CN108219196A - A kind of preparation method of modified chlorinated phosphate ester fire retardant - Google Patents
A kind of preparation method of modified chlorinated phosphate ester fire retardant Download PDFInfo
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- CN108219196A CN108219196A CN201810015076.XA CN201810015076A CN108219196A CN 108219196 A CN108219196 A CN 108219196A CN 201810015076 A CN201810015076 A CN 201810015076A CN 108219196 A CN108219196 A CN 108219196A
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- modified
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- fire retardant
- phosphate ester
- trichloroethyl phosphate
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethylene
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
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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
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fireproofing Substances (AREA)
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Abstract
The present invention relates to field of fire-proof technology more particularly to a kind of preparation methods of modified chlorinated phosphate ester fire retardant, include the following steps：（1）Phosphorus oxychloride is added in photo catalysis reactor, ethylene oxide is added dropwise, adds nano boric acid bronzing catalyst, under the irradiation of visible ray xenon lamp, is stirred to react, obtains thick trichloroethyl phosphate；（2）Purifying, vacuum drying obtain copper borate and are modified trichloroethyl phosphate；（3）Outer surface coats microcapsules, and copper borate is made and is modified trichloroethyl phosphate microcapsule flame retardant.Using visible light catalytic organic synthesis trichloroethyl phosphate, using nano boric acid copper simultaneously as visible light catalyst and modifying agent, and pass through the cladding of microcapsules, the form that copper borate is modified trichloroethyl phosphate is changed, under non-flame resistant state, can effectively prevent to volatilize, it is more environmentally protective, heat decomposition temperature is improved simultaneously, avoids oozing out in the materials such as PU, PE, improves flame retarding efficiency.
Description
Technical field
The present invention relates to field of fire-proof technology more particularly to a kind of preparation methods of modified chlorinated phosphate ester fire retardant.
Background technology
Fire proofing is a kind of protection materials, it is the material that can prevent to burn and be not easy to itself burning, is one
Kind can make combustible material burning slow down, terminate or be difficult to the substance to burn.Fire proofing belongs to the new material that country vigorously supports
Field, the middle and high-end market of any product are all the market that technology and product quality are dominated.In phosphorus chlorine-based flame retardant anti-flammability and
One of best kind of persistence, although there is a small amount of production both at home and abroad, production scale is little, limits the product in foreign countries
High-end household items, automobile, high ferro, the industries such as aircraft industry use, so premium quality product is still needed to from U.S. both at home and abroad at present
The import of the country such as state, West Europe.
Trichloroethyl phosphate, abbreviation TCEP, a kind of outstanding organic phosphorus flame retardant, due to elemental chlorine and phosphorus in molecule
And ester bond, become high molecular material excellent fire retardant and plasticizer.But TCEP also has phosphonium flame retardant simultaneously
Common defects are such as：The easy frosting of product, softness decline, are easily oozed out in the materials such as PU, PE, reduce its flame retarding efficiency.Cause
The modified research and development of trichloroethyl phosphate fire retardant are had important research significance by this.
Invention content
The present invention provides a kind of modified chlorinated phosphate ester fire retardant to overcome the above-mentioned problems of the prior art
Preparation method.
To achieve these goals, the present invention uses following technical scheme：
A kind of preparation method of modified chlorinated phosphate ester fire retardant, includes the following steps：
（1）Phosphorus oxychloride is added in photo catalysis reactor, ethylene oxide is added dropwise, adds the catalysis of nano boric acid bronzing
Agent under the irradiation of visible ray xenon lamp, reacts under stirring condition, obtains thick trichloroethyl phosphate；
（2）By the purifying of thick trichloroethyl phosphate, vacuum drying, obtain copper borate and be modified trichloroethyl phosphate；
（3）Copper borate is modified trichloroethyl phosphate fire retardant outer cladding microcapsules, copper borate is made and is modified trichloroethyl phosphorus
Acid esters microcapsule flame retardant.
The energy gap of nano boric acid copper can be used as visible light catalyst to be applied to organic synthesis in 2.34 ~ 3.30eV,
While also there is excellent flame-retarding characteristic, the present invention is used as visible light catalyst and modifying agent simultaneously using nano boric acid copper,
Under the irradiation of visible ray xenon lamp, with ethylene oxide under nano boric acid copper catalysis esterification occurs for phosphorus oxychloride, it is seen that photocatalysis
Then organic synthesis trichloroethyl phosphate obtains copper borate with copper borate doping vario-property and is modified trichloroethyl phosphate, then
Cladding microcapsules are carried out to its outer surface by conventional technical means, copper borate is made and is modified the resistance of trichloroethyl phosphate microcapsules
Fire agent.The present invention synthesizes trichloroethyl phosphate using visible light catalytic, without adding additional catalyst, used photocatalysis agent
Continue to use as modifying agent after completion of the reaction, enhance flame retardant property.On the one hand it economizes on resources, on the other hand improves reaction
Conversion ratio, and then improve yield.By the cladding of microcapsules, the form that copper borate is modified trichloroethyl phosphate is changed, together
When improve heat decomposition temperature, avoid oozing out in the materials such as PU, PE, improve flame retarding efficiency.
Preferably, the amount ratio of the substance of the phosphorus oxychloride, ethylene oxide and nano boric acid bronzing catalyst is 1：（3~
5）：（0.01~1）.
Preferably, the microcapsules are using gelatin and gum arabic as capsule material.
Preferably, the nano boric acid bronzing catalyst is nanometer Cu3B2O6Or nanometer CuB2O4。
Preferably, step（1）In, the rate of addition of ethylene oxide is 2 ~ 5mL/min, and rate of addition is too fast or excessively slow,
All it is unfavorable for the high yield of esterification.
Preferably, step（2）In, vacuum drying temperature is 80 ~ 90 DEG C, and vacuum degree control is in 0.08 ~ 0.1MPa.
Preferably, step（1）In, the optical power density of the visible ray xenon lamp is 1000 ~ 2000mw/cm2。
Therefore, the present invention has the advantages that：Using visible light catalytic organic synthesis trichloroethyl phosphate, use
Nano boric acid copper changes copper borate and is modified three simultaneously as visible light catalyst and modifying agent, and pass through the cladding of microcapsules
The form of chloroethylphosphate under non-flame resistant state, can effectively prevent to volatilize, more environmentally protective, while improve heat point
Temperature is solved, avoids oozing out in the materials such as PU, PE, improves flame retarding efficiency.
Specific embodiment
Below by specific embodiment, the technical solutions of the present invention will be further described.
In the present invention, if not refering in particular to, all devices and raw material is commercially available or the industry is common are following
Method in embodiment is this field conventional method unless otherwise instructed.
Embodiment 1
（1）Amount ratio according to the substance of phosphorus oxychloride, ethylene oxide and nano boric acid bronzing catalyst is 1： 3：0.01 weighs
Each substance, for use；
（2）Phosphorus oxychloride is added in photo catalysis reactor, ethylene oxide is added dropwise for 2mL/min according to rate of addition,
Add a nanometer Cu3B2O6Photochemical catalyst, in optical power density be 1000mw/cm2Visible ray xenon lamp irradiation under, stirring condition
Lower reaction, obtains thick trichloroethyl phosphate；
（3）Thick trichloroethyl phosphate is purified, at a temperature of 80 DEG C, is dried in vacuo under 0.1MPa vacuum degree conditions, obtains boron
Sour copper is modified trichloroethyl phosphate；
（4）Copper borate is modified trichloroethyl phosphate fire retardant outer cladding using gelatin and gum arabic as the micro- of capsule material
Capsule is made copper borate and is modified trichloroethyl phosphate microcapsule flame retardant.
Embodiment 2
（1）Amount ratio according to the substance of phosphorus oxychloride, ethylene oxide and nano boric acid bronzing catalyst is 1：5：1 weighs each object
Matter, for use；
（2）Phosphorus oxychloride is added in photo catalysis reactor, ethylene oxide is added dropwise for 5mL/min according to rate of addition,
Add a nanometer CuB2O4Photochemical catalyst, in optical power density be 2000mw/cm2Visible ray xenon lamp irradiation under, under stirring condition
Reaction, obtains thick trichloroethyl phosphate；
（3）Thick trichloroethyl phosphate is purified, at a temperature of 90 DEG C, is dried in vacuo under 0.08MPa vacuum degree conditions, obtains boron
Sour copper is modified trichloroethyl phosphate；
（4）Copper borate is modified trichloroethyl phosphate fire retardant outer cladding using gelatin and gum arabic as the micro- of capsule material
Capsule is made copper borate and is modified trichloroethyl phosphate microcapsule flame retardant.
Embodiment 3
（1）Amount ratio according to the substance of phosphorus oxychloride, ethylene oxide and nano boric acid bronzing catalyst is 1：4：0.5 weighs each object
Matter, for use；
（2）Phosphorus oxychloride is added in photo catalysis reactor, ethylene oxide is added dropwise for 3mL/min according to rate of addition,
Add a nanometer Cu3B2O6Photochemical catalyst, in optical power density be 1500mw/cm2Visible ray xenon lamp irradiation under, stirring condition
Lower reaction, obtains thick trichloroethyl phosphate；
（3）Thick trichloroethyl phosphate is purified, at a temperature of 85 DEG C, is dried in vacuo under 0.09MPa vacuum degree conditions, obtains boron
Sour copper is modified trichloroethyl phosphate；
（4）Copper borate is modified trichloroethyl phosphate fire retardant outer cladding using gelatin and gum arabic as the micro- of capsule material
Capsule is made copper borate and is modified trichloroethyl phosphate microcapsule flame retardant.
The performance indicator that trichloroethyl phosphate microcapsule flame retardant is modified to the copper borate of embodiment 1-3 detects, and ties
Fruit is as shown in table 1：
1. testing result of table
| Performance indicator | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Heat resisting temperature | 350 | 300 | 320 |
| Fire-retardant index | V-0 | V-0 | V-0 |
As can be seen from Table 1, copper borate of the invention be modified trichloroethyl phosphate microcapsule flame retardant have it is higher heat-resisting
Temperature avoids oozing out in the materials such as PU, PE, and flame retarding efficiency is high.
The foregoing is merely presently preferred embodiments of the present invention, not makees limitation in any form to the present invention, is not surpassing
There are other variants and remodeling under the premise of going out the technical solution recorded in claim.
Claims (7)
1. a kind of preparation method of modified chlorinated phosphate ester fire retardant, which is characterized in that include the following steps：
（1）Phosphorus oxychloride is added in photo catalysis reactor, ethylene oxide is added dropwise, adds the catalysis of nano boric acid bronzing
Agent under the irradiation of visible ray xenon lamp, reacts under stirring condition, obtains thick trichloroethyl phosphate；
（2）By the purifying of thick trichloroethyl phosphate, vacuum drying, obtain copper borate and be modified trichloroethyl phosphate；
（3）Copper borate is modified trichloroethyl phosphate fire retardant outer cladding microcapsules, copper borate is made and is modified trichloroethyl phosphorus
Acid esters microcapsule flame retardant.
2. the preparation method of a kind of modified chlorinated phosphate ester fire retardant according to claim 1, which is characterized in that described three
The amount ratio of the substance of chlorethoxyfos, ethylene oxide and nano boric acid bronzing catalyst is 1：（3~5）：（0.01~1）.
3. the preparation method of a kind of modified chlorinated phosphate ester fire retardant according to claim 1, which is characterized in that described micro-
Capsule is using gelatin and gum arabic as capsule material.
4. the preparation method of a kind of modified chlorinated phosphate ester fire retardant according to claim 1, which is characterized in that described to receive
Rice copper borate photochemical catalyst is nanometer Cu3B2O6Or nanometer CuB2O4。
5. according to a kind of preparation method of any modified chlorinated phosphate ester fire retardants of claim 1-4, which is characterized in that step
Suddenly（1）In, the rate of addition of ethylene oxide is 2 ~ 5mL/min.
6. according to a kind of preparation method of any modified chlorinated phosphate ester fire retardants of claim 1-4, which is characterized in that step
Suddenly（2）In, vacuum drying temperature is 80 ~ 90 DEG C, and vacuum degree control is in 0.08 ~ 0.1MPa.
7. according to a kind of preparation method of modified chlorinated phosphate ester fire retardant described in claim 6, which is characterized in that step（1）
In, the optical power density of the visible ray xenon lamp is 1000 ~ 2000mw/cm2。
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| CN201810015076.XA CN108219196B (en) | 2018-01-08 | 2018-01-08 | A kind of preparation method of modified chlorinated phosphate ester fire retardant |
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| CN201810015076.XA CN108219196B (en) | 2018-01-08 | 2018-01-08 | A kind of preparation method of modified chlorinated phosphate ester fire retardant |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110747528A (en) * | 2019-11-29 | 2020-02-04 | 河北科技大学 | A kind of flame retardant microcapsule and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156775A (en) * | 1991-10-17 | 1992-10-20 | Blount David H | Flame retardant compositions |
| CN101885859A (en) * | 2009-05-11 | 2010-11-17 | 中国科学院化学研究所 | Flame retardant microcapsule and application thereof |
| CN102277176A (en) * | 2011-05-12 | 2011-12-14 | 寿光卫东化工有限公司 | Chloroalkyl polyphosphate ester fire retardant and synthetic technology thereof |
| CN105968591A (en) * | 2016-07-15 | 2016-09-28 | 株洲时代新材料科技股份有限公司 | Flame-retardant shock-absorption EPDM vulcanized rubber and preparation method thereof |
-
2018
- 2018-01-08 CN CN201810015076.XA patent/CN108219196B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156775A (en) * | 1991-10-17 | 1992-10-20 | Blount David H | Flame retardant compositions |
| CN101885859A (en) * | 2009-05-11 | 2010-11-17 | 中国科学院化学研究所 | Flame retardant microcapsule and application thereof |
| CN102277176A (en) * | 2011-05-12 | 2011-12-14 | 寿光卫东化工有限公司 | Chloroalkyl polyphosphate ester fire retardant and synthetic technology thereof |
| CN105968591A (en) * | 2016-07-15 | 2016-09-28 | 株洲时代新材料科技股份有限公司 | Flame-retardant shock-absorption EPDM vulcanized rubber and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110747528A (en) * | 2019-11-29 | 2020-02-04 | 河北科技大学 | A kind of flame retardant microcapsule and its preparation method and application |
| CN110747528B (en) * | 2019-11-29 | 2022-03-25 | 河北科技大学 | Flame-retardant microcapsule and preparation method and application thereof |
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Denomination of invention: Preparation Method of a Modified Chlorophosphate Flame Retardant Effective date of registration: 20221024 Granted publication date: 20191029 Pledgee: Zhejiang Suichang Rural Commercial Bank Co.,Ltd. Pledgor: ZHEJIANG HONGHAO TECHNOLOGY CO.,LTD. Registration number: Y2022330002781 |