CN109485677A - Organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds and preparation method thereof - Google Patents
Organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds and preparation method thereof Download PDFInfo
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- CN109485677A CN109485677A CN201811297656.9A CN201811297656A CN109485677A CN 109485677 A CN109485677 A CN 109485677A CN 201811297656 A CN201811297656 A CN 201811297656A CN 109485677 A CN109485677 A CN 109485677A
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- alcohol ester
- phosphonic acid
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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
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
Abstract
The present invention relates to a kind of organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds and preparation method thereof, which is shown below:
Description
Technical field
The present invention relates to a kind of organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds and preparation method thereof, tools
Body is related to a kind of organic silicon-phosphorus fire retardant diphenyl phosphonic acid, and { 1- methyl-1-sila-2,6,7- trioxa-l-phosphabicyclo [2,2,2] are pungent
Alkyl-(4)-methylene } ester compounds and preparation method thereof, which is suitable as polyester, polyamide, polyurethane, epoxy
The fire retardant of the materials such as resin, unsaturated-resin, polyolefin.
Background technique
With advances in technology, quick raising, the reinforcing of environmental consciousness of people's living standard applies court to fire retardant
Non-halogen direction conversion, pursued in research and application it is fire-retardant it is dynamical more emphasize its nontoxic and environmental-protecting performance simultaneously,
Wherein organosilicon and organophosphorous fire retardant are all market suddenly non-halogen substitutes leaved for development；From herbicide interactions conceptual design,
Siliceous and phosphorous compound in same molecule, i.e. silicon phosphorus dual element synergistic fire retardant, silicon phosphorus synergistic is excellent with that can play when burning
Different flame retardant effect has critically important research and development meaning.
The invention discloses a kind of organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds and preparation method thereof.
The present invention is using pentaerythritol methylsilicate and diphenyl phosphinyl chloride as raw material, and one-step method prepares the compound, technique letter
Single, equipment investment is few, easy to operate, at low cost, is easily converted into industrialized production；Fire retardant of the present invention, with siliceous, phosphorus is dual
Ignition-proof element, flame-retarded efficiency be high, the good, symmetrical configuration and material compatibility is good, does not generate toxic gas in combustion process at charcoal
The advantages that.Therefore, fire retardant of the present invention has extraordinary application and development prospect.
Summary of the invention
It is an object of the present invention to proposing a kind of organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds,
Silicon, two kinds of ignition-proof elements of phosphorus, symmetrical configuration, polarity are moderate and material compatibility is good, in combustion process with containing for the compound
Not the advantages that not generating toxic gas；It is adapted for use as polyester, polyamide, polyurethane, epoxy resin, unsaturated-resin, polyolefin
The fire retardant of equal materials, can overcome deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions:
A kind of organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds, which is characterized in that the knot of the compound
Structure is shown below:
Another object of the present invention is to propose a kind of organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds
Preparation method, simple process is easy to large-scale production, and raw material is cheap and easy to get, and equipment investment is few, low in cost.
This method are as follows:
Blender, thermometer, reflux condenser are being housed and are being connected in dry and hydrogen chloride absorption device reactor, is being added
Enter organic solvent, pentaerythritol methylsilicate, be warming up to 35 DEG C, under nitrogen protection, starts that diphenyl phosphinyl chloride is added dropwise,
The molar ratio of diphenyl phosphinyl chloride and pentaerythritol methylsilicate is controlled 1: 1-1: 1.25, after dripping off, is warming up to 90-
130 DEG C, insulation reaction 4-8h is adjusted to pH=6.5-8 with acid binding agent, is cooled to 25 DEG C, filters, filter cake product theory quality gram
The cold water of 2 times of volumes ml of number washs, and drying obtains white solid diphenyl phosphonic acid silicon cage alcohol ester.
Organic solvent as described above is ethylene glycol diethyl ether, tetrachloroethanes, diethylene glycol dimethyl ether or methyl phenyl ethers anisole, is used
Amount volume ml is 4-6 times of pentaerythritol methylsilicate quality number.
Acid binding agent as described above is triethylamine, pyridine or n,N-Dimethylaniline.
Pentaerythritol methylsilicate as described above is 1- methyl-1-sila-2,6, and 7- trioxa-4- methylol is bicyclic
[2,2,2] octyl, structure are shown below:
Organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds of the present invention are white solid, decomposition temperature: 365
± 5 DEG C, density (25 DEG C): 1.462g/cm3, product yield is 84.6~93.0%, is suitable as polyester, polyamide, poly- ammonia
The fire retardant of the materials such as ester, epoxy resin, unsaturated-resin, polyolefin.Its organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage
The preparation principle of alcohol ester compounds is as follows:
Compared with prior art, the beneficial effects of the present invention are:
1. organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds of the present invention are siliceous, the dual ignition-proof element of phosphorus,
Flame-retarded efficiency is high, and cage ring structural symmetry is good, and phenyl ring has multidirectionalization of electronic structure, and product structure is stablized, decomposition temperature
Height, it is good with material compatibility, there is preferable processing performance.
2. organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds of the present invention, acid source, charcoal source are abundant, at charcoal
It is good, belong to the friendly fire-retardant carbon forming agent of efficient context, has preferably into the anti-melting drip effect of charcoal.
3. the preparation method that the present invention has organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds is that a step is anti-
It answers, simple process, equipment investment is few, and it is easy to operate, it is at low cost, it is easy to scale conversion and production.
Detailed description of the invention
Following attached drawing is provided in order to further illustrate the structure and performance spy of product.
Fig. 1 is the infrared spectrogram of diphenyl phosphonic acid silicon cage alcohol ester；Fig. 1 shows 3082cm-1It is c h bond on phenyl ring
Stretching vibration peak；2990cm-1And 2921cm-1It is the stretching vibration peak of c h bond；1430cm-1It is the flexural vibrations peak of c h bond；
1241cm-1It is the stretching vibration peak of P=O key；1000cm-1It is the stretching vibration peak of Si-O-C key；948cm-1It is Si-O-C key
Flexural vibrations peak；875cm-1It is the stretching vibration peak of P-O-C key；750cm-1It is the stretching vibration peak of Si-C key.
Fig. 2 is diphenyl phosphonic acid silicon cage alcohol ester nuclear magnetic spectrogram；Fig. 2 shows using deuterated DMSO as solvent, δ 0.08-
0.12 is CH3Methyl hydrogen peak on-Si；δ 1.08-1.25 is C-CH2Methylene hydrogen peak on O-P；δ 3.3-3.5 is Si-OCH2C
On methylene hydrogen peak；It is the hydrogen peak on phenyl ring at δ 7.0-7.1；δ 2.5 is the H in DMSO solvent2Hydrogen peak in O.
Fig. 3 is diphenyl phosphonic acid silicon cage alcohol ester differential thermal spectrogram；Fig. 3 shows to start to lose when temperature rises to 365 DEG C or so
Weight；When being heated to 410 DEG C, the weight-loss ratio of product reaches 50%；After final temperature reaches 800 DEG C, still there is 18%
Residue illustrates that the product of the synthesis has good thermal stability.
Specific embodiment
Below in conjunction with specific embodiment, technical scheme is described further.
Embodiment 1 is being equipped with blender, thermometer, reflux condensing tube and is being connected to drying tube and hydrogen chloride absorption suitable for reading
In the 250ml three-necked flask of device, 0.10mol (17.60g) pentaerythritol methylsilicate and 90ml ethylene glycol diethyl is added
Ether.Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (22.05g) diphenyl phosphinyl chloride is added dropwise, after dripping off, reflux
90 DEG C, insulation reaction 8h are gradually heated to, is adjusted to pH=6.5-8 with triethylamine acid binding agent, is cooled to 25 DEG C, 50ml is used in filtering
Cold water washing, drying obtain white solid diphenyl phosphonic acid silicon cage alcohol ester, decomposition temperature: 365 ± 5 DEG C, density (25 DEG C):
1.462g/cm3；Yield is 84.6%.
Embodiment 2 is being equipped with blender, thermometer, reflux condensing tube and is being connected to drying tube and hydrogen chloride absorption suitable for reading
In the 250ml three-necked flask of device, 0.105mol (18.48g) pentaerythritol methylsilicate and 110ml tetrachloroethanes is added,
Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (22.05g) diphenyl phosphinyl chloride is added dropwise, after dripping off, reflux is gradually
100 DEG C, insulation reaction 8h are warming up to, is adjusted to pH=6.5-8 with pyridine acid binding agent, is cooled to 25 DEG C, filtering is washed with 50ml cold water
It washs, dries, obtain white solid diphenyl phosphonic acid silicon cage alcohol ester, decomposition temperature: 365 ± 5 DEG C, density (25 DEG C): 1.462g/
cm3；Yield is 89.0%.
Embodiment 3 is being equipped with blender, thermometer, reflux condensing tube and is being connected to drying tube and hydrogen chloride absorption suitable for reading
In the 250ml three-necked flask of device, 0.11mol (19.36g) pentaerythritol methylsilicate and 90ml diethylene glycol diformazan is added
Ether.Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (22.05g) diphenyl phosphinyl chloride is added dropwise, after dripping off, reflux
110 DEG C, insulation reaction 9h are gradually heated to, is adjusted to pH=6.5-8 with triethylamine acid binding agent, is cooled to 25 DEG C, 50ml is used in filtering
Cold water washing, drying obtain white solid diphenyl phosphonic acid silicon cage alcohol ester, decomposition temperature: 365 ± 5 DEG C, density (25 DEG C):
1.462g/cm3；Yield is 92.1%.
Embodiment 4 is being equipped with blender, thermometer, reflux condensing tube and is being connected to drying tube and hydrogen chloride absorption suitable for reading
In the 250ml three-necked flask of device, 0.115mol (20.42g) pentaerythritol methylsilicate and 90ml methyl phenyl ethers anisole is added.In nitrogen
Under gas shielded, 35 DEG C are warming up to, starts that 0.05mol (22.05g) diphenyl phosphinyl chloride is added dropwise, after dripping off, is warming up to 130 DEG C,
Insulation reaction 12h is adjusted to pH=6.5-8 with triethylamine acid binding agent, is cooled to 25 DEG C, and filtering is washed with 50ml cold water, dries,
White solid diphenyl phosphonic acid silicon cage alcohol ester is obtained, decomposition temperature: 365 ± 5 DEG C, density (25 DEG C): 1.462g/cm3；Yield
It is 95.5%.
Embodiment 5 is being equipped with blender, thermometer, reflux condensing tube and is being connected to drying tube and hydrogen chloride absorption suitable for reading
In the 250ml three-necked flask of device, 0.12mol (21.12g) pentaerythritol methylsilicate and 90ml tetrachloroethanes is added.?
Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (22.05g) diphenyl phosphinyl chloride is added dropwise, after dripping off, reflux is gradually risen
Temperature is adjusted to pH=6.5-8 to 120 DEG C, insulation reaction 7h, with pyridine acid binding agent, is cooled to 25 DEG C, and filtering is washed with 50ml cold water
It washs, dries, obtain white solid diphenyl phosphonic acid silicon cage alcohol ester, decomposition temperature: 365 ± 5 DEG C, density (25 DEG C): 1.462g/
cm3；Yield is 93.0%.
Embodiment 6 is being equipped with blender, thermometer, reflux condensing tube and is being connected to drying tube and hydrogen chloride absorption suitable for reading
In the 250ml three-necked flask of device, 0.11mol (19.36g) pentaerythritol methylsilicate and 110ml diethylene glycol two is added
Methyl ether.Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (22.05g) diphenyl phosphinyl chloride is added dropwise, after dripping off, is returned
Stream is gradually heated to 120 DEG C, insulation reaction 9h, is adjusted to pH=6.5-8 with triethylamine acid binding agent, is cooled to 25 DEG C, filters, and uses
The washing of 50ml cold water, drying obtain white solid diphenyl phosphonic acid silicon cage alcohol ester, decomposition temperature: 365 ± 5 DEG C, density (25
DEG C): 1.462g/cm3；Yield is 92.6%.
1 preparation example main technologic parameters of table
The product tricresyl phosphate silicon cage alcohol ester of above-mentioned preparation is also applied in poly- polypropylene (PP) by inventor, with difference
Ratio be uniformly mixed, squeezed out at 200 DEG C by XJ-01 type single screw extrusion machine, be made long 15cm, the batten of diameter 3mm,
And the test of fire-retardant and dropping performance and the experiment of UL-94 vertical combustion, experiment knot are carried out to the modified PP batten squeezed out
Fruit is shown in Table 2:
Flame test result of the 2 diphenyl phosphonic acid silicon cage alcohol ester of table in PP
It is modified by upper table 2 it is found that when additive amount of the diphenyl phosphonic acid silicon cage alcohol ester of the present invention in PP is 15%
PP batten limit oxygen index is up to 27%, V-0 grades；When the additive amount of fire retardant reaches 25%, limit oxygen index can be up to
31% or more, can also obviously observe will not occur to melt drip phenomenon in the PP batten combustion process after being modified, and at
Charcoal speed is fast, it is possible to it is fire-retardant at charcoal effect well to find out that tricresyl phosphate silicon cage alcohol ester of the present invention has PP.
Claims (4)
1. a kind of organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds, which is characterized in that the structure of the compound
It is as follows:
2. a kind of preparation of organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds compound as described in claim 1
Method, which is characterized in that this method are as follows:
Blender, thermometer, reflux condenser are being housed and are being connected in dry and hydrogen chloride absorption device reactor, addition has
Solvent, pentaerythritol methylsilicate are warming up to 35 DEG C, under nitrogen protection, start that diphenyl phosphinyl chloride, control is added dropwise
The molar ratio of diphenyl phosphinyl chloride and pentaerythritol methylsilicate after dripping off, is warming up to 90-130 DEG C 1: 1-1: 1.25,
Insulation reaction 4-8h is adjusted to pH=6.5-8 with acid binding agent, is cooled to 25 DEG C, filtering, filter cake is with 2 times of product theory quality grams
The cold water of volume ml washs, and drying obtains white solid diphenyl phosphonic acid silicon cage alcohol ester；
Pentaerythritol methylsilicate as described above is 1- methyl-1-sila-2,6,7- trioxa-4- methylol it is bicyclic [2,
2,2] octyl, structure are shown below:
3. a kind of preparation method of two silicon cage alcohol ester compounds of organic silicon-phosphorus fire retardant phenyl-phosphonic acid as claimed in claim 2,
It is characterized in that:
The organic solvent is ethylene glycol diethyl ether, tetrachloroethanes, diethylene glycol dimethyl ether or methyl phenyl ethers anisole, dosage volume milli
Rise 4-6 times that number is pentaerythritol methylsilicate quality number.
4. a kind of preparation method of two silicon cage alcohol ester compounds of organic silicon-phosphorus fire retardant phenyl-phosphonic acid as claimed in claim 2,
It is characterized in that:
The acid binding agent is triethylamine, pyridine or n,N-Dimethylaniline.
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| CN201811297656.9A CN109485677A (en) | 2018-10-23 | 2018-10-23 | Organic silicon-phosphorus fire retardant diphenyl phosphonic acid silicon cage alcohol ester compounds and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231312A (en) * | 2014-09-26 | 2014-12-24 | 苏州科技学院相城研究院 | Triazine triphenyl phosphinic acid ethyl ester flame retardant composition and application method thereof |
| CN105713042A (en) * | 2016-01-19 | 2016-06-29 | 苏州科技学院 | Preparation method of bis(PEPA) phenylphosphonate compound |
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2018
- 2018-10-23 CN CN201811297656.9A patent/CN109485677A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231312A (en) * | 2014-09-26 | 2014-12-24 | 苏州科技学院相城研究院 | Triazine triphenyl phosphinic acid ethyl ester flame retardant composition and application method thereof |
| CN105713042A (en) * | 2016-01-19 | 2016-06-29 | 苏州科技学院 | Preparation method of bis(PEPA) phenylphosphonate compound |
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