CN109575078A - Organic silicon-phosphorus sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds and preparation method thereof - Google Patents
Organic silicon-phosphorus sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds and preparation method thereof Download PDFInfo
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- CN109575078A CN109575078A CN201811297659.2A CN201811297659A CN109575078A CN 109575078 A CN109575078 A CN 109575078A CN 201811297659 A CN201811297659 A CN 201811297659A CN 109575078 A CN109575078 A CN 109575078A
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- alcohol ester
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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
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
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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 sulphur fire retardant tri o cresyl thiophosphate 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 sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds and preparation method thereof, tools
Body is related to a kind of organic silicon-phosphorus sulphur fire retardant tri o cresyl thiophosphate, 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 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 feature of environmental protection, i.e. fire retardant
Just develop towards non-halogen direction, wherein organosilicon and organophosphorous fire retardant are all market suddenly non-halogen products leaved for development；From
Herbicide interactions angle design compound siliceous and phosphorous etc. in same molecule, i.e. silicon phosphorus multielement fire retardant, when burning, are more
Element, which mutually cooperates with, can play excellent flame effect, there is critically important research and development meaning.
The invention discloses a kind of organic silicon-phosphorus sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds and preparation method thereof.
The present invention is using pentaerythritol methylsilicate and phosphorus thiochloride as raw material, and one-step method prepares the compound, simple process, equipment
Small investment, it is easy to operate, it is at low cost, easily it is converted into industrialized production；Fire retardant of the present invention, have siliceous, phosphorus, three kinds of sulphur it is fire-retardant
Element, flame-retarded efficiency be high, the good, symmetrical configuration and material compatibility is good, it is excellent not generate toxic gas etc. in combustion process at charcoal
Point.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 sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds,
The compound has moderate, good, burned with material compatibility containing silicon, phosphorus, three kinds of ignition-proof elements of sulphur, symmetrical configuration, polarity
Not the advantages that toxic gas is not generated in journey；It is adapted for use as polyester, polyamide, polyurethane, epoxy resin, unsaturated-resin, gathers
The fire retardant of the materials such as alkene can overcome deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions:
A kind of organic silicon-phosphorus sulphur fire retardant tri o cresyl thiophosphate 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 sulphur fire retardant tri o cresyl thiophosphate 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 phosphorus thiochloride, control three is added dropwise
The molar ratio of chlorothion 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 tri o cresyl thiophosphate 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 sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds of the present invention are white solid, decomposition temperature: 350
± 5 DEG C, density (25 DEG C): 1.391g/cm3, product yield is 85.6~95.2%, 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 sulphur fire retardant tri o cresyl thiophosphate 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 sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds of the present invention are siliceous, phosphorus, the triple fire-retardant members of sulphur
Element, flame-retarded efficiency is high, and cage ring structural symmetry is good, and product is stablized, and decomposition temperature is high, there is preferable processing performance.
2. organic silicon-phosphorus sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds of the present invention, good at charcoal, belong to efficient context
Friendly fire-retardant carbon forming agent, has preferably into the anti-melting drip effect of charcoal.
3. the preparation method that the present invention has organic silicon-phosphorus sulphur fire retardant tri o cresyl thiophosphate 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 tri o cresyl thiophosphate silicon cage alcohol ester；Fig. 1 shows 2951cm-1And 2888cm-1It is c h bond
Stretching vibration peak；1464cm-1And 1393cm-1It is the flexural vibrations peak of c h bond；1267cm-1It is the stretching vibration of P=S key
Peak；1153cm-1It is the stretching vibration peak of Si-O key；1086cm-1And 1043cm-1It is the stretching vibration doublet of C-O key,
1113cm-1It is the stretching vibration peak of Si-O-C key；885cm-1It is the flexural vibrations peak of Si-O-C key；980cm-1It is P-O-C key
Stretching vibration peak；760cm-1It is the stretching vibration peak of Si-C key.
Fig. 2 is tri o cresyl thiophosphate silicon cage alcohol ester nuclear magnetic spectrogram；Fig. 2 shows that using deuterated DMSO as solvent, δ 0.09 is
CH3Methyl hydrogen peak on-Si；
δ 1.9-2.1 is C-CH2Methylene hydrogen peak on O-P；
δ 3.3-3.5 is Si-OCH2Methylene hydrogen peak on C；
δ 2.5 is the H in DMSO solvent2Hydrogen peak in O.
Fig. 3 tri o cresyl thiophosphate silicon cage alcohol ester differential thermal spectrogram；Fig. 3 shows to start weightlessness when temperature rises to 350 DEG C or so；
When being heated to 380 DEG C, the weight-loss ratio of product reaches 50%；After final temperature reaches 800 DEG C, still there are 20% remnants
Object 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 (8.48g) phosphorus thiochloride 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 tri o cresyl thiophosphate silicon cage alcohol ester, decomposition temperature: 350 ± 5 DEG C, density (25 DEG C): 1.391g/cm3；
Yield is 85.6%.
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, 0.155mol (27.28g) pentaerythritol methylsilicate and 100ml tetrachloroethanes is added,
Under nitrogen protection, 35 DEG C are warming up to, starts that 0.05mol (8.48g) phosphorus thiochloride 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, the sour three silicon cage alcohol esters of white solid thiophosphoric acid are obtained, decomposition temperature: 350 ± 5 DEG C, density (25 DEG C): 1.391g/cm3；
Yield is 91.5%.
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 (8.48g) phosphorus thiochloride 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 tri o cresyl thiophosphate silicon cage alcohol ester, decomposition temperature: 350 ± 5 DEG C, density (25 DEG C): 1.391g/
cm3；Yield is 94.5%.
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 (8.48g) phosphorus thiochloride 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
Solid tri o cresyl thiophosphate silicon cage alcohol ester, decomposition temperature: 350 ± 5 DEG C, density (25 DEG C): 1.391g/cm3；Yield is
94.7%.
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 (8.48g) phosphorus thiochloride 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 tri o cresyl thiophosphate silicon cage alcohol ester is obtained, decomposition temperature: 350 ± 5 DEG C, density (25 DEG C): 1.391g/cm3；Yield is
95.0%.
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, 0.16mol (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 (8.48g) phosphorus thiochloride 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 tri o cresyl thiophosphate silicon cage alcohol ester, decomposition temperature: 350 ± 5 DEG C, density (25 DEG C): 1.391g/
cm3；Yield is 95.2%.
1 preparation example main technologic parameters of table
The product tri o cresyl thiophosphate silicon cage alcohol ester of above-mentioned preparation is also applied in poly- polypropylene (PP) by inventor, with
Different ratios is uniformly mixed, and is squeezed out at 200 DEG C by XJ-01 type single screw extrusion machine, long 15cm is made, diameter 3mm's
Batten, and the test of fire-retardant and dropping performance and the experiment of UL-94 vertical combustion have been carried out to the modified PP batten squeezed out, it is real
It tests and the results are 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 tri o cresyl thiophosphate 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 29.5%, V-0 grades；Work as fire retardant
Additive amount when reaching 25%, limit oxygen index can be up to 32.5% or more, can also obviously observe it is modified after PP
It will not occur to melt drip phenomenon in batten combustion process, and fast at charcoal speed, it is possible to find out tri o cresyl thiophosphate of the present invention
Silicon cage alcohol ester has PP fire-retardant at charcoal effect well.
Claims (4)
1. a kind of organic silicon-phosphorus sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds, which is characterized in that the structure of the compound
It is as follows:
2. a kind of preparation method of organic silicon-phosphorus sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds as described in claim 1,
It 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 phosphorus thiochloride 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 tri o cresyl thiophosphate 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 sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds as claimed in claim 2,
It is characterized by:
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 sulphur fire retardant tri o cresyl thiophosphate silicon cage alcohol ester compounds as claimed in claim 2,
It is characterized by:
The acid binding agent is triethylamine, pyridine or n,N-Dimethylaniline.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| 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 CN201811297659.2A patent/CN109575078A/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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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: 20190405 |