CN112898553A - Efficient intrinsic flame-retardant polycarbonate and preparation method thereof - Google Patents
Efficient intrinsic flame-retardant polycarbonate and preparation method thereof Download PDFInfo
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- CN112898553A CN112898553A CN202110098391.5A CN202110098391A CN112898553A CN 112898553 A CN112898553 A CN 112898553A CN 202110098391 A CN202110098391 A CN 202110098391A CN 112898553 A CN112898553 A CN 112898553A
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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
- C08G64/18—Block or graft polymers
- C08G64/186—Block or graft polymers containing polysiloxane sequences
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- 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
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
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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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
- C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
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Abstract
The invention relates to the field of functional polymer materials, in particular to efficient intrinsic flame-retardant polycarbonate and a preparation method thereof. The structural formula is as follows:
wherein a is 10 to 2000, b is 1 to 100, and c is 1 to 100. Bisphenol A/bisphenol S/siloxane copolycarbonate is prepared by polymerization using the triphosgene method. The aromatic sulfonate in the bisphenol S structure has a high-efficiency flame retardant effect, and the silicon flame retardant structure in the siloxane structure and the aromatic sulfonate have a synergistic flame retardant effect, so that the flame retardant property of the polycarbonate is further improved.
Description
Technical Field
The invention relates to the field of functional polymer materials, in particular to efficient intrinsic flame-retardant polycarbonate and a preparation method thereof.
Background
The polycarbonate is an engineering plastic with excellent comprehensive performance, is colorless, tasteless and nontoxic, has the characteristics of high strength, high toughness, stronger heat resistance and cold resistance, has excellent dielectric property, excellent color and size stability, and is second to polyamide in six engineering plastic consumption. Polycarbonate products have been penetrated into the industries of automobiles, construction, machinery, clothing, medicine, electronic and electric appliances and the like, and are closely related to the life of people. However, the limiting oxygen index of the polycarbonate is only 21-26%, the vertical burning is UL 94V-2 grade, and the flame retardant property is poor.
At present, the flame retardant property of polycarbonate is mainly improved by adding flame retardants, such as phosphorus flame retardants, boron flame retardants, magnesium hydroxide, aluminum hydroxide and the like. However, phosphorus flame retardants are prone to corrode molds, and magnesium hydroxide and aluminum hydroxide generally need to be added in large amounts to achieve the flame retardant effect, so that the mechanical properties and the like of the polymer are rapidly reduced. The sulfonate flame retardant is a flame retardant with remarkable flame retardant effect, and can obtain good flame retardant effect only by adding a very small amount of the sulfonate flame retardant into polycarbonate. However, since the amount of the sulfonate added is small, it is difficult to mix uniformly in the polycarbonate.
The phosgene method is a traditional polycarbonate production technology, but the phosgene method has large investment route, methylene dichloride discharged in the production process is suspected to be cancerogenic, and COCl is simultaneously used2Is a highly toxic product with great danger, and is used for treating COCl in various countries of the world2Have very strict legal regulations and limits both in production and application.
Disclosure of Invention
The invention aims to provide efficient intrinsic flame-retardant polycarbonate and a preparation method thereof, and bisphenol A/bisphenol S/siloxane copolycarbonate is prepared by polymerization with a triphosgene method. The aromatic sulfonate in the bisphenol S structure has a high-efficiency flame retardant effect, and the silicon flame retardant structure in the siloxane structure and the aromatic sulfonate have a synergistic flame retardant effect, so that the flame retardant property of the polycarbonate is further improved.
In order to achieve the purpose, the invention provides the following technical scheme:
a highly efficient intrinsic flame retardant polycarbonate having the structural formula:
wherein a is 10 to 2000, b is 1 to 100, and c is 1 to 100.
The preparation method of the high-efficiency intrinsic flame-retardant polycarbonate comprises the following steps:
s1, adding a certain amount of bisphenol A and bisphenol S into a three-neck flask, adding a certain amount of NaOH aqueous solution, and stirring to fully dissolve the bisphenol A and the bisphenol S;
s2, adding a certain amount of triethylamine, sodium bisulfite and siloxane into the three-neck flask, stirring and heating to a certain temperature to completely dissolve the triethylamine, the sodium bisulfite and the siloxane; wherein triethylamine is used as a catalyst, and sodium bisulfite is used as an antioxidant;
s3, dissolving triphosgene in dichloromethane, dropwise adding the solution into a three-neck flask by using a constant-pressure dropping funnel, and continuing to react after the dropwise adding is finished;
s4, stopping the reaction after the reaction is carried out for a certain time, and standing the substances in the three-neck flask for a certain time;
s5, pouring out the supernatant of the three-neck flask to obtain a lower turbid liquid, washing the lower turbid liquid to be neutral by using deionized water, adding absolute ethyl alcohol to obtain a precipitate product, filtering, and drying in an oven to obtain the high-efficiency intrinsic flame-retardant polycarbonate.
In a further scheme, in the step S1, the adding amount of the bisphenol S is 0.5-20% of the adding amount of the bisphenol A by mass. The addition amount of bisphenol S is preferably 2-10% of the addition amount of bisphenol A.
In a further scheme, in the step S2, the adding amount of the siloxane is 2% -10% of that of the bisphenol A by mass. Preferably, the siloxane is added in an amount of 4% to 8% of the bisphenol A.
Further, in the step S2, the stirring and heating temperature is 0-40 ℃. The heating temperature is preferably 10-20 ℃.
Further, in step S3, the triphosgene solution is added dropwise to the three-necked flask for a period of time ranging from 10 minutes to 1 hour. The preferable time for dripping the triphosgene solution into the three-neck flask is 20-40 minutes.
Further, in step S4, the three-necked flask is allowed to stand for 10 minutes to 2 hours. The three-necked flask is preferably allowed to stand for 30 minutes to 1 hour.
Further, in the step S5, the drying time is 6-24 hours, and the drying temperature is 60-120 ℃. Preferably, the drying time is 8-12 hours; the preferable drying temperature is 80-100 ℃.
Compared with the prior art, the invention has the advantages that:
1. bisphenol A and siloxane are added into bisphenol A, and the polymerization is carried out by using triphosgene method to prepare bisphenol A/bisphenol S/siloxane copolycarbonate. The intrinsic flame-retardant polycarbonate molecular chain structure obtained by the method contains the efficient flame-retardant aromatic sulfonate and the silicon flame-retardant structure at the same time, so that the flame-retardant property of the polycarbonate can be obviously improved. Wherein the limit oxygen index is improved from 26% to 38%, and the vertical combustion performance is improved from V-2 level to V-0 level.
2. The preparation method provided by the invention avoids the defects of high toxicity and danger caused by the traditional phosgene method, is simple and feasible, is easy to operate, and is green and environment-friendly.
3. The polycarbonate prepared by the method is an intrinsic flame-retardant polycarbonate, and overcomes the defects of uneven dispersion of an additive flame retardant, reduced flame-retardant effect along with time extension and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a nuclear magnetic hydrogen spectrum of a highly effective intrinsic flame retardant polycarbonate;
FIG. 2 is a graph of the thermal weight loss of highly effective inherently flame retardant polycarbonate.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a250 ml three-necked flask was charged with 26.54g of bisphenol A and 0.9g of bisphenol S, and a predetermined amount of an aqueous NaOH solution was added thereto and sufficiently dissolved by stirring. Then 0.22g triethylamine, 1.65g siloxane and 0.18g sodium bisulfite were added, stirred rapidly and raised to 35 ℃ to allow complete dissolution. 13.024g of triphosgene was dissolved in 160ml of methylene chloride, and the solution was dropped into a three-necked flask using a constant pressure dropping funnel, and the reaction was continued for 1 hour after the dropping was completed. And (3) standing the substances in the three-neck flask for 1 hour, pouring out the supernatant, washing the lower turbid liquid with deionized water to be neutral, then precipitating the product with 200ml of absolute ethyl alcohol, filtering, and then putting into an oven to be dried for 12 hours at 100 ℃ to obtain the intrinsic flame-retardant polycarbonate.
Example 2:
to a 250ml three-necked flask, 25.72g of bisphenol A and 1.8g of bisphenol S were charged, and a certain amount of an aqueous NaOH solution was further added and sufficiently dissolved by stirring. Then 0.22g triethylamine, 1.65g siloxane and 0.18g sodium bisulfite were added, stirred rapidly and raised to 35 ℃ to allow complete dissolution. 13.024g of triphosgene was dissolved in 160ml of methylene chloride, and the solution was dropped into a three-necked flask using a constant pressure dropping funnel, and the reaction was continued for 1 hour after the dropping was completed. And (3) standing the substances in the three-neck flask for 1 hour, pouring out the supernatant, washing the lower turbid liquid with deionized water to be neutral, then precipitating the product with 200ml of absolute ethyl alcohol, filtering, and then putting into an oven to be dried for 12 hours at 100 ℃ to obtain the intrinsic flame-retardant polycarbonate.
Example 3:
a250 ml three-necked flask was charged with 24.90g of bisphenol A and 2.7g of bisphenol S, and a predetermined amount of an aqueous NaOH solution was added thereto and sufficiently dissolved by stirring. Then 0.22g triethylamine, 1.65g siloxane and 0.18g sodium bisulfite were added, stirred rapidly and raised to 35 ℃ to allow complete dissolution. 13.024g of triphosgene was dissolved in 160ml of methylene chloride, and the solution was dropped into a three-necked flask using a constant pressure dropping funnel, and the reaction was continued for 1 hour after the dropping was completed. And (3) standing the substances in the three-neck flask for 1 hour, pouring out the supernatant, washing the lower turbid liquid with deionized water to be neutral, then precipitating the product with 200ml of absolute ethyl alcohol, filtering, and then putting into an oven to be dried for 12 hours at 100 ℃ to obtain the intrinsic flame-retardant polycarbonate.
Example 4:
a250 ml three-necked flask was charged with 24.08g of bisphenol A and 3.6g of bisphenol S, and a predetermined amount of an aqueous NaOH solution was added thereto and sufficiently dissolved by stirring. Then 0.22g triethylamine, 1.65g siloxane and 0.18g sodium bisulfite were added, stirred rapidly and raised to 35 ℃ to allow complete dissolution. 13.024g of triphosgene was dissolved in 160ml of methylene chloride, and the solution was dropped into a three-necked flask using a constant pressure dropping funnel, and the reaction was continued for 1 hour after the dropping was completed. And (3) standing the substances in the three-neck flask for 1 hour, pouring out the supernatant, washing the lower turbid liquid with deionized water to be neutral, then precipitating the product with 200ml of absolute ethyl alcohol, filtering, and then putting into an oven to be dried for 12 hours at 100 ℃ to obtain the intrinsic flame-retardant polycarbonate.
Example 5:
to a 250ml three-necked flask, 45.6g of bisphenol A and 0.025g of bisphenol S were charged, and a certain amount of an aqueous NaOH solution was added and sufficiently dissolved by stirring. Then 0.45g triethylamine, 0.036g siloxane and 0.36g sodium bisulfite were added, stirred rapidly and warmed to 35 ℃ to allow complete dissolution. 26g of triphosgene is dissolved in 320ml of dichloromethane, and the solution is dripped into a three-neck flask by using a constant pressure dropping funnel, and the reaction is continued for 6 hours after the dripping is finished. And (3) standing the substances in the three-neck flask for 1 hour, pouring out the supernatant, washing the lower turbid liquid with deionized water to be neutral, then precipitating the product with 400ml of absolute ethyl alcohol, filtering, and then putting into an oven to be dried for 12 hours at 100 ℃ to obtain the intrinsic flame-retardant polycarbonate.
Example 6:
to a 250ml three-necked flask, 45.6g of bisphenol A and 2.5g of bisphenol S were charged, and a certain amount of an aqueous NaOH solution was further added and sufficiently dissolved by stirring. Then 0.45g triethylamine, 3.6g siloxane and 0.36g sodium bisulfite were added, stirred rapidly and raised to 35 ℃ to allow complete dissolution. 26g of triphosgene is dissolved in 320ml of dichloromethane, and the solution is dripped into a three-neck flask by using a constant pressure dropping funnel, and the reaction is continued for 6 hours after the dripping is finished. And (3) standing the substances in the three-neck flask for 1 hour, pouring out the supernatant, washing the lower turbid liquid with deionized water to be neutral, then precipitating the product with 400ml of absolute ethyl alcohol, filtering, and then putting into an oven to be dried for 12 hours at 100 ℃ to obtain the intrinsic flame-retardant polycarbonate.
Example 7:
a250 ml three-necked flask was charged with 22.8g of bisphenol A and 2.5g of bisphenol S, and a predetermined amount of an aqueous NaOH solution was added thereto and sufficiently dissolved by stirring. Then 0.22g triethylamine, 3.6g siloxane and 0.18g sodium bisulfite were added, stirred rapidly and raised to 35 ℃ to allow complete dissolution. 13.024g of triphosgene was dissolved in 160ml of methylene chloride, and the solution was added dropwise to a three-necked flask using a dropping funnel having a constant pressure, and the reaction was continued for 0.5 hour after the completion of the addition. And (3) standing the substances in the three-neck flask for 1 hour, pouring out the supernatant, washing the lower turbid liquid with deionized water to be neutral, then precipitating the product with 200ml of absolute ethyl alcohol, filtering, and then putting into an oven to be dried for 12 hours at 100 ℃ to obtain the intrinsic flame-retardant polycarbonate.
Table 1:
limiting oxygen index and vertical combustion result of high-efficiency intrinsic flame-retardant polycarbonate
As shown in Table 1, the results of the flame retardant test of example 1 show that the intrinsic flame retardant modified polycarbonate prepared by the method has a limiting oxygen index of 37 and passes the UL-94V-0 rating;
the flame retardant test results of example 2 show that the intrinsic flame retardant modified polycarbonate prepared by the method has a limiting oxygen index of 38, passing UL-94V-0 rating;
the flame retardant test results of example 3 show that the intrinsic flame retardant modified polycarbonate prepared by the method has a limiting oxygen index of 38, passing UL-94V-0 rating;
example 4 the results of the flame retardant test show that the intrinsic flame retardant modified polycarbonate prepared by this method has a limiting oxygen index of 36, passing the UL-94V-0 rating.
As shown in FIG. 1, the peak with chemical shift δ of 0.1ppm is-Si-CH in siloxane3The characteristic absorption peak is-C-CH of bisphenol A with a chemical shift delta being 1.7ppm3The peak with chemical shift delta of 7.25ppm belongs to benzene ring. The above results demonstrate that the process successfully produces the desired product, an inherently flame retardant polycarbonate.
As shown in FIG. 2, the initial degradation temperatures T of the inherently flame retardant polycarbonates prepared in examples 1-35％Both exceeding 400 ℃ and the initial degradation temperature T of the inherently flame-retardant polycarbonate prepared in example 45％Over 350 deg.c. The residual carbon content at 700 ℃ is more than 20 percent. The above results show that the intrinsic flame retardant polycarbonate prepared by the method has excellent thermal stability.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A highly efficient intrinsic flame retardant polycarbonate is characterized in that the structural formula is as follows:
wherein a is 10 to 2000, b is 1 to 100, and c is 1 to 100.
2. The highly efficient inherently flame retardant polycarbonate of claim 1, wherein the method of preparation comprises the steps of:
s1, adding bisphenol A and bisphenol S into a three-neck flask, adding NaOH aqueous solution, and stirring to fully dissolve the mixture;
s2, adding triethylamine, sodium bisulfite and siloxane into the three-neck flask, stirring and heating to completely dissolve the triethylamine, the sodium bisulfite and the siloxane;
s3, dissolving triphosgene in dichloromethane, dropwise adding the solution into a three-neck flask by using a constant-pressure dropping funnel, and continuing to react after the dropwise adding is finished;
s4, stopping the reaction after reacting for a certain time, and standing the substances in the three-neck flask;
s5, pouring out the supernatant of the three-neck flask to obtain a lower turbid liquid, washing the lower turbid liquid to be neutral by using deionized water, adding absolute ethyl alcohol to obtain a precipitate product, filtering, and drying in an oven to obtain the high-efficiency intrinsic flame-retardant polycarbonate.
3. The method of claim 2, wherein in step S1, the amount of bisphenol S added is 0.5-20% of the amount of bisphenol A added.
4. The method of claim 2, wherein in step S2, the siloxane is added in an amount of 2-20% by weight of the bisphenol A.
5. The method for preparing highly efficient intrinsic flame retardant polycarbonate according to claim 2, wherein the temperature of stirring and heating in step S2 is 0-40 ℃.
6. The method of claim 2, wherein the triphosgene solution is added dropwise to the three-necked flask in step S3 for 10 minutes to 1 hour.
7. The method of claim 2, wherein the three-necked flask is left to stand for 10 minutes to 2 hours in step S4.
8. The method for preparing the highly efficient intrinsic flame retardant polycarbonate according to claim 2, wherein in step S5, the drying time is 6-24 hours, and the drying temperature is 60-120 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456366A (en) * | 2022-01-27 | 2022-05-10 | 四川大学 | Low-smoke low-heat intrinsic flame-retardant copolycarbonate, and preparation method and application thereof |
| CN115819747A (en) * | 2022-11-04 | 2023-03-21 | 重庆清徽节能环保科技有限公司 | Flame-retardant polycarbonate prepolymer with intrinsic sulfonate and compound thereof |
| CN117209743A (en) * | 2023-10-11 | 2023-12-12 | 江苏福赛乙德药业有限公司 | Modified bisphenol AF polycarbonate material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610714A (en) * | 2001-10-09 | 2005-04-27 | 通用电气公司 | Polycarbonate-siloxane copolymers |
| CN103755942A (en) * | 2013-12-31 | 2014-04-30 | 吴江市东泰电力特种开关有限公司 | High-flame-retardance polycarbonate material and preparation method thereof |
| CN107278214A (en) * | 2016-02-01 | 2017-10-20 | 株式会社Lg化学 | New polysiloxane and the Copolycarbonate prepared using the polysiloxane |
| CN107406593A (en) * | 2014-12-30 | 2017-11-28 | 莫门蒂夫性能材料股份有限公司 | Siloxanes coordination polymer |
-
2021
- 2021-01-25 CN CN202110098391.5A patent/CN112898553A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1610714A (en) * | 2001-10-09 | 2005-04-27 | 通用电气公司 | Polycarbonate-siloxane copolymers |
| CN103755942A (en) * | 2013-12-31 | 2014-04-30 | 吴江市东泰电力特种开关有限公司 | High-flame-retardance polycarbonate material and preparation method thereof |
| CN107406593A (en) * | 2014-12-30 | 2017-11-28 | 莫门蒂夫性能材料股份有限公司 | Siloxanes coordination polymer |
| CN107278214A (en) * | 2016-02-01 | 2017-10-20 | 株式会社Lg化学 | New polysiloxane and the Copolycarbonate prepared using the polysiloxane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456366A (en) * | 2022-01-27 | 2022-05-10 | 四川大学 | Low-smoke low-heat intrinsic flame-retardant copolycarbonate, and preparation method and application thereof |
| CN115819747A (en) * | 2022-11-04 | 2023-03-21 | 重庆清徽节能环保科技有限公司 | Flame-retardant polycarbonate prepolymer with intrinsic sulfonate and compound thereof |
| CN117209743A (en) * | 2023-10-11 | 2023-12-12 | 江苏福赛乙德药业有限公司 | Modified bisphenol AF polycarbonate material and preparation method thereof |
| CN117209743B (en) * | 2023-10-11 | 2024-03-29 | 江苏福赛乙德药业有限公司 | Modified bisphenol AF polycarbonate material and preparation method thereof |
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Application publication date: 20210604 |