CN110804166A - Preparation method of novel anti-ultraviolet copolymerized polycarbonate - Google Patents
Preparation method of novel anti-ultraviolet copolymerized polycarbonate Download PDFInfo
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- CN110804166A CN110804166A CN201911165908.7A CN201911165908A CN110804166A CN 110804166 A CN110804166 A CN 110804166A CN 201911165908 A CN201911165908 A CN 201911165908A CN 110804166 A CN110804166 A CN 110804166A
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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
- C08G64/307—General preparatory processes using carbonates 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
Abstract
The invention relates to the field of copolymerized polycarbonate, in particular to a preparation method of novel ultraviolet-resistant copolymerized polycarbonate. The preparation method comprises the following steps: (a) adding BPA, DPC and 4, 4' -dihydroxy benzophenone in a certain molar ratio into a reaction kettle provided with a temperature controller, a stirrer and a nitrogen protection device together, and reacting for a period of time at a certain temperature; (b) and raising the temperature, and continuing to react for a certain time to obtain the anti-ultraviolet copolymerized polycarbonate. The ultraviolet-resistant copolymerized polycarbonate prepared by the invention has excellent ultraviolet resistance, excellent rigidity and transparency, and is excellent molding processability engineering plastic.
Description
Technical Field
The invention relates to the field of copolymerization polymers, in particular to a preparation method of novel ultraviolet-resistant copolymerization polycarbonate.
Background
Polycarbonate is a linear polycarbonate in which the carbonate groups alternate with other groups, which may be aromatic, aliphatic, or both. Bisphenol a polycarbonate is the most important commercial product. Almost colorless amorphous polymers in glass state are widely used in the fields of glass assembly industry, automobile industry, electronics and electrical appliance industry, medical and health care, construction and the like. With the wide application of polycarbonate, the application of polycarbonate in special fields is also promoted to a certain extent, but the application in special fields has higher requirements on the performance of polycarbonate.
In order to apply polycarbonate resins to specific fields and obtain higher quality polycarbonates, it is necessary to modify polycarbonates. Copolymerization is a simple and effective important means for adjusting and improving the properties of polymer materials. The copolymerization ensures that the modified product has uniform material and less influence on the optical performance.
The polycarbonate resin has better thermal stability, and has the ultraviolet resistance of UL94V-2 grade without adding an ultraviolet resistance agent. However, to meet higher demands, better UV resistance is still required.
In the prior art, polycarbonate and an anti-ultraviolet agent are generally mixed to prepare a composite material, so that the anti-ultraviolet performance of the polycarbonate is improved. However, the added uvioresistant agent is often poor in dispersibility in polycarbonate and compatibility, and further influences the mechanical property of the composite material.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of novel ultraviolet-resistant copolymerized polycarbonate.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of novel uvioresistant copolymerized polycarbonate comprises the following steps:
(b) taking an anti-ultraviolet agent, BPA and DPC as raw materials, and reacting under a preset condition to generate a prepolymer;
(b) and (b) performing polycondensation reaction on the prepolymer in the step (a) to prepare the uvioresistant polycarbonate copolycarbonate.
Specifically, the preparation method comprises the following steps:
(a) under the protection atmosphere of inert gas, firstly placing DPC in a reaction kettle, heating to melt the DPC, then uniformly dispersing the uvioresistant agent in the molten DPC, uniformly stirring, then adding BPA and a catalyst, and reacting for 2-4h at 230 ℃ of 200-;
(b) raising the temperature of the prepolymer prepared in the step (a) to 240-290 ℃, and then stirring to continue reacting for 0.5-2h to obtain the uvioresistant polycarbonate copolycarbonate.
Further, the anti-ultraviolet agent is: 4, 4' -dihydroxybenzophenone.
Furthermore, the molar ratio of the DPC, the BPA and the anti-ultraviolet agent is n (DPC): (BPA): n (4, 4' -dihydroxy benzophenone): 1.02-1.1): 0.7-0.75): 0.3-0.35.
Further, the catalyst is an organic base catalyst.
Further, the organic base catalyst comprises a metal alkyl compound, and the metal alkyl compound comprises one or more of tert-butyl lithium, tert-butyl cesium, tert-butyl potassium and tert-butyl sodium.
Further, the molar ratio of the catalyst to BPA was 1: (1 to 5X 10)-4)。
Further, the stirring speed in the step (a) is 600-.
Further, the stirring speed in the step (b) is 400-.
Further, in the anti-ultraviolet copolymerized polycarbonate, catalysts are respectively added in the step (a) and the step (b), and simultaneously, the temperature regulation and the stirring speed adopt a gradient control mode, so that the copolymerization of the anti-ultraviolet agent and the copolymerized polycarbonate is facilitated. In the polycondensation reaction, the viscosity of the resulting copolymer increases and the reaction proceeds slowly, particularly as the reaction proceeds, and the reaction becomes more difficult in the entire reaction system, particularly as the ultraviolet-resistant agent increases, so that it is necessary to appropriately adjust the reaction conditions and improve the polycondensation reaction. Meanwhile, the generated copolymerized polycarbonate is prevented from being degraded and oxidized, so that the mechanical property and the stability of the copolymerized polycarbonate are influenced.
(1) The ultraviolet-resistant copolymerized polycarbonate material prepared by the invention does not influence the optical property of bisphenol A polycarbonate.
(2) The uvioresistant copolymerized polycarbonate is prepared by introducing uvioresistant agent into the main chain of polycarbonate, belongs to block copolymerization and ensures the consistency and uniformity of products.
(3) A small amount of uvioresistant agent is introduced into the copolymerized polycarbonate material prepared by the method, so that the mechanical property of the material is improved, and the uvioresistant property of the polycarbonate is also improved.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
The experimental procedures in the following examples are conventional unless otherwise specified.
The test materials used in the following examples were purchased from a conventional reagent store unless otherwise specified.
The following description is made with reference to specific embodiments:
example one
(a) Diphenyl carbonate (DPC) is placed in a reaction kettle with a nitrogen protection device and heated to be melted, 4' -dihydroxy benzophenone ultraviolet-resistant agent and bisphenol A (BPA) are added, the DPC, the BPA and the ultraviolet-resistant agent (the molar ratio n (DPC) to n (BPA)) to n (BPA) (n (ultraviolet-resistant agent) is 1.02 to 0.7 to 0.3), the mixture is stirred uniformly, and tert-butyl potassium catalyst is added, wherein the molar ratio of the catalyst to the BPA is 1: (1X 10)-4) Adding the melted ingredients into a reaction kettle provided with a temperature controller, a stirrer and a nitrogen protection device together, and stirring at a speedThe reaction is carried out for 4 hours at the temperature of 200 ℃ with the rate adjusted to 800 r/min; (b) and adjusting the temperature to 250 ℃, adjusting the stirring speed to 600r/min, and reacting for 2h to obtain the anti-ultraviolet copolymerized polycarbonate.
Example two
(a) Diphenyl carbonate (DPC) is placed in a reaction kettle with a nitrogen protection device and heated to be melted, 4' -dihydroxy benzophenone ultraviolet-resistant agent and bisphenol A (BPA) are added, the DPC, the BPA and the ultraviolet-resistant agent (the molar ratio n (DPC) to n (BPA)) to n (BPA) to n (ultraviolet-resistant agent) is 1.1:0.75:0.35, the mixture is stirred uniformly, tert-butyl cesium catalyst is added, and the molar ratio of the catalyst to the BPA is 1: (3.5X 10)-4) Melting and mixing materials, adding the materials into a reaction kettle provided with a temperature controller, a stirrer and a nitrogen protection device, adjusting the stirring speed to 600r/min, and reacting for 2 hours at the temperature of 220 ℃; (b) adjusting the temperature to 260 ℃, adjusting the stirring speed to 400r/min, and reacting for 0.5h to obtain the anti-ultraviolet copolymerized polycarbonate.
EXAMPLE III
(a) Diphenyl carbonate (DPC) is placed in a reaction kettle with a nitrogen protection device and heated to be melted, 4' -dihydroxy benzophenone ultraviolet-resistant agent and bisphenol A (BPA) are added, the DPC, the BPA and the ultraviolet-resistant agent (the molar ratio n (DPC) to n (BPA) to n (ultraviolet-resistant agent) is 1.08 to 0.72 to 0.32), the mixture is stirred uniformly, and tert-butyl sodium catalyst is added, wherein the molar ratio of the catalyst to the BPA is 1: (3X 10)-4) Melting and mixing materials, adding the materials into a reaction kettle provided with a temperature controller, a stirrer and a nitrogen protection device, adjusting the stirring speed to 700r/min, and reacting for 3 hours at the temperature of 230 ℃; (b) adjusting the temperature to 290 ℃, adjusting the stirring speed to 500r/min, and reacting for 1.5h to obtain the anti-ultraviolet copolymerized polycarbonate.
Example four
(a) Diphenyl carbonate (DPC) is placed in a reaction kettle with a nitrogen protection device and heated to be melted, bisphenol A (BPA) and 4, 4' -dihydroxy benzophenone ultraviolet resistant agent are added, the DPC, the BPA and the ultraviolet resistant agent (the mol ratio n (DPC) to n (BPA) to n (ultraviolet resistant agent) is 1.05:0.72:0.32), the mixture is stirred evenly, tert-butyl lithium catalyst is added, the mol ratio of the catalyst to the BPA is 1: (5X 10)-4) Adding the materials after melting and mixing into a stirrer with a temperature control meterIn a reaction kettle with a nitrogen protection device, the stirring speed is adjusted to 750r/min, and the reaction is carried out for 2.5h at the temperature of 230 ℃; (b) adjusting the temperature to 280 ℃, adjusting the stirring speed to 550r/min, and reacting for 1h to obtain the anti-ultraviolet copolymerized polycarbonate.
EXAMPLE five
(a) Diphenyl carbonate (DPC) is placed in a reaction kettle which is provided with a nitrogen protection device and heated to be melted, 4' -dihydroxy benzophenone ultraviolet-resistant agent and bisphenol A (BPA) are added, the DPC, the BPA and the ultraviolet-resistant agent (the mol ratio n (DPC) to n (BPA) to n (ultraviolet-resistant agent) is 1.08 to 0.88 to 0.12), the mixture is stirred uniformly, and tert-butyl lithium catalyst is added, the mol ratio of the catalyst to the BPA is 1: (3X 10)-4) Melting and mixing materials, adding the materials into a reaction kettle provided with a temperature controller, a stirrer and a nitrogen protection device, adjusting the stirring speed to 700r/min, and reacting for 3 hours at the temperature of 230 ℃; (b) adjusting the temperature to 280 ℃, and continuously adding a tert-butyl sodium catalyst; the catalyst is added at this time in an amount of n (BPA): n (catalyst): 1: 0.5X 10-4And adjusting the stirring speed to 500r/min, reacting for 0.5h, adjusting the temperature to 260 ℃, adjusting the stirring speed to 400r/min, and reacting for 1h to obtain the anti-ultraviolet copolymerized polycarbonate.
Comparative example 1
(a) Diphenyl carbonate (DPC) is put in a reaction kettle which is provided with a nitrogen protection device and heated to be melted, bisphenol A (BPA) is added, the DPC and the BPA (the molar ratio n (DPC) to n (BPA) is 1.1:1), the mixture is stirred uniformly, and a tert-butyl lithium catalyst is added, wherein the molar ratio of the catalyst to the BPA is 1: (3X 10)-4) Melting and mixing materials, adding the materials into a reaction kettle provided with a temperature controller, a stirrer and a nitrogen protection device, adjusting the stirring speed to 600r/min, and reacting for 2 hours at the temperature of 220 ℃; (b) the temperature is adjusted to 260 ℃, the stirring speed is adjusted to 400r/min, and the reaction is carried out for 0.5h, thus obtaining the polycarbonate.
Comparative example No. two
(a) Diphenyl carbonate (DPC) is put in a reaction kettle which is provided with a nitrogen protection device and heated to be melted, bisphenol A (BPA) is added, the DPC and the BPA (the molar ratio n (DPC) to n (BPA) is 1.1:1), the mixture is stirred uniformly, and a tert-butyl lithium catalyst is added, wherein the molar ratio of the catalyst to the BPA is 1: (3X 10)-4) Melting ofAfter the materials are mixed, the mixture is added into a reaction kettle provided with a temperature controller, a stirrer and a nitrogen protection device, the stirring speed is adjusted to 600r/min, and the mixture reacts for 2 hours at the temperature of 220 ℃;
(b) adjusting the temperature to 260 ℃, adjusting the stirring speed to 400r/min, and reacting for 0.5h to obtain polycarbonate;
(c) and (c) blending the polycarbonate obtained in the step (b) with 4, 4' -dihydroxy benzophenone, wherein the molar ratio n (BPA) to n (anti-ultraviolet agent) is 0.72:0.32, and BPA and the anti-ultraviolet agent are mixed to prepare the anti-ultraviolet polycarbonate composite material.
Experimental example 1
The products obtained in examples 1 to 5 and comparative examples 1 to 2 were prepared into test specimens having a length of 127mm, a length of 12.7mm, and a thickness of 12.7 mm.
1. And (3) ultraviolet resistance performance determination: measuring the sample at 0 with a spectrophotometer0Angle of incidence and 450The transmittance of the incident angle is measured in the wavelength range of 300-380 nm.
2. And (3) flexural modulus measurement: measured according to GB/T9341, speed 2mm/min, span 64mm, bar size: (80. + -. 2) mmX (10. + -. 0.2) mmX (4. + -. 0.2) mm.
The results of the property measurements of the test samples are shown in table 1 below:
TABLE 1 results of property measurements of the samples
As can be seen from the above table, the novel anti-ultraviolet copolymerized polycarbonate prepared by the invention introduces an anti-ultraviolet agent on the main chain of the polycarbonate, belongs to block copolymerization, and simultaneously introduces bisphenol A. Compared with the prior art that the ultraviolet-resistant raw material is directly added into the polycarbonate, the compatibility is better, and the prepared polycarbonate has better mechanical property. Compared with the comparative examples 1-2, the ultraviolet resistant copolymerized polycarbonate prepared in the examples 1-5 of the invention has improved light aging resistance, and under the irradiation of ultraviolet light at the same time, the ultraviolet resistant copolymerized polycarbonate prepared in the invention is not easy to turn yellow, while the comparative examples 1-2 are easy to turn yellow. Therefore, the uvioresistant copolymerized polycarbonate prepared by the invention has good heat resistance and stability, excellent rigidity and transparency, good uvioresistant performance and is an excellent molding processing engineering material.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. A preparation method of novel uvioresistant copolymerized polycarbonate is characterized by comprising the following steps: the preparation method comprises the following steps:
(a) taking an anti-ultraviolet agent, BPA and DPC as raw materials, and reacting under a preset condition to generate a prepolymer;
(b) and (b) performing polycondensation reaction on the prepolymer in the step (a) to prepare the uvioresistant polycarbonate copolycarbonate.
2. The method for preparing a novel UV resistant copolycarbonate according to claim 1, wherein:
(a) under the protection atmosphere of inert gas, firstly placing DPC in a reaction kettle, heating to melt the DPC, then uniformly dispersing the uvioresistant agent in the molten DPC, uniformly stirring, then adding BPA and a catalyst, and reacting for 2-4h at 230 ℃ of 200-;
(b) raising the temperature of the prepolymer prepared in the step (a) to 240-290 ℃, and then stirring to continue reacting for 0.5-2h to obtain the uvioresistant polycarbonate copolycarbonate.
3. The method for preparing a novel UV resistant copolycarbonate according to claim 1, wherein: the uvioresistant agent is 4, 4' -dihydroxy benzophenone.
4. The method for preparing a novel UV resistant copolycarbonate according to claim 2, wherein: the molar ratio of the DPC, the BPA and the anti-ultraviolet agent is n (DPC), n (BPA), n (4, 4' -dihydroxy benzophenone) (1.02-1.1), 0.7-0.75 and 0.3-0.35.
5. The method for preparing a novel UV resistant copolycarbonate according to claim 1, wherein: the catalyst is an organic base catalyst.
6. The method for preparing a novel UV resistant copolycarbonate according to claim 5, wherein: the organic base catalyst comprises an alkyl metal compound, and the alkyl metal compound comprises one or more of tert-butyl lithium, tert-butyl cesium, tert-butyl potassium and tert-butyl sodium.
7. The method for preparing a novel UV resistant copolycarbonate according to claim 2, wherein: the molar ratio of the catalyst to BPA is 1: (1 to 5X 10)-4)。
8. The method for preparing a novel UV resistant copolycarbonate according to claim 2, wherein: the stirring speed in the step (a) is 600-800 r/min.
9. The method for preparing a novel UV resistant copolycarbonate according to claim 2, wherein: the stirring speed in the step (b) is 400-600 r/min.
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| US20150315380A1 (en) * | 2013-07-01 | 2015-11-05 | Lg Chem, Ltd. | Polyorganosiloxane compound, method for preparing the same, and copolycarbonate resin comprising the same |
| CN106459397A (en) * | 2014-06-20 | 2017-02-22 | 沙特基础工业全球技术有限公司 | Melt reaction process for crosslinkable polycarbonates |
| CN107075237A (en) * | 2014-06-20 | 2017-08-18 | 沙特基础全球技术有限公司 | Bridging property makrolon and the design method by its product formed |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1726246A (en) * | 2002-11-04 | 2006-01-25 | 通用电气公司 | Method for making stable, homogeneous melt solutions |
| US20150315380A1 (en) * | 2013-07-01 | 2015-11-05 | Lg Chem, Ltd. | Polyorganosiloxane compound, method for preparing the same, and copolycarbonate resin comprising the same |
| CN106459397A (en) * | 2014-06-20 | 2017-02-22 | 沙特基础工业全球技术有限公司 | Melt reaction process for crosslinkable polycarbonates |
| CN107075237A (en) * | 2014-06-20 | 2017-08-18 | 沙特基础全球技术有限公司 | Bridging property makrolon and the design method by its product formed |
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