CN106349288A - Tris(hydroxymethyl)phosphine oxide glycidyl ether and preparation method thereof - Google Patents
Tris(hydroxymethyl)phosphine oxide glycidyl ether and preparation method thereof Download PDFInfo
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- CN106349288A CN106349288A CN201610735549.4A CN201610735549A CN106349288A CN 106349288 A CN106349288 A CN 106349288A CN 201610735549 A CN201610735549 A CN 201610735549A CN 106349288 A CN106349288 A CN 106349288A
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- phosphine oxide
- trihydroxy methyl
- methyl phosphine
- glycidyl ether
- ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
Abstract
The invention provides tris(hydroxymethyl)phosphine oxide glycidyl ether and a preparation method thereof. The preparation method includes the steps of firstly, mixing tris(hydroxymethyl)phosphine oxide, a solvent and a catalyst, heating to reach a ring-opening reaction temperature and adding epoxy chloropropane prior to holding ring-opening reaction; secondly, decreasing the temperature to reach a ring-closure reaction temperature, and adding alkali prior to holding ring-closure reaction; thirdly, separating, washing and distilling so as to obtain the tris(hydroxymethyl)phosphine oxide glycidyl ether. The tris(hydroxymethyl)phosphine oxide glycidyl ether contains 10-15.8 wt% of phosphorus, reaches an initial thermal decomposition temperature above 260 DEG C, can be widely applied to the fields of flame-retardant plastics, flame-retardant coating and flame-retardant textiles as a reactive flame retardant and can be also used as a thermal stabilizer for high polymer materials.
Description
Technical field
The invention belongs to flame retardant area, it is related to a kind of glycerin ester and preparation method thereof, particularly to a kind of three hydroxyls
Methyl oxidation phosphine glycidyl ether and preparation method thereof.
Background technology
With the fast development of macromolecular material, the range of application of fire proofing is also constantly widened, in fire proofing process
In the requirement of other auxiliary agents also improve therewith.Due to the enhancing of people's environmental consciousness, while not affecting material properties,
It is also required to have friendly to environment, so the research and development of new product is increasingly taken seriously.
Epoxy resin is resin matrix for advanced composite materials body commonly used at present, and the epoxy resin after solidification has excellent
Physical and mechanical propertiess, electrical insulation capability, resistance to chemical corrosion, heat-resisting and adhesive property, be therefore widely used in coating, electricity
Son is electric, the multiple fields such as composite, civil construction.Due to its poor flame retardant properties, oxygen index (OI) (loi) is 19.8 about, difficult
To meet the requirement of special engineering technology, limit the application in a lot of key areas for the epoxy resin, thus epoxy resin is entered
Row is flame-retardant modified imperative.Introduce P elements in the epoxy, good thermostability and anti-flammability can be made it have.Work as ring
In oxygen tree fat composition, phosphorus content reaches 0.8-8wt% so that it may have excellent anti-flammability.
Trihydroxy methyl phosphine oxide glycidyl ether due to containing phosphorus-to-carbon bonds in molecule, has that hydrolytic resistance is good and good stability
Advantage, be important polymerized monomer and organic synthesis intermediate, can be used for field of fine chemical it is also possible to make high molecular fire retardant
Agent and heat stabilizer.However, only synthesizing to materials such as trimethylolpropane glycidyl ether, dilute propyl glycidyl ether at present
The report description of method, and there are no report and the description of trihydroxy methyl phosphine oxide glycidyl ether preparation method.By simple
Reaction prepare trihydroxy methyl phosphine oxide glycidyl ether, and be used as the flame retardant activity diluent of epoxy resin, be expected to
The flame-retardant modified middle acquisition applications well of epoxy resin.
Content of the invention
It is an object of the invention to provide a kind of trihydroxy methyl phosphine oxide glycidyl ether and preparation method thereof.
For reaching above-mentioned purpose, the technical solution used in the present invention is:
A kind of trihydroxy methyl phosphine oxide glycidyl ether, the general structure of described trihydroxy methyl phosphine oxide glycidyl ether is such as
Shown in lower:
Wherein, n=0 in said structure formula, 1,2；
During n=0, described trihydroxy methyl phosphine oxide glycidyl ether is trihydroxy methyl phosphine oxide triglycidyl ether；N=1
When, described trihydroxy methyl phosphine oxide glycidyl ether is trihydroxy methyl phosphine oxide diglycidyl ether；During n=2, described three hydroxyl first
Base phosphine oxide glycidyl ether is trihydroxy methyl phosphine oxide one glycidyl ether；
Described trihydroxy methyl phosphine oxide glycidyl ether is trihydroxy methyl phosphine oxide one glycidyl ether, trihydroxy methyl oxidation
One or more of phosphine diglycidyl ether and trihydroxy methyl phosphine oxide triglycidyl ether；
Described trihydroxy methyl phosphine oxide glycidyl ether phosphorus content is 10～15.8wt%, and initial heat decomposition temperature is 260
More than DEG C.
Present invention also offers a kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, solvent and catalyst mixing post-heating to ring-opening reaction temperature, add epoxy chloropropionate
Carry out after alkane being incubated ring-opening reaction；Reaction equation is as follows:
Wherein, n=0 in said structure formula, 1,2；
2) it is cooled to ring-closure reaction temperature, carry out after adding alkali being incubated ring-closure reaction；Reaction equation is as follows:
Wherein, n=0 in said structure formula, 1,2；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separating, wash and distilling.
As preferred technical scheme:
Preparation method as above, described solvent is aromatic hydrocarbons, alkane, halogenated hydrocarbons, acetone, Ketohexamethylene or methyl-isobutyl
Ketone；Described aromatic hydrocarbons is benzene, toluene or dimethylbenzene, and described alkane is hexamethylene or normal hexane, and described halogenated hydrocarbons are dichloroethanes, four
Chlorination carbon or sym-tetrachloroethane.
Preparation method as above, described catalyst is boron trifluoride diethyl etherate, the chloride of boron trifluoride diethyl etherate/stannum is multiple
Close catalyst, lewis acid catalyst or quaternary ammonium salt catalyst；The chloride of described stannum is stannum dichloride and/or butter of tin,
Described lewis acid catalyst is aluminum trichloride (anhydrous), boron trifluoride or bromination antimony, and described quaternary ammonium salt catalyst is tetramethyl chlorine
Change ammonium, tetrabutylammonium chloride, tetrabutyl ammonium bromide or benzyltrimethylammonium chloride.
Preparation method as above, described alkali is sodium hydroxide, potassium hydroxide or organic amine, described alkali be solid base or
Aqueous slkali, the mass percent of described aqueous slkali is 25%～45%；Described organic amine is dimethyl acetylamide or n, n- diformazan
Ethylethanolamine.
Preparation method as above, described trihydroxy methyl phosphine oxide is 1:1～5 with the volume ratio of solvent, described catalysis
The consumption of agent is the 1%～10% of trihydroxy methyl phosphine oxide quality, described trihydroxy methyl phosphine oxide and epoxychloropropane mole
For 1:1.5～3.3, described trihydroxy methyl phosphine oxide is 1:1.5～3.5 with the mol ratio of alkali to ratio.
Preparation method as above, described ring-opening reaction temperature is 50～120 DEG C, the time of described insulation ring-opening reaction
For 1～6h, described ring-closure reaction temperature is 30～70 DEG C, and the time of described insulation ring-closure reaction is 2～8h, the temperature of described distillation
Spend for 130～155 DEG C.
Beneficial effect:
1) preparation method that the present invention provides is simple to operate, and reacting balance is easy to control, and cost is relatively low, and properties of product are steady
Fixed, environmental protection；
2) the trihydroxy methyl phosphine oxide glycidyl ether phosphorus content of present invention preparation is high, and heat stability is good, can extensively apply
In fields such as flame retardant plastics, anti-flaming dope and flame retardant textiles, and the heat stabilizer as macromolecular material.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Fixed scope.
Embodiment 1
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, benzene and boron trifluoride diethyl etherate mixing post-heating to ring-opening reaction temperature 50 C, add
Carry out after epoxychloropropane being incubated ring-opening reaction 1h；Wherein, trihydroxy methyl phosphine oxide and the volume ratio of benzene are 1:1, boron trifluoride
The consumption of ether is the 1% of trihydroxy methyl phosphine oxide quality, and trihydroxy methyl phosphine oxide is 1 with the mol ratio of epoxychloropropane:
1.5；
2) it is cooled to 30 DEG C of ring-closure reaction temperature, carry out after adding solid sodium hydroxide being incubated ring-closure reaction 2h；Wherein, three
Methylol phosphine oxide is 1:1.5 with the mol ratio of solid sodium hydroxide；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 130 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining is trihydroxy methyl phosphine oxide triglycidyl ether,
Structural formula is as follows:
The phosphorus content of trihydroxy methyl phosphine oxide triglycidyl ether is 10wt%, and initial heat decomposition temperature is 260 DEG C.
Embodiment 2
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) boron trifluoride diethyl etherate/stannum dichloride composite catalyzing for 1:0.1 by trihydroxy methyl phosphine oxide, toluene and mol ratio
Agent mixing post-heating, to 55 DEG C of ring-opening reaction temperature, carries out after adding epoxychloropropane being incubated ring-opening reaction 1.5h；Wherein, three hydroxyl
Methyl oxidation phosphine is 1:1.2 with the volume ratio of toluene, and the consumption of boron trifluoride diethyl etherate/stannum dichloride composite catalyst is three hydroxyl first
The 2% of base phosphine oxide quality, trihydroxy methyl phosphine oxide is 1:1.7 with the mol ratio of epoxychloropropane；
2) it is cooled to 30 DEG C of ring-closure reaction temperature, carry out after adding solid potassium hydroxide being incubated ring-closure reaction 2.5h；Wherein,
Trihydroxy methyl phosphine oxide is 1:1.6 with the mol ratio of solid potassium hydroxide；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 132 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining is trihydroxy methyl phosphine oxide diglycidyl ether,
Structural formula is as follows:
The phosphorus content of trihydroxy methyl phosphine oxide diglycidyl ether is 12.3wt%, and initial heat decomposition temperature is 268 DEG C.
Embodiment 3
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) boron trifluoride diethyl etherate/butter of tin that trihydroxy methyl phosphine oxide, dimethylbenzene and mol ratio are 1:0.5 is combined and urges
Agent mixing post-heating, to ring-opening reaction temperature 60 C, carries out after adding epoxychloropropane being incubated ring-opening reaction 2h；Wherein, three hydroxyl
Methyl oxidation phosphine is 1:1.6 with the volume ratio of dimethylbenzene, and the consumption of boron trifluoride diethyl etherate/butter of tin composite catalyst is three hydroxyls
The 3% of methyl oxidation phosphine quality, trihydroxy methyl phosphine oxide is 1:1.9 with the mol ratio of epoxychloropropane；
2) it is cooled to 35 DEG C of ring-closure reaction temperature, carry out after adding the dimethylacetamide solution that mass percent is 28%
Insulation ring-closure reaction 3h；Wherein, trihydroxy methyl phosphine oxide and the mol ratio of dimethyl acetylamide are 1:1.9；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 135 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining is trihydroxy methyl phosphine oxide one glycidyl ether,
Structural formula is as follows:
The phosphorus content of trihydroxy methyl phosphine oxide one glycidyl ether is 15.8wt%, and initial heat decomposition temperature is at 280 DEG C.
Embodiment 4
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, hexamethylene and mol ratio be 1:0.1:0.5 boron trifluoride diethyl etherate/stannum dichloride/
Butter of tin composite catalyst mixing post-heating, to 66 DEG C of ring-opening reaction temperature, carries out being incubated open loop anti-after adding epoxychloropropane
Answer 2.5h；Wherein, trihydroxy methyl phosphine oxide and the volume ratio of hexamethylene are 1:2, boron trifluoride diethyl etherate/stannum dichloride/tetra- chlorination
The consumption of stannum composite catalyst is the 4% of trihydroxy methyl phosphine oxide quality, trihydroxy methyl phosphine oxide and epoxychloropropane mole
Than for 1:2.1；
2) it is cooled to 40 DEG C of ring-closure reaction temperature, carry out after adding solid sodium hydroxide being incubated ring-closure reaction 3.5h；Wherein,
Trihydroxy methyl phosphine oxide is 1:2 with the mol ratio of solid sodium hydroxide；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 137 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining be trihydroxy methyl phosphine oxide triglycidyl ether and
The mixture of trihydroxy methyl phosphine oxide diglycidyl ether, trihydroxy methyl phosphine oxide triglycidyl ether and trihydroxy methyl phosphine oxide
The mol ratio of diglycidyl ether is 1:1, and the phosphorus content of trihydroxy methyl phosphine oxide glycidyl ether is 11.1wt%, initiates heat point
Solution temperature is 264 DEG C.
Embodiment 5
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, normal hexane and aluminum trichloride (anhydrous) mixing post-heating to 72 DEG C of ring-opening reaction temperature,
Carry out after adding epoxychloropropane being incubated ring-opening reaction 3h；Wherein, trihydroxy methyl phosphine oxide and the volume ratio of normal hexane are 1:
2.5, the consumption of aluminum trichloride (anhydrous) is the 5% of trihydroxy methyl phosphine oxide quality, trihydroxy methyl phosphine oxide and epoxychloropropane
Mol ratio is 1:2.3；
2) it is cooled to ring-closure reaction temperature 45 C, carry out after adding solid potassium hydroxide being incubated ring-closure reaction 4h；Wherein, three
Methylol phosphine oxide is 1:2.2 with the mol ratio of solid potassium hydroxide；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 139 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining be trihydroxy methyl phosphine oxide triglycidyl ether and
The mixture of trihydroxy methyl phosphine oxide one glycidyl ether, trihydroxy methyl phosphine oxide triglycidyl ether and trihydroxy methyl phosphine oxide
The mol ratio of one glycidyl ether is 2:1, and the phosphorus content of trihydroxy methyl phosphine oxide glycidyl ether is 11.5wt%, initiates heat point
Solution temperature is 266 DEG C.
Embodiment 6
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, dichloroethanes and boron trifluoride mixing post-heating to 78 DEG C of ring-opening reaction temperature, plus
Carry out after entering epoxychloropropane being incubated ring-opening reaction 3.5h；Wherein, trihydroxy methyl phosphine oxide and the volume ratio of dichloroethanes are 1:
2.8, the consumption of boron trifluoride is the 5% of trihydroxy methyl phosphine oxide quality, trihydroxy methyl phosphine oxide and epoxychloropropane mole
Than for 1:2.5；
2) it is cooled to ring-closure reaction temperature 50 C, add the n that mass percent is 30%, after n- dimethylethanolaminesolution solution
Carry out being incubated ring-closure reaction 4.5h；Wherein, trihydroxy methyl phosphine oxide and n, the mol ratio of n- dimethylethanolamine is 1:2.4；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 142 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining be trihydroxy methyl phosphine oxide one glycidyl ether and
The mixture of trihydroxy methyl phosphine oxide diglycidyl ether, trihydroxy methyl phosphine oxide one glycidyl ether and trihydroxy methyl phosphine oxide
The mol ratio of diglycidyl ether is 1:2, and the phosphorus content of trihydroxy methyl phosphine oxide glycidyl ether is 13.3wt%, initiates heat point
Solution temperature is 272 DEG C.
Embodiment 7
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, carbon tetrachloride and bromination antimony mixing post-heating to 88 DEG C of ring-opening reaction temperature, add
Carry out after epoxychloropropane being incubated ring-opening reaction 4h；Wherein, trihydroxy methyl phosphine oxide and the volume ratio of carbon tetrachloride are 1:3, bromine
The consumption changing antimony is the 6% of trihydroxy methyl phosphine oxide quality, and trihydroxy methyl phosphine oxide is 1 with the mol ratio of epoxychloropropane:
2.7；
2) it is cooled to 55 DEG C of ring-closure reaction temperature, be incubated after adding the sodium hydroxide solution that mass percent is 25%
Ring-closure reaction 5h；Wherein, trihydroxy methyl phosphine oxide and the mol ratio of sodium hydroxide are 1:2.6；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 144 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining be trihydroxy methyl phosphine oxide one glycidyl ether,
Trihydroxy methyl phosphine oxide diglycidyl ether and the mixture of trihydroxy methyl phosphine oxide triglycidyl ether, trihydroxy methyl phosphine oxide
The mol ratio of one glycidyl ether, trihydroxy methyl phosphine oxide diglycidyl ether and trihydroxy methyl phosphine oxide triglycidyl ether is
1:1:1, the phosphorus content of trihydroxy methyl phosphine oxide glycidyl ether is 12.3wt%, and initial heat decomposition temperature is 268 DEG C.
Embodiment 8
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, sym-tetrachloroethane and tetramethyl ammonium chloride mixing post-heating to ring-opening reaction temperature 95
DEG C, carry out after adding epoxychloropropane being incubated ring-opening reaction 4.5h；Wherein, the volume ratio of trihydroxy methyl phosphine oxide and sym-tetrachloroethane
For 1:3.2, the consumption of tetramethyl ammonium chloride is the 7% of trihydroxy methyl phosphine oxide quality, trihydroxy methyl phosphine oxide and epoxy chloropropionate
The mol ratio of alkane is 1:2.9；
2) it is cooled to ring-closure reaction temperature 60 C, be incubated after adding the sodium hydroxide solution that mass percent is 30%
Ring-closure reaction 5.5h；Wherein, trihydroxy methyl phosphine oxide and the mol ratio of sodium hydroxide are 1:2.8；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 146 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining be trihydroxy methyl phosphine oxide one glycidyl ether,
Trihydroxy methyl phosphine oxide diglycidyl ether and the mixture of trihydroxy methyl phosphine oxide triglycidyl ether, trihydroxy methyl phosphine oxide
The mol ratio of one glycidyl ether, trihydroxy methyl phosphine oxide diglycidyl ether and trihydroxy methyl phosphine oxide triglycidyl ether is
1:2:1, the phosphorus content of trihydroxy methyl phosphine oxide glycidyl ether is 11.5wt%, and initial heat decomposition temperature is 266 DEG C.
Embodiment 9
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, acetone and tetrabutylammonium chloride mixing post-heating to 100 DEG C of ring-opening reaction temperature, plus
Carry out after entering epoxychloropropane being incubated ring-opening reaction 5h；Wherein, trihydroxy methyl phosphine oxide and the volume ratio of acetone are 1:3.6, four
The consumption of butyl ammonium chloride is the 8% of trihydroxy methyl phosphine oxide quality, the mol ratio of trihydroxy methyl phosphine oxide and epoxychloropropane
For 1:3；
2) it is cooled to 65 DEG C of ring-closure reaction temperature, be incubated after adding the potassium hydroxide solution that mass percent is 30%
Ring-closure reaction 6h；Wherein, trihydroxy methyl phosphine oxide and the mol ratio of potassium hydroxide are 1:3；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 148 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining be trihydroxy methyl phosphine oxide triglycidyl ether and
The mixture of trihydroxy methyl phosphine oxide one glycidyl ether, trihydroxy methyl phosphine oxide triglycidyl ether and trihydroxy methyl phosphine oxide
The mol ratio of one glycidyl ether is 1:2, and the phosphorus content of trihydroxy methyl phosphine oxide glycidyl ether is 13.3wt%, initiates heat point
Solution temperature is 272 DEG C.
Embodiment 10
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, Ketohexamethylene and tetrabutyl ammonium bromide mixing post-heating to 105 DEG C of ring-opening reaction temperature,
Carry out after adding epoxychloropropane being incubated ring-opening reaction 5h；Wherein, trihydroxy methyl phosphine oxide and the volume ratio of Ketohexamethylene are 1:4,
The consumption of tetrabutyl ammonium bromide is the 9% of trihydroxy methyl phosphine oxide quality, trihydroxy methyl phosphine oxide and epoxychloropropane mole
Than for 1:3.1；
2) it is cooled to ring-closure reaction temperature 70 C, be incubated after adding the potassium hydroxide solution that mass percent is 35%
Ring-closure reaction 7h；Wherein, trihydroxy methyl phosphine oxide and the mol ratio of potassium hydroxide are 1:3.2；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 150 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining be trihydroxy methyl phosphine oxide one glycidyl ether and
The mixture of trihydroxy methyl phosphine oxide diglycidyl ether, trihydroxy methyl phosphine oxide one glycidyl ether and trihydroxy methyl phosphine oxide
The mol ratio of diglycidyl ether is 2:1, and the phosphorus content of trihydroxy methyl phosphine oxide glycidyl ether is 14.4wt%, initiates heat point
Solution temperature is 277 DEG C.
Embodiment 11
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, methyl iso-butyl ketone (MIBK) and benzyltrimethylammonium chloride mixing post-heating to ring-opening reaction
110 DEG C of temperature, carries out after adding epoxychloropropane being incubated ring-opening reaction 5.5h；Wherein, trihydroxy methyl phosphine oxide and methyl tert-butyl
The volume ratio of base ketone is 1:4.8, and the consumption of benzyltrimethylammonium chloride is the 10% of trihydroxy methyl phosphine oxide quality, trihydroxy methyl
Phosphine oxide is 1:4.6 with the mol ratio of epoxychloropropane；
2) it is cooled to ring-closure reaction temperature 70 C, carry out after adding the dimethylacetamide solution that mass percent is 40%
Insulation ring-closure reaction 8h；Wherein, trihydroxy methyl phosphine oxide and the mol ratio of dimethyl acetylamide are 1:3.4；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 152 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining be trihydroxy methyl phosphine oxide one glycidyl ether,
Trihydroxy methyl phosphine oxide diglycidyl ether and the mixture of trihydroxy methyl phosphine oxide triglycidyl ether, trihydroxy methyl phosphine oxide
The mol ratio of one glycidyl ether, trihydroxy methyl phosphine oxide diglycidyl ether and trihydroxy methyl phosphine oxide triglycidyl ether is
2:1:1, the phosphorus content of trihydroxy methyl phosphine oxide glycidyl ether is 13wt%, and initial heat decomposition temperature is 270 DEG C.
Embodiment 12
A kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether, step is as follows:
1) by trihydroxy methyl phosphine oxide, toluene and bromination antimony mixing post-heating to 120 DEG C of ring-opening reaction temperature, add epoxy
Carry out after chloropropane being incubated ring-opening reaction 6h；Wherein, trihydroxy methyl phosphine oxide and the volume ratio of toluene are 1:5, the use of bromination antimony
Measure 10% for trihydroxy methyl phosphine oxide quality, trihydroxy methyl phosphine oxide is 1:3.3 with the mol ratio of epoxychloropropane；
2) it is cooled to ring-closure reaction temperature 70 C, add the n that mass percent is 45%, after n- dimethylethanolaminesolution solution
Carry out being incubated ring-closure reaction 8h；Wherein, trihydroxy methyl phosphine oxide and n, the mol ratio of n- dimethylethanolamine is 1:3.5；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separation, washing and 155 DEG C of distillations.
Test shows, the trihydroxy methyl phosphine oxide glycidyl ether obtaining be trihydroxy methyl phosphine oxide one glycidyl ether,
Trihydroxy methyl phosphine oxide diglycidyl ether and the mixture of trihydroxy methyl phosphine oxide triglycidyl ether, trihydroxy methyl phosphine oxide
The mol ratio of one glycidyl ether, trihydroxy methyl phosphine oxide diglycidyl ether and trihydroxy methyl phosphine oxide triglycidyl ether is
1:1:2, the phosphorus content of trihydroxy methyl phosphine oxide glycidyl ether is 11.7wt%, and initial heat decomposition temperature is 267 DEG C.
Claims (7)
1. a kind of trihydroxy methyl phosphine oxide glycidyl ether, is characterized in that: the knot of described trihydroxy methyl phosphine oxide glycidyl ether
Structure formula is as follows:
Wherein, n=0,1,2；
Described trihydroxy methyl phosphine oxide glycidyl ether is trihydroxy methyl phosphine oxide one glycidyl ether, trihydroxy methyl phosphine oxide two
One or more of glycidyl ether and trihydroxy methyl phosphine oxide triglycidyl ether；
The phosphorus content of described trihydroxy methyl phosphine oxide glycidyl ether is 10～15.8wt%, and initial heat decomposition temperature is at 260 DEG C
More than.
2. a kind of preparation method of trihydroxy methyl phosphine oxide glycidyl ether as claimed in claim 1, is characterized in that, step is such as
Under:
1) by trihydroxy methyl phosphine oxide, solvent and catalyst mixing post-heating to ring-opening reaction temperature, after adding epoxychloropropane
Carry out being incubated ring-opening reaction；
2) it is cooled to ring-closure reaction temperature, carry out after adding alkali being incubated ring-closure reaction；
3) obtain trihydroxy methyl phosphine oxide glycidyl ether after separating, wash and distilling.
3. preparation method according to claim 2 it is characterised in that described solvent be aromatic hydrocarbons, alkane, halogenated hydrocarbons, acetone,
Ketohexamethylene or methyl iso-butyl ketone (MIBK)；Described aromatic hydrocarbons is benzene, toluene or dimethylbenzene, and described alkane is hexamethylene or normal hexane, described
Halogenated hydrocarbons are dichloroethanes, carbon tetrachloride or sym-tetrachloroethane.
4. preparation method according to claim 2 is it is characterised in that described catalyst is boron trifluoride diethyl etherate, borontrifluoride
The chloride composite catalyst of borate ether/stannum, lewis acid catalyst or quaternary ammonium salt catalyst；The chloride of described stannum is dichloro
Change stannum and/or butter of tin, described lewis acid catalyst is aluminum trichloride (anhydrous), boron trifluoride or bromination antimony, described quaternary ammonium
Salt catalyst is tetramethyl ammonium chloride, tetrabutylammonium chloride, tetrabutyl ammonium bromide or benzyltrimethylammonium chloride.
5. preparation method according to claim 2 is it is characterised in that described alkali is sodium hydroxide, potassium hydroxide or organic
Amine, described alkali is solid base or aqueous slkali, and the mass percent of described aqueous slkali is 25%～45%；Described organic amine is diformazan
Yl acetamide or n, n- dimethylethanolamine.
6. preparation method according to claim 2 is it is characterised in that the volume ratio of described trihydroxy methyl phosphine oxide and solvent
For 1:1～5, the consumption of described catalyst is the 1%～10% of trihydroxy methyl phosphine oxide quality, described trihydroxy methyl phosphine oxide with
The mol ratio of epoxychloropropane is 1:1.5～3.3, and described trihydroxy methyl phosphine oxide is 1:1.5～3.5 with the mol ratio of alkali.
7. preparation method according to claim 2 is it is characterised in that described ring-opening reaction temperature is 50～120 DEG C, described
Insulation ring-opening reaction time be 1～6h, described ring-closure reaction temperature be 30～70 DEG C, described insulation ring-closure reaction time be
2～8h, the temperature of described distillation is 130～155 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110527140A (en) * | 2019-08-30 | 2019-12-03 | 苏州科技大学 | A kind of phosphorus fire retardant and preparation method thereof containing epoxy group |
| CN112876737A (en) * | 2020-09-21 | 2021-06-01 | 武汉宜田科技发展有限公司 | Low-chlorine hydrolysis-resistant phosphorus-containing polyfunctional group reaction type flame retardant and preparation method thereof |
| WO2022238196A1 (en) * | 2021-05-11 | 2022-11-17 | Clariant International Ltd | Alkoxylates of methylol-organyl-phosphine oxides, process for manufacture thereof, flame-retardant polymers and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1045212A1 (en) * | 1982-05-25 | 1983-09-30 | Казанский Научно-Исследовательский Технологический И Проектный Институт Химико-Фотографической Промышленности | Composition of polymer receiving layer of color diffusion photo set positive material |
| EP0675131A1 (en) * | 1994-03-24 | 1995-10-04 | Shell Internationale Researchmaatschappij B.V. | Fire retardant epoxy resin composition |
| CN103113620A (en) * | 2013-02-05 | 2013-05-22 | 东华大学 | Phosphine-oxide flame retardant and preparation method thereof |
-
2016
- 2016-08-26 CN CN201610735549.4A patent/CN106349288A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1045212A1 (en) * | 1982-05-25 | 1983-09-30 | Казанский Научно-Исследовательский Технологический И Проектный Институт Химико-Фотографической Промышленности | Composition of polymer receiving layer of color diffusion photo set positive material |
| EP0675131A1 (en) * | 1994-03-24 | 1995-10-04 | Shell Internationale Researchmaatschappij B.V. | Fire retardant epoxy resin composition |
| CN103113620A (en) * | 2013-02-05 | 2013-05-22 | 东华大学 | Phosphine-oxide flame retardant and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 《化工百科全书》编辑委员会: "《树脂与塑料》", 31 January 2003, 化学工业出版社 * |
| 郝晓斌等: "三羟甲基氧化膦中水分的测定", 《山东化工》 * |
| 陈声锐: "三羟甲基丙烷缩水甘油醚", 《第六次全国环氧树脂应用技术学术交流会论文集》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110527140A (en) * | 2019-08-30 | 2019-12-03 | 苏州科技大学 | A kind of phosphorus fire retardant and preparation method thereof containing epoxy group |
| CN112876737A (en) * | 2020-09-21 | 2021-06-01 | 武汉宜田科技发展有限公司 | Low-chlorine hydrolysis-resistant phosphorus-containing polyfunctional group reaction type flame retardant and preparation method thereof |
| WO2022238196A1 (en) * | 2021-05-11 | 2022-11-17 | Clariant International Ltd | Alkoxylates of methylol-organyl-phosphine oxides, process for manufacture thereof, flame-retardant polymers and use thereof |
| CN117242111A (en) * | 2021-05-11 | 2023-12-15 | 科莱恩国际有限公司 | Hydroxymethyl-organo-phosphine oxide alkoxylates, process for their production, flame-retardant polymers and their use |
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