CN107955150A - A kind of organic synthesis type flame-retardant polycarbonate material and preparation method thereof - Google Patents
A kind of organic synthesis type flame-retardant polycarbonate material and preparation method thereof Download PDFInfo
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- CN107955150A CN107955150A CN201711185457.4A CN201711185457A CN107955150A CN 107955150 A CN107955150 A CN 107955150A CN 201711185457 A CN201711185457 A CN 201711185457A CN 107955150 A CN107955150 A CN 107955150A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Abstract
The invention discloses a kind of organic synthesis type flame-retardant polycarbonate material and preparation method thereof, the material of the present invention has good fire retardant performance, silica is formed by organic reaction and carbonate monomer and is crosslinked, then polymerisation is passed through, silica is effectively distributed in polymeric matrix, reunion is effectively reduced, improves the stability_intensity of finished-product material.
Description
Technical field
The present invention relates to Material Field, especially a kind of organic synthesis type flame-retardant polycarbonate material and preparation method thereof.
Background technology
Makrolon is among five large-engineering plastics, and a kind of development extremely rapid general engineering plastic, it develops at present
The impetus is very swift and violent, just promptly extends and is dissolved into computer manufacture, in terms of the industrial industrialization such as aerospace, blue light, relates to
And to many high-technology fields, additionally since the particularity of its performance, under the collective effect of other resins, to carrying out together
Mixed mode, forms copolymer or alloy type product, makes its performance more perfect, the product property of gained is very excellent, can
The environment of a variety of specific application areas is adapted to completely, and the requirement simultaneously for manufacture cost, properties is also to comply fully with mark
It is accurate.Configuration aspects, contain phenyl ring on the main chain of makrolon, in its combustion reaction, can carry out being condensed into aroma type charcoal thing
Matter, it is higher with respect to charring rate, and can self-extinguishment, the standard that its flame retardant rating can reach, polymerize relative to common thermoplastic
Thing, although its anti-flammability relative ideal in contrast, it is still in flammable category, and makrolon material is burned
Cheng Zhong, can melt and the hot melt that drips flows out, it is more likely that after causing the material combustion on periphery, neighbouring material to be ignited, cause
The generation of fire, for this point, at present in above application field, be difficult still to reach preferable fire-retardant fireproof standard,
Therefore in production and to the application of the true extension of material among, it is necessary to for the combustion phenomena and property of material, to its into
Row flame retardant treatment.But the poor compatibility of traditional inorganic combustion inhibitor and polyester matrix, it is easily reduced the stability of finished product.
The content of the invention
It is an object of the invention to asking for the poor compatibility of traditional inorganic combustion inhibitor and polyester matrix in the prior art
A kind of topic, there is provided preparation method of organic synthesis type flame-retardant polycarbonate material.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of organic synthesis type flame-retardant polycarbonate material, comprises the following steps：
(1) hexabromocyclododecane of 3-4 parts by weight is taken, is added to 40-50 times of its weight, 76-80% ethanol solution
In, stir evenly, obtain alcoholic solution；
(2) carbonic acid of 60-70 parts by weight is taken, is added in the deionized water of 38-40 times of its weight, stirs evenly；
(3) ethyl orthosilicate of 10-15 parts by weight is taken, is added in the deionized water of 30-35 times of its weight, concentration is added dropwise
For the ammonium hydroxide of 6-10%, adjusting pH is 10-11, when stirring reaction 1-2 is small, obtains Ludox；
(4) the catalyst mixing of 2, the 4- xylenols, 0.1-0.2 parts by weight of 5-7 parts by weight is taken, stirs evenly, rises
High-temperature is 110-116 DEG C, and above-mentioned carbon acid solution is added dropwise, and it is 90-95 DEG C that temperature is reduced after being added dropwise, and adds 1-2 parts by weight
Resorcinol, when stirring reaction 5-6 is small, it is 40-50 DEG C to reduce temperature, adds above-mentioned alcoholic solution, reduces temperature to room temperature, obtains
Acylated carbonate solution；
(5) above-mentioned Ludox, acylated carbonate solution mixing are taken, stirs evenly, the 10-14mol/l of 7-9 parts by weight is added dropwise
Hydrochloric acid solution, stirred evenly after being added dropwise, filter, filter cake is washed, air drying, obtains carbonate monomer colloidal sol；
(6) carbonate monomer colloidal sol is taken, with 1, the 6- hexylene glycols of 3-4 parts by weight, the stannous octoate of 1-2 parts by weight, 30-40
The dry toluene mixing of parts by weight, is put into dry polymerization pipe, is passed through argon gas, tube sealing under vacuum, is placed in 120-130 DEG C
When insulation reaction 20-25 is small in oil bath, product is cooled down, is filtered, precipitation is washed, when drying 1-2 is small at 70-75 DEG C of vacuum,
Cooling, up to the organic synthesis type flame-retardant polycarbonate material.
Preferably, in order to which the present invention is better achieved, the catalyst is aluminum trichloride (anhydrous).
Preferably, in order to which the present invention is better achieved, the speed that carbon acid solution is added dropwise in step (4) is 23-40 drops/min.
Preferably, in order to be better achieved the present invention, the speed of hydrochloric acid solution is 32-45 drops/min in step (5).
Advantages of the present invention：
The present invention uses ethyl orthosilicate to obtain Ludox for presoma, is then raw material with 2,4- xylenols, nothing
Water alchlor is catalyst, is mixed with carbon acid solution, by esterification, obtained acylation carbonate solution and silicon is molten
Glue is mixed and modified, obtains carbonic ester, Ludox cross-linking monomer, and the colloidal sol added in the monomer can promote uniform fine and close carbon-coating
Formation, and the carbon-coating can effectively prevent the thermal decomposition product of material internal from entering flame zone, and prevent the oxygen of outside
Into in matrices of composite material, hexabromocyclododecane is also added into the monomer, the effect of cooperative flame retardant is formd with Ludox,
The fire retardant performance of finished-product material is improved, silica is formed and handed over by the present invention by organic reaction and carbonate monomer
Connection, then by polymerisation, silica is effectively distributed in polymeric matrix, effectively reduces reunion, is improved
The stability_intensity of finished-product material.
Embodiment
The present invention is described in further detail with reference to embodiment, but the implementation of the present invention is not limited to this,
Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, various replace is made
Change and change, should all be included within the scope of the invention.
Embodiment 1
A kind of preparation method of organic synthesis type flame-retardant polycarbonate material, comprises the following steps：
(1) hexabromocyclododecane of 3 parts by weight is taken, is added in 40 times of its weight, 76% ethanol solution, stirring is equal
It is even, obtain alcoholic solution；
(2) carbonic acid of 60 parts by weight is taken, is added in the deionized water of 38 times of its weight, stirs evenly；
(3) ethyl orthosilicate of 10 parts by weight is taken, is added in the deionized water of 30 times of its weight, it is 6% that concentration, which is added dropwise,
Ammonium hydroxide, adjust pH be 10, stirring reaction 1 it is small when, obtain Ludox；
(4) the aluminum trichloride (anhydrous) mixing of 2, the 4- xylenols, 0.1 parts by weight of 5 parts by weight is taken, stirs evenly, rises
High-temperature is 110 DEG C, above-mentioned carbon acid solution is added dropwise, it is preferred that the speed that carbon acid solution is added dropwise is 23-40 drops/min, is dripped
It is 90-95 DEG C that temperature is reduced after finishing, and adds the resorcinol of 1 parts by weight, and when stirring reaction 5 is small, it is 40 DEG C to reduce temperature, is added
Above-mentioned alcoholic solution, reduces temperature to room temperature, obtains acylated carbonate solution；
(5) above-mentioned Ludox, acylated carbonate solution mixing are taken, stirs evenly, the salt of the 10mol/l of 7 parts by weight is added dropwise
Acid solution, it is preferred that the speed that hydrochloric acid solution is added dropwise is 32-45 drops/min, is stirred evenly after being added dropwise, and is filtered, by filter cake
Washing, air drying, obtains carbonate monomer colloidal sol；
(6) carbonate monomer colloidal sol is taken, the stannous octoate of 1,6- hexylene glycols, 1 parts by weight with 3 parts by weight, 30 parts by weight
Dry toluene mixing, be put into dry polymerization pipe, be passed through argon gas, tube sealing under vacuum, is placed in 120 DEG C of oil bath and keeps the temperature
React 20 it is small when, product is cooled down, is filtered, will precipitation washing, at 70 DEG C of vacuum it is dry 1 it is small when, cooling, up to organic conjunction
It is molded flame-retardant polycarbonate material.
Embodiment 2
A kind of preparation method of organic synthesis type flame-retardant polycarbonate material, comprises the following steps：
(1) hexabromocyclododecane of 4 parts by weight is taken, is added in 50 times of its weight, 80% ethanol solution, stirring is equal
It is even, obtain alcoholic solution；
(2) carbonic acid of 70 parts by weight is taken, is added in the deionized water of 40 times of its weight, stirs evenly；
(3) ethyl orthosilicate of 15 parts by weight is taken, is added in the deionized water of 35 times of its weight, it is 10% that concentration, which is added dropwise,
Ammonium hydroxide, adjust pH be 11, stirring reaction 2 it is small when, obtain Ludox；
(4) the aluminum trichloride (anhydrous) mixing of 2, the 4- xylenols, 0.2 parts by weight of 7 parts by weight is taken, stirs evenly, rises
High-temperature is 116 DEG C, and above-mentioned carbon acid solution is added dropwise, and it is 95 DEG C that temperature is reduced after being added dropwise, and adds the isophthalic two of 2 parts by weight
Phenol, when stirring reaction 6 is small, it is 50 DEG C to reduce temperature, adds above-mentioned alcoholic solution, reduces temperature to room temperature, it is molten to obtain acylated carbonic ester
Liquid；
(5) above-mentioned Ludox, acylated carbonate solution mixing are taken, stirs evenly, the salt of the 14mol/l of 9 parts by weight is added dropwise
Acid solution, stirs evenly after being added dropwise, and filters, filter cake is washed, air drying, obtain carbonate monomer colloidal sol；
(6) carbonate monomer colloidal sol is taken, the stannous octoate of 1,6- hexylene glycols, 2 parts by weight with 3-4 parts by weight, 40 weight
Part dry toluene mixing, be put into dry polymerization pipe, be passed through argon gas, tube sealing under vacuum, is placed in 130 DEG C of oil bath and protects
When temperature reaction 25 is small, product is cooled down, is filtered, will precipitation washing, at 75 DEG C of vacuum it is dry 2 it is small when, cooling, up to described organic
Synthesis type flame-retardant polycarbonate material.
Embodiment 3
A kind of preparation method of organic synthesis type flame-retardant polycarbonate material, comprises the following steps：
(1) hexabromocyclododecane of 3 parts by weight is taken, is added in 48 times of its weight, 76% ethanol solution, stirring is equal
It is even, obtain alcoholic solution；
(2) carbonic acid of 67 parts by weight is taken, is added in the deionized water of 38-40 times of its weight, stirs evenly；
(3) ethyl orthosilicate of 14 parts by weight is taken, is added in the deionized water of 34 times of its weight, it is 8% that concentration, which is added dropwise,
Ammonium hydroxide, adjust pH be 10, stirring reaction 1 it is small when, obtain Ludox；
(4) the aluminum trichloride (anhydrous) mixing of 2, the 4- xylenols, 0.17 parts by weight of 5 parts by weight is taken, stirs evenly, rises
High-temperature is 115 DEG C, and above-mentioned carbon acid solution is added dropwise, and it is 90-95 DEG C that temperature is reduced after being added dropwise, and adds the isophthalic of 1 parts by weight
Diphenol, when stirring reaction 5 is small, it is 40 DEG C to reduce temperature, adds above-mentioned alcoholic solution, reduces temperature to room temperature, obtains acylated carbonic ester
Solution；
(5) above-mentioned Ludox, acylated carbonate solution mixing are taken, stirs evenly, the salt of the 13mol/l of 7 parts by weight is added dropwise
Acid solution, stirs evenly after being added dropwise, and filters, filter cake is washed, air drying, obtain carbonate monomer colloidal sol；
(6) carbonate monomer colloidal sol is taken, the stannous octoate of 1,6- hexylene glycols, 1-2 parts by weight with 3 parts by weight, 37 weight
Part dry toluene mixing, be put into dry polymerization pipe, be passed through argon gas, tube sealing under vacuum, is placed in 126 DEG C of oil bath and protects
When temperature reaction 20 is small, product is cooled down, is filtered, will precipitation washing, at 70 DEG C of vacuum it is dry 1 it is small when, cooling, up to described organic
Synthesis type flame-retardant polycarbonate material.
Embodiment 4
A kind of preparation method of organic synthesis type flame-retardant polycarbonate material, comprises the following steps：
(1) hexabromocyclododecane of 3.5 parts by weight is taken, is added in 45 times of its weight, 78% ethanol solution, stirring
Uniformly, alcoholic solution is obtained；
(2) carbonic acid of 65 parts by weight is taken, is added in the deionized water of 39 times of its weight, stirs evenly；
(3) ethyl orthosilicate of 13 parts by weight is taken, is added in the deionized water of 33 times of its weight, it is 8% that concentration, which is added dropwise,
Ammonium hydroxide, adjust pH be 10, stirring reaction 1 it is small when, obtain Ludox；
(4) the aluminum trichloride (anhydrous) mixing of 2, the 4- xylenols, 0.15 parts by weight of 6 parts by weight is taken, stirs evenly, rises
High-temperature is 114 DEG C, and above-mentioned carbon acid solution is added dropwise, and it is 93 DEG C that temperature is reduced after being added dropwise, and adds the isophthalic two of 1.5 parts by weight
Phenol, when stirring reaction 5.5 is small, it is 45 DEG C to reduce temperature, adds above-mentioned alcoholic solution, reduces temperature to room temperature, obtains acylated carbonic ester
Solution；
(5) above-mentioned Ludox, acylated carbonate solution mixing are taken, stirs evenly, the salt of the 13mol/l of 8 parts by weight is added dropwise
Acid solution, stirs evenly after being added dropwise, and filters, filter cake is washed, air drying, obtain carbonate monomer colloidal sol；
(6) carbonate monomer colloidal sol is taken, stannous octoate, 35 weights of 1,6- hexylene glycols, 1.5 parts by weight with 3.5 parts by weight
The dry toluene mixing of part is measured, is put into dry polymerization pipe, is passed through argon gas, tube sealing under vacuum, is placed in 120 DEG C of oil bath
When insulation reaction 23 is small, product is cooled down, is filtered, precipitation is washed, when drying 1.5 is small at 75 DEG C of vacuum, cooling, up to described
Organic synthesis type flame-retardant polycarbonate material.
Performance test：
The performance for the organic synthesis type flame-retardant polycarbonate material that 1~3 method according to embodiments of the present invention of table 1 is prepared is surveyed
Test result
Conclusion：As can be seen that the organic synthesis type flame-retardant polycarbonate material of the present invention has good fire resistance.
Claims (4)
1. a kind of preparation method of organic synthesis type flame-retardant polycarbonate material, it is characterised in that comprise the following steps：
(1) hexabromocyclododecane of 3-4 parts by weight is taken, in ethanol solution that be added to 40-50 times of its weight, 76-80%, is stirred
Mix uniformly, obtain alcoholic solution；
(2) carbonic acid of 60-70 parts by weight is taken, is added in the deionized water of 38-40 times of its weight, stirs evenly；
(3) ethyl orthosilicate of 10-15 parts by weight is taken, is added in the deionized water of 30-35 times of its weight, dropwise addition concentration is 6-
10% ammonium hydroxide, adjusting pH are 10-11, when stirring reaction 1-2 is small, obtain Ludox；
(4) the catalyst mixing of 2, the 4- xylenols, 0.1-0.2 parts by weight of 5-7 parts by weight is taken, is stirred evenly, rise temperature
Spend for 110-116 DEG C, above-mentioned carbon acid solution is added dropwise, it is 90-95 DEG C that temperature is reduced after being added dropwise, and is added between 1-2 parts by weight
Benzenediol, when stirring reaction 5-6 is small, it is 40-50 DEG C to reduce temperature, adds above-mentioned alcoholic solution, reduces temperature to room temperature, obtains acylation
Carbonate solution；
(5) above-mentioned Ludox, acylated carbonate solution mixing are taken, stirs evenly, the salt of the 10-14mol/l of 7-9 parts by weight is added dropwise
Acid solution, stirs evenly after being added dropwise, and filters, filter cake is washed, air drying, obtain carbonate monomer colloidal sol；
(6) carbonate monomer colloidal sol is taken, with 1, the 6- hexylene glycols of 3-4 parts by weight, the stannous octoate of 1-2 parts by weight, 30-40 weight
Part dry toluene mixing, be put into dry polymerization pipe, be passed through argon gas, tube sealing under vacuum, is placed in 120-130 DEG C of oil bath
When middle insulation reaction 20-25 is small, product is cooled down, is filtered, will precipitation washing, when dry 1-2 is small at 70-75 DEG C of vacuum, cooling,
Up to the organic synthesis type flame-retardant polycarbonate material.
A kind of 2. preparation method of organic synthesis type flame-retardant polycarbonate material according to claim 1, it is characterised in that
The catalyst is aluminum trichloride (anhydrous).
A kind of 3. preparation method of organic synthesis type flame-retardant polycarbonate material according to claim 2, it is characterised in that
The speed that carbon acid solution is added dropwise in step (4) is 23-40 drops/min.
4. according to a kind of preparation method of organic synthesis type flame-retardant polycarbonate material of claim 1-3 any one of them, its
It is characterized in that, the speed of hydrochloric acid solution is 32-45 drops/min in step (5).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100437A (en) * | 1993-05-24 | 1995-03-22 | 通用电气公司 | Method for making flame retardant polycarbonate |
| CN1569919A (en) * | 2004-04-30 | 2005-01-26 | 武汉化工学院 | Bisphenol type flame-retardant polycarbonate interface method preparation method |
| CN101628973A (en) * | 2008-07-17 | 2010-01-20 | 帝人株式会社 | Flame-resistant copolymerized panlite |
| CN105482091A (en) * | 2015-12-28 | 2016-04-13 | 甘肃银光聚银化工有限公司 | Preparation method of low-molecular-weight halogen flame-retardant polycarbonate |
-
2017
- 2017-11-23 CN CN201711185457.4A patent/CN107955150A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100437A (en) * | 1993-05-24 | 1995-03-22 | 通用电气公司 | Method for making flame retardant polycarbonate |
| CN1569919A (en) * | 2004-04-30 | 2005-01-26 | 武汉化工学院 | Bisphenol type flame-retardant polycarbonate interface method preparation method |
| CN101628973A (en) * | 2008-07-17 | 2010-01-20 | 帝人株式会社 | Flame-resistant copolymerized panlite |
| CN105482091A (en) * | 2015-12-28 | 2016-04-13 | 甘肃银光聚银化工有限公司 | Preparation method of low-molecular-weight halogen flame-retardant polycarbonate |
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Application publication date: 20180424 |