CN109400652A - Organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds and preparation method thereof - Google Patents
Organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds and preparation method thereof Download PDFInfo
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- CN109400652A CN109400652A CN201811298988.9A CN201811298988A CN109400652A CN 109400652 A CN109400652 A CN 109400652A CN 201811298988 A CN201811298988 A CN 201811298988A CN 109400652 A CN109400652 A CN 109400652A
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- alcohol ester
- tricresyl phosphate
- silicon
- fire retardant
- phosphorus
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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
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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
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The present invention relates to a kind of organic silicon-phosphorus fire retardant tricresyl phosphate 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 tricresyl phosphate silicon cage alcohol ester compounds and preparation method thereof, and in particular to
A kind of organic silicon-phosphorus fire retardant tricresyl phosphate { 1- methyl-1-sila-2,6,7- trioxa-l-phosphabicyclo [2,2,2] octyl-(4)-methylene
Base } ester compounds and preparation method thereof, which is suitable as polyester, polyamide, polyurethane, epoxy resin, unsaturated tree
The fire retardant of the materials such as rouge, polyolefin.
Background technique
With the development of science and technology continuous improvement of people's living standards, the constantly enhancing of the safe and environment-friendly consciousness of entire society,
The mankind have higher requirement to fire retardant, while requiring flame-retarded efficiency, more focus on its nontoxic and environmental-protecting performance, i.e., fire-retardant
Agent just develops towards non-halogen direction, and wherein organosilicon and organophosphorous fire retardant are all market suddenly non-halogen products leaved for development；
The compound siliceous and phosphorous in same molecule from herbicide interactions angle design, i.e. silicon, phosphorus dual element fire retardant, when burning
Silicon, phosphorus, which mutually cooperate with, can play excellent flame effect, there is critically important research and development meaning.
The invention discloses a kind of organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds and preparation method thereof.The present invention
It is using pentaerythritol methylsilicate and phosphorus oxychloride as raw material, one-step method prepares the compound, simple process, equipment investment
It is few, it is easy to operate, it is at low cost, easily it is converted into industrialized production；Fire retardant of the present invention has siliceous, the dual ignition-proof element of phosphorus, resistance
Fuel efficiency can it is high, at charcoal good, symmetrical configuration and material compatibility is good, the advantages that not generating toxic gas in combustion process.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 propose a kind of organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds, the chemical combination
Object has containing silicon, two kinds of ignition-proof elements of phosphorus, symmetrical configuration, polarity are moderate, with material compatibility is good, does not generate in combustion process
The advantages that toxic gas；It is adapted for use as the materials such as polyester, polyamide, polyurethane, epoxy resin, unsaturated-resin, polyolefin
Fire retardant, deficiency in the prior art can be overcome.
For achieving the above object, present invention employs following technical solutions:
A kind of organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds, which is characterized in that the structure of the compound is as follows
Shown in formula:
Another object of the present invention is to propose a kind of preparation of organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds
Method, simple process are 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 phosphorus oxychloride, control three is added dropwise
The molar ratio of chlorethoxyfos and pentaerythritol methylsilicate is 1: 3-1: 3.4, 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 2 times of volume milliliters of product theory quality grams
Several cold water washings, drying obtain white solid tricresyl phosphate 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 3-5 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 tricresyl phosphate silicon cage alcohol ester compounds of the present invention be white solid, decomposition temperature: 360 ± 5 DEG C,
Density (25 DEG C): 1.426g/cm3, product yield is 87.8~96.1%, is suitable as polyester, polyamide, polyurethane, ring
The fire retardant of the materials such as oxygen resin, unsaturated-resin, polyolefin.Its organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds
Preparation principle is as follows:
Compared with prior art, the beneficial effects of the present invention are:
1. organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds of the present invention are siliceous, the dual ignition-proof element of phosphorus, fire-retardant effect
Can be high, cage ring structural symmetry is good, and product is stablized, and decomposition temperature is high, there is preferable processing performance.
2. organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds of the present invention, good at charcoal, belong to efficient context close friend resistance
Carbon forming agent is fired, is had preferably into the anti-melting drip effect of charcoal.
3. the preparation method that the present invention has organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds is single step reaction, technique
Simply, equipment investment is few, easy to operate, at low cost, 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 tricresyl phosphate silicon cage alcohol ester；Fig. 1 shows 1406.4 and 1276.8cm-1Place is that C-Si key is stretched
Contracting vibration peak, 669.8cm-1Place is the flexural vibrations peak of C-Si key；1016cm-1Place is the stretching vibration peak of Si-O- (C) key,
2951cm-1And 2888cm-1It is the stretching vibration peak of c h bond；1464cm-1And 1393cm-1It is the flexural vibrations peak of c h bond；
1267cm-1It is the stretching vibration peak of P=O key；1186cm-1It is the stretching vibration peak of P-O key；1153cm-1It is stretching for-Si-O- key
Contracting vibration peak；1086cm-1And 1043cm-1It is the stretching vibration doublet of C-O key.
Fig. 2 is tricresyl phosphate silicon cage alcohol ester nuclear magnetic spectrogram；Fig. 2 shows that using deuterated DMSO as solvent, δ 0.08 is CH3-Si
On methyl hydrogen peak；δ 1.9-2.1 is C-CH2Methylene hydrogen peak on O-P；δ 3.3-3.5 is Si-OCH2Methylene hydrogen on C
Peak；δ 2.5 is the H in DMSO solvent2Hydrogen peak in O.
Fig. 3 tricresyl phosphate silicon cage alcohol ester differential thermal spectrogram；Fig. 3 shows to start weightlessness when temperature rises to 360 DEG C or so；When adding
When heat is to 380 DEG C, the weight-loss ratio of product reaches 50%；Still have after final temperature reaches 800 DEG C, in crucible 26% it is residual
Excess 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, 0.15mol (26.40g) pentaerythritol methylsilicate and 130ml ethylene glycol diethyl is added
Ether.Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (7.68g) phosphorus oxychloride is added dropwise, after dripping off, reflux is gradually warmed up
To 90 DEG C, insulation reaction 8h, it is adjusted to pH=6.5-8 with triethylamine acid binding agent, is cooled to 25 DEG C, filtering is washed with 60ml cold water,
Drying, obtains white solid tricresyl phosphate silicon cage alcohol ester, decomposition temperature: 360 ± 5 DEG C, density (25 DEG C): 1.426g/cm3；Yield
It is 87.8%.
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, 0.155mol (27.28g) pentaerythritol methylsilicate and 100ml tetrachloroethanes is added,
Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (7.68g) phosphorus oxychloride is added dropwise, after dripping off, reflux is gradually heated to
100 DEG C, insulation reaction 5h, it is adjusted to pH=6.5-8 with pyridine acid binding agent, is cooled to 25 DEG C, filtering is washed with 60ml cold water, is dried
It is dry, three silicon cage alcohol ester of white solid phosphoric acid is obtained, decomposition temperature: 360 ± 5 DEG C, density (25 DEG C): 1.426g/cm3；Yield
It is 92.4%.
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, 0.16mol (28.40g) pentaerythritol methylsilicate and 100ml diethylene glycol two is added
Methyl ether.Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (7.68g) phosphorus oxychloride is added dropwise, after dripping off, reflux is gradually risen
Temperature is adjusted to pH=6.5-8 to 110 DEG C, insulation reaction 6h, with triethylamine acid binding agent, is cooled to 25 DEG C, and filtering is washed with 60ml cold water
It washs, dries, obtain white solid tricresyl phosphate silicon cage alcohol ester, decomposition temperature: 360 ± 5 DEG C, density (25 DEG C): 1.426g/cm3；It produces
Rate is 95.2%.
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, 0.165mol (29.04g) pentaerythritol methylsilicate and 110ml methyl phenyl ethers anisole is added.?
Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (7.68g) phosphorus oxychloride is added dropwise, after dripping off, is warming up to 130 DEG C, heat preservation
7h is reacted, is adjusted to pH=6.5-8 with triethylamine acid binding agent, is cooled to 25 DEG C, filtering is washed with 60ml cold water, is dried, is obtained white
Three silicon cage alcohol ester of solid phosphoric acid, decomposition temperature: 360 ± 5 DEG C, density (25 DEG C): 1.426g/cm3；Yield is 95.8%.
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, 0.17mol (29.92g) pentaerythritol methylsilicate and 90ml tetrachloroethanes is added.?
Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (7.68g) phosphorus oxychloride is added dropwise, after dripping off, reflux is gradually heated to 120
DEG C, insulation reaction 4h is adjusted to pH=6.5-8 with pyridine acid binding agent, is cooled to 25 DEG C, and filtering is washed with 60ml cold water, it dries,
White solid tricresyl phosphate silicon cage alcohol ester is obtained, decomposition temperature: 360 ± 5 DEG C, density (25 DEG C): 1.426g/cm3；Yield is
96.1%.
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, 0.16mol (28.40g) pentaerythritol methylsilicate and 120ml diethylene glycol two is added
Methyl ether.Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (7.68g) phosphorus oxychloride is added dropwise, after dripping off, reflux is gradually risen
Temperature is adjusted to pH=6.5-8 to 120 DEG C, insulation reaction 6h, with triethylamine acid binding agent, is cooled to 25 DEG C, and filtering is washed with 60ml cold water
It washs, dries, obtain white solid tricresyl phosphate silicon cage alcohol ester, decomposition temperature: 360 ± 5 DEG C, density (25 DEG C): 1.426g/cm3；It produces
Rate is 95.7%.
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 tricresyl phosphate silicon cage alcohol ester of table in PP
By upper table 2 it is found that when additive amount of the tricresyl phosphate silicon cage alcohol ester of the present invention in PP is 20%, modified PP batten
Limit oxygen index is much larger than 27%, i.e. substrate already belongs to nonflammable material rank up to 29%, V-0 grades；When the addition of fire retardant
When amount reaches 25%, limit oxygen index can be up to 32% or more, can also obviously observe the PP batten burning after being modified
It will not occur to melt drip phenomenon in the process, and fast at charcoal speed, it is possible to find out tricresyl phosphate silicon cage alcohol ester of the present invention to PP
Have fire-retardant at charcoal effect well.
Claims (4)
1. a kind of organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds, which is characterized in that the following institute of the structure of the compound
Show:
2. a kind of preparation method of organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds as described in claim 1, feature
It is, 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 phosphorus oxychloride is added dropwise, control trichlorine oxygen
The molar ratio of phosphorus and pentaerythritol methylsilicate is 1: 3-1: 3.4, after dripping off, is warming up to 90-130 DEG C, insulation reaction 4-8h,
It is adjusted to pH=6.5-8 with acid binding agent, is cooled to 25 DEG C, is filtered, filter cake is cold with 2 times of volumes ml of product theory quality grams
Water washing, drying, obtains white solid tricresyl phosphate 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 organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds as claimed in claim 2, feature
It is:
The organic solvent is ethylene glycol diethyl ether, tetrachloroethanes, diethylene glycol dimethyl ether or methyl phenyl ethers anisole, dosage volume milli
Rise 3-5 times that number is pentaerythritol methylsilicate quality number.
4. a kind of preparation method of organic silicon-phosphorus fire retardant tricresyl phosphate silicon cage alcohol ester compounds as claimed in claim 2, feature
It is:
The acid binding agent is triethylamine, pyridine or n,N-Dimethylaniline.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978351A (en) * | 2020-08-06 | 2020-11-24 | 苏州科技大学 | Fire retardant cage-shaped organic silicon phosphoramide compound and preparation method thereof |
| CN117343276A (en) * | 2023-12-04 | 2024-01-05 | 烟台万华聚氨酯合成材料有限公司 | Preparation method of flame-retardant double-component polyurethane pouring sealant |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195642A (en) * | 2007-12-26 | 2008-06-11 | 北京理工大学 | Method for synthesizing fire resistant clathrate multi-ring phosphoric acid ester for engineering plastic |
| 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 |
-
2018
- 2018-10-23 CN CN201811298988.9A patent/CN109400652A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195642A (en) * | 2007-12-26 | 2008-06-11 | 北京理工大学 | Method for synthesizing fire resistant clathrate multi-ring phosphoric acid ester for engineering plastic |
| 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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111978351A (en) * | 2020-08-06 | 2020-11-24 | 苏州科技大学 | Fire retardant cage-shaped organic silicon phosphoramide compound and preparation method thereof |
| CN111978351B (en) * | 2020-08-06 | 2022-04-26 | 苏州科技大学 | Fire retardant cage-shaped organic silicon phosphoramide compound and preparation method thereof |
| CN117343276A (en) * | 2023-12-04 | 2024-01-05 | 烟台万华聚氨酯合成材料有限公司 | Preparation method of flame-retardant double-component polyurethane pouring sealant |
| CN117343276B (en) * | 2023-12-04 | 2024-02-06 | 烟台万华聚氨酯合成材料有限公司 | Preparation method of flame-retardant double-component polyurethane pouring sealant |
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Application publication date: 20190301 |