described solvent is one or more mixed solvents of benzene,toluene,xylene, tetrahydrofuran (THF), sherwood oil, methylene dichloride, chloroform, tetracol phenixin, acetone, benzene, ethyl acetate;
Selected described three oxyhalogen phosphorus are phosphorus oxychloride, tribromo oxygen phosphorus;
Described tertiary amine is triethylamine, Tri-n-Propylamine, tri-isopropyl amine, triallylamine, pyridine, N, accelerine, N, N-dimethyl benzylamine, N, N-Diethyl Aniline, N, the mixture of one or more of N-diethyl benzylamine;
The structural formula of described alicyclic olefin alcoholate is as follows:
M is 0 to 10 positive integer; R is a hydrogen, C
1-C
5Alkyl (CH
3～-C
5H
11), phenyl, or benzyl; N is the positive integer of 0-5;
(2) purifying of alicyclic olefin phosphoric acid ester
With the carboxylate of top gained,, extremely neutral with deionized water wash again with the sodium hydroxide solution washing to not showing acid, add siccative, siccative is anhydrous sodium sulphate, anhydrous magnesium sulfate, Calcium Chloride Powder Anhydrous, anhydrous calciumsulphate; Remove by filter siccative, slough solvent, underpressure distillation or separate with column chromatography can get pure product.
7. according to the preparation method of a kind of phosphate type liquid alicyclic olefin compound of claim 6, it is characterized in that the described alicyclic olefin alcoholate and the ratio of phosphorus oxychloride are 3.0: 0.9-1.1.
8. according to the preparation method of a kind of phosphate type liquid alicyclic olefin compound of claim 6, it is characterized in that the described alicyclic olefin alcoholate and the ratio of tertiary amine are 3: 3.1-4.0.
9. according to the preparation method of a kind of phosphate type liquid alicyclic olefin compound of claim 6, it is characterized in that described solvent is a benzene; Described three oxyhalogen phosphorus are phosphorus oxychloride; Described tertiary amine is triethylamine, N, accelerine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829647A (en) * | 2014-04-10 | 2015-08-12 | 北京理工阻燃科技有限公司 | Phosphorus-containing polyether ester preparation method and application thereof |
| CN106957332A (en) * | 2017-03-30 | 2017-07-18 | 石家庄圣泰化工有限公司 | Triallyl phosphate synthesis method |
-
2002
- 2002-05-14 CN CNB021197431A patent/CN1179965C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829647A (en) * | 2014-04-10 | 2015-08-12 | 北京理工阻燃科技有限公司 | Phosphorus-containing polyether ester preparation method and application thereof |
| CN106957332A (en) * | 2017-03-30 | 2017-07-18 | 石家庄圣泰化工有限公司 | Triallyl phosphate synthesis method |
| CN106957332B (en) * | 2017-03-30 | 2019-04-16 | 石家庄圣泰化工有限公司 | Triallyl phosphate synthesis method |
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|---|---|
| CN1179965C (en) | 2004-12-15 |
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