CN112661949B - Low-yellowness polycarbonate material and preparation method thereof - Google Patents
Low-yellowness polycarbonate material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a low-yellowness polycarbonate material and a preparation method thereof, wherein a solvent removal stabilizer and a metal removal agent are added into a polycarbonate solution, wherein the dosage of the solvent removal stabilizer is 50-1000ppm, and the dosage of the metal removal agent is 50-1000 ppm. By adding the two auxiliary agents and optimizing the preparation method, on one hand, the polycarbonate solution can be ensured to be stable and not yellow in the process of removing the solvent by steam; on the other hand, the residual chromogenic metal elements in the polycarbonate solution can be complexed to form colorless substances, so that the low-yellowness polycarbonate material is obtained.
Description
Technical Field
The invention relates to a low-yellowness polycarbonate material and a preparation method thereof.
Background
Polycarbonate materials have been widely used in the fields of electronic and electric appliances, automobiles, daily necessities, and the like because of their excellent properties such as heat resistance, impact strength, and the like. At present, the production process of polycarbonate mainly adopts an interfacial phosgene method and a molten ester exchange method. When the polycarbonate material is actually processed and applied, particularly in the application fields of films, optical parts, car lamps and the like, the parts are required to avoid yellowing of colors, and the polycarbonate material is required to have low yellowness and good thermal stability. In order to obtain a polycarbonate material with low yellowness, a number of related invention patents are disclosed.
For example, patent CN 101412808A "method for producing polycarbonate" discloses a method for removing and detecting formate in sodium dithionite, which can control the content of formate in sodium dithionite, thereby inhibiting yellowing of polycarbonate caused by thermal processing. The invention patent CN 1170870C "preparation method of bisphenol sodium solution", controls the dissolved oxygen of bisphenol sodium solution of BPA batching to be lower through modes such as inert gas protection, BPA molten state batching, oxygen removal in water, thus obtain the polycarbonate material of low yellowness. Although the two methods can inhibit the processing yellowing of the polycarbonate to a certain extent by controlling the impurity content of the raw materials, on one hand, the raw materials need to be pretreated, so that the process complexity is increased, and on the other hand, the yellowing caused by metal impurities introduced by equipment and the raw materials cannot be controlled.
In patent CN 104093783B, "polycarbonate resin composition and molded article", phosphorus antioxidant and epoxidation stabilizer are added, wherein the epoxidation stabilizer can effectively inhibit the hydrolysis performance of the phosphorus antioxidant. The polycarbonate resin composition thus produced contains an antioxidant in a suitable amount, and is less likely to be discolored even if it is retained in an injection molding machine. However, this method only uses a phosphorus antioxidant to solve a part of factors causing yellowing of polycarbonate, but does not solve yellowing caused by metal impurities.
The invention patent US 8962788B 2 describes the influence of various metal elements on the yellowness of polycarbonate, wherein metal impurities such as iron, chromium and the like are introduced with equipment and raw materials, thereby influencing the yellowness of the polycarbonate.
According to the invention, the solvent removal stabilizer and the metal removal agent are added, so that the polycarbonate solution can be kept stable and not yellow in the process of removing the solvent by steam; on the other hand, the residual chromogenic metal elements in the polycarbonate solution can be complexed to form colorless substances, so that the low-yellowness polycarbonate material is obtained. And the added solvent removal stabilizer is a liquid auxiliary agent with a large molecular weight, so that the solvent removal stabilizer is not easy to migrate and separate out to the surface, and the prepared polycarbonate material has excellent surface performance.
Disclosure of Invention
The invention relates to a low-yellowness polycarbonate material and a preparation method thereof. The polycarbonate material prepared by the invention has the advantages of low yellowness, excellent surface performance and good comprehensive performance, and has good application value in the field of polycarbonate materials.
The invention aims to provide a preparation method of a low-yellowness polycarbonate material, which is characterized by comprising the following steps:
a. adding a solvent removal stabilizer and a metal removal agent into a polycarbonate solution;
b. filtering the polycarbonate solution;
c. and removing the solvent in the polycarbonate solution.
In the invention, the solvent in the polycarbonate solution is preferably removed by using steam, the solvent removal stabilizer can ensure that the polycarbonate material is kept stable and does not yellow in the process of removing the solvent by using the steam, and the metal removal agent can form a colorless complex with metal impurities and is removed by a filter before the solvent is removed, so that the polycarbonate material is prevented from being colored and yellow when the metal impurities are processed.
Furthermore, the solvent used by the polycarbonate solution is dichloromethane or chlorobenzene. The polycarbonate solution can be prepared by a phosgene method, and the solvent is a solvent in the preparation process, wherein the concentration of the polycarbonate solution is 10-50 wt%, and the weight average molecular weight of the polycarbonate is 18000-40000.
Further, the temperature of the polycarbonate solution is controlled at 20-100 ℃ in step a.
Further, the solvent removal stabilizer is a liquid phosphite antioxidant. The amount of the solvent-removing stabilizer is 50 to 1000ppm, preferably 100-800ppm, more preferably 200-600ppm, relative to the mass of the polycarbonate itself. The molecular weight of the solvent removal stabilizer is preferably more than 1000 (for example, 1100-; EGPHOS DHOP (liquid phosphite antioxidant, molecular weight 2100). The liquid phosphite antioxidant with large molecular weight is used, on one hand, the liquid phosphite antioxidant is easy to form good dispersion and mixing with the polycarbonate solution, and good effect under low dosage can be realized; on the other hand, the high molecular weight assistant is not easy to migrate and separate out to the surface of the material, and the surface performance of the material is good.
Further, the metal remover is N-salicylic acid amide phthalimide. Such as N-salicylamidophthalein phthalimide, N-salicylamidophthalein maleimide, N-salicylamidophthalein glutarimide, N-salicylamidophthalein succinimide. N-salicylic acid amide phthalyl phthalimide is preferred, and the specific molecular formula is as follows. The amount of the metal remover is 50 to 1000ppm, preferably 150-700ppm, more preferably 300-600ppm, relative to the mass of the polycarbonate itself.
The metal remover can be purchased from the market, such as MDA-5, N-salicylamidophthalimide produced by Shanghai Shinetien chemical technology Co., Ltd., molecular weight 282.
The filter accuracy (i.e. the pore size of the filter cartridge, the maximum particle size that the solution containing the impurities will pass through when passing through the filter mesh) is less than 10 μm, preferably less than 5 μm, more preferably less than 3 μm. The metal impurities forming the complex can be effectively filtered.
The steam temperature is 100-220 ℃, preferably 120-200 ℃, and more preferably 150-200 ℃. Under the steam condition, the solvent of the polycarbonate solution is effectively volatilized and removed, and the polycarbonate material is kept stable and does not yellow.
Further, the step c is carried out in a reaction kettle with a stirring speed of 50-500rpm and a gas condensation recovery system, high-temperature steam is introduced into the polycarbonate solution, and the mass ratio of the steam amount to the polycarbonate solution is controlled to be 1:5-1: 20. The polycarbonate solution is subjected to solvent removal at a certain stirring rate for 1-4h, and the removed solvent is condensed and then recovered. The steam, after condensation, forms a PC slurry with the polycarbonate.
The invention further relates to a low yellowness polycarbonate material prepared by the above method. Typically, the polycarbonate material prepared is injection molded into 3mm test pieces having a yellowness YI of less than 1.5 as measured according to ASTM E313.
The invention has the advantages that: by adding the solvent removal stabilizer and the metal removal agent, on one hand, the polycarbonate solution can be ensured to be stable and not yellow in the process of removing the solvent by steam; on the other hand, the residual chromogenic metal elements in the polycarbonate solution can be complexed to form colorless substances, so that the low-yellowness polycarbonate material is obtained. And the added solvent removal stabilizer is a liquid auxiliary agent with a large molecular weight, so that the solvent removal stabilizer is not easy to migrate and separate out to the surface, and the prepared polycarbonate material has excellent surface performance. The method is simple and easy to implement, has good effect, and has excellent effect when being applied to the field of polycarbonate material production.
Detailed Description
The present invention may be understood more readily by reference to the following detailed description of the invention and the examples included therein. It should be noted that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
The following examples and comparative examples used the following raw materials:
solvent 1: dichloromethane, manufactured by Tianjin Kemi Europe chemical reagent company;
solvent 2: the reaction mixture of chlorobenzene,
solvent removal stabilizer 1: EGPHOS 1500, liquid phosphite antioxidant, molecular weight 1112, produced by New Material science and technology Limited of evergreen trees of Jiangsu province;
solvent removal stabilizer 2: EGPHOS DHOP, liquid phosphite antioxidant, molecular weight of 2100, produced by New Material science and technology Limited of evergreen trees of Jiangsu province;
solvent removal stabilizer 3: EGPHOS DPP, liquid phosphite antioxidant, molecular weight 234, produced by Jiangsu evergreen new material science and technology limited;
solvent removal stabilizer 4: ST-330, a solid hindered phenol antioxidant, a molecular weight of 775, produced by Shanghai Shinetien chemical technology Co., Ltd;
solvent removal stabilizer 5: ST-9228, a solid phosphite antioxidant with a molecular weight of 853, produced by Shanghai Shi Xinier chemical technology Co., Ltd;
metal removing agent: MDA-5, N-salicylic acid aminophthalimide with a molecular weight of 282, produced by Shanghai Shihua Xinie chemical science and technology Co., Ltd;
example 1
Adding 50ppm (based on polycarbonate, the same below) of a solvent removal stabilizer 2 and 500ppm of a metal removal agent into a polycarbonate solution using a solvent 1 (the concentration of the polycarbonate solution is 25 wt%, the weight average molecular weight is 28000), filtering the polycarbonate solution through a filter with the precision of 1 mu m, putting the filtered polycarbonate solution into a reaction kettle (1000L) with a gas condensation recovery system at the stirring speed of 200rpm, introducing high-temperature steam (180 ℃ steam) into the polycarbonate solution, controlling the mass ratio of the steam amount to the polycarbonate solution to be 1:15, removing the solvent from the polycarbonate solution for 2 hours at a certain stirring speed, and condensing and recovering the removed solvent to obtain a polycarbonate product.
Example 2
Similar to example 1, a polycarbonate solution using solvent 1 was added with 200ppm of solvent removal stabilizer 2 and 500ppm of metal removal agent, filtered through a filter with a precision of 1 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 3
Similar to example 1, the polycarbonate solution using solvent 1 was added with 800ppm of solvent removal stabilizer 2 and 500ppm of metal removal agent, filtered through a filter with a precision of 1 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 4
Similar to example 1, the polycarbonate solution using solvent 1 was added with 1000ppm of solvent removal stabilizer 2 and 500ppm of metal removal agent, filtered through a filter with a precision of 1 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 5
Similar to example 1, the polycarbonate solution using solvent 1 was added with 500ppm of solvent removal stabilizer 2 and 50ppm of metal removal agent, filtered through a filter with a precision of 1 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 6
Similar to example 1, the polycarbonate solution using solvent 1 was added with 500ppm of solvent removal stabilizer 2 and 200ppm of metal removal agent, filtered through a filter with a precision of 1 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 7
Similar to example 1, 500ppm of solvent removal stabilizer 2 and 500ppm of metal removal agent were added to a polycarbonate solution using solvent 1, and the solution was filtered through a filter having a precision of 1 μm and the solvent was removed under the influence of steam at 180 ℃ to obtain a polycarbonate product.
Example 8
Similar to example 1, the polycarbonate solution using solvent 1 was added with 500ppm of solvent removal stabilizer 2 and 800ppm of metal removal agent, filtered through a filter with a precision of 1 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 9
Similar to example 1, the polycarbonate solution using solvent 1 was added with 500ppm of solvent removal stabilizer 2 and 1000ppm of metal removal agent, filtered through a filter with a precision of 1 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 10
Similar to example 1, 500ppm of solvent removal stabilizer 1 and 500ppm of metal removal agent were added to a polycarbonate solution using solvent 1, and the solution was filtered through a filter having a precision of 1 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 11
Similar to example 1, the polycarbonate solution using solvent 2 was added with 500ppm of solvent-removing stabilizer 2 and 500ppm of metal-removing agent, filtered through a filter with a precision of 1 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 12
Similar to example 1, 500ppm of solvent removal stabilizer 2 and 500ppm of metal removal agent were added to a polycarbonate solution using solvent 1, and the solution was filtered through a filter with a precision of 3 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 13
Similar to example 1, 500ppm of solvent removal stabilizer 2 and 500ppm of metal removal agent were added to a polycarbonate solution using solvent 1, and the solution was filtered through a filter having a precision of 10 μm, and the solvent was removed under the action of steam at 180 ℃ to obtain a polycarbonate product.
Example 14
Adding 500ppm of solvent removal stabilizer 2 and 500ppm of metal removal agent into a polycarbonate solution using solvent 1, filtering by a filter with the precision of 1 mu m, and removing the solvent under the action of steam at 100 ℃ to obtain a polycarbonate product.
Example 15
Adding 500ppm of solvent removal stabilizer 2 and 500ppm of metal removal agent into a polycarbonate solution using solvent 1, filtering by a filter with the precision of 1 mu m, and removing the solvent under the action of steam at 220 ℃ to obtain a polycarbonate product.
Comparative example 1
Adding 500ppm of solvent removal stabilizer 3 and 500ppm of metal removal agent into a polycarbonate solution using solvent 1, filtering by a filter with the precision of 1 mu m, and removing the solvent under the action of steam at 180 ℃ to obtain a polycarbonate product.
Comparative example 2
Adding 500ppm of solvent removal stabilizer 4 and 500ppm of metal removal agent into a polycarbonate solution using solvent 1, filtering by a filter with the precision of 1 mu m, and removing the solvent under the action of steam at 180 ℃ to obtain a polycarbonate product.
Comparative example 3
Adding 500ppm of solvent removal stabilizer 5 and 500ppm of metal removal agent into a polycarbonate solution using a solvent 1, filtering by a filter with the precision of 1 mu m, and removing the solvent under the action of steam at 180 ℃ to obtain a polycarbonate product.
Comparative example 4
Adding 500ppm of solvent removal stabilizer 2 and 500ppm of metal removal agent into polycarbonate solution using solvent 1, filtering by a filter with the precision of 20um, and removing the solvent under the action of steam at 180 ℃ to obtain a polycarbonate product.
Comparative example 5
Adding 500ppm of solvent removal stabilizer 2 and 500ppm of metal removal agent into a polycarbonate solution using solvent 1, filtering by a filter with the precision of 1 mu m, and removing the solvent under the action of steam at 250 ℃ to obtain a polycarbonate product.
Comparative example 6
Adding 500ppm of solvent to a polycarbonate solution using a solvent 1 to remove a stabilizer 2, filtering the solution through a filter with the precision of 1 mu m, and removing the solvent under the action of steam at 180 ℃ to obtain a polycarbonate product.
Comparative example 7
Adding 500ppm of metal remover into a polycarbonate solution using a solvent 1, filtering by a filter with the precision of 1 mu m, and removing the solvent under the action of steam at 180 ℃ to obtain a polycarbonate product.
The polycarbonate products prepared in the above examples and comparative examples were dried and injection molded to test their performance, wherein the drying and injection molding processes are all known parameters in the polycarbonate processing industry, and the parameters and processing equipment used in the examples and comparative examples were consistent.
The results of testing the properties of the injection-molded articles of polycarbonate material prepared in the examples and comparative examples are given in table 1, wherein:
yellowness of test piece: the yellowness YI of the 3mm test pieces was measured according to ASTM E313, the measuring instrument being a VIS color difference meter from HUNTER LAB.
Haze and light transmittance: the test pieces were 3mm thick and the test apparatus was a HAZE meter of HAZE-GARP PLUS from BYK, measured according to ASTM D1003.
Notched impact strength was measured according to ASTM D256 under 23 ℃ and with a tester of the type CEAST9050 pendulum impact tester.
The tensile strength was measured according to ASTM D638 under the test conditions of a tensile speed of 50mm/min and a test apparatus of a CMT4104-BZ microcomputer-controlled electronic universal tester available from MTS.
TABLE 1 table of properties of examples and comparative examples
When the polycarbonate material is actually processed and applied, the requirements on the yellowness, the surface property, the mechanical property and the like are high. The surface properties are mainly reflected in haze and light transmittance, and the mechanical properties are represented by impact strength and tensile strength.
As can be seen from the comparative examples, the addition of the solvent removal stabilizer with a low molecular weight or in a solid state, the use of a low-precision filter, the removal of the solvent at an excessively high temperature, the absence of the addition of a metal removal agent, the absence of the addition of a solvent removal stabilizer, and the like does not allow the achievement of low yellowness and good surface properties.
In conclusion, the low-yellowness polycarbonate material disclosed by the invention has the characteristics of low yellowness, good surface property and excellent mechanical property by adding the solvent removal stabilizer and the metal removal agent into the polycarbonate solution and optimizing the preparation process, and the comprehensive property of the low-yellowness polycarbonate material is far better than that of each comparative example.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (13)
1. A preparation method of a low-yellowness polycarbonate material is characterized by comprising the following steps:
a. adding a solvent removal stabilizer and a metal removal agent into a polycarbonate solution;
b. filtering the polycarbonate solution through a filter;
c. the solvent in the polycarbonate solution is removed,
wherein the solvent removal stabilizer is a liquid phosphite antioxidant;
in the step c, the solvent in the polycarbonate solution is removed by adopting steam,
the molecular weight of the solvent removal stabilizer is more than 1000,
the metal remover is N-salicylic acid aminophthalimide with the following molecular formula:
the precision of the filter is less than 10 mu m,
the steam temperature is 100-220 ℃.
2. The method according to claim 1, wherein the solvent used in the polycarbonate solution is dichloromethane or chlorobenzene.
3. The method according to claim 1 or 2, wherein the polycarbonate solution is a polycarbonate solution prepared by a phosgene method, and the solvent is a solvent contained in the preparation process, wherein the concentration of the polycarbonate solution is 10wt% to 50wt%, and the weight average molecular weight of the polycarbonate is 18000-40000.
4. The method according to claim 1, wherein the temperature of the polycarbonate solution in the step a is controlled to be 20 to 100 ℃.
5. The process according to claim 1 or 2, wherein the amount of the solvent-removing stabilizer is 50 to 1000ppm based on the mass of the polycarbonate itself.
6. The process according to claim 5, wherein the amount of the solvent-removal stabilizer is 100-800ppm relative to the mass of the polycarbonate itself.
7. The process according to claim 6, wherein the amount of the solvent-removal stabilizer is 200-600ppm relative to the mass of the polycarbonate itself.
8. The method of claim 1, wherein the filter precision is less than 5 μm.
9. The method of claim 8, wherein the filter precision is less than 3 μm.
10. The method as claimed in claim 1, wherein the steam temperature is 120-200 ℃.
11. The method as claimed in claim 10, wherein the steam temperature is 150 ℃ to 200 ℃.
12. The method according to claim 1 or 2, wherein the step c is performed in a reaction kettle with a stirring speed of 50-500rpm and a gas condensation recovery system, high-temperature steam is introduced into the polycarbonate solution, and the mass ratio of the steam amount to the polycarbonate solution is controlled to be 1:5-1: 20.
13. The method according to claim 12, wherein the polycarbonate solution is removed for 1 to 4 hours, and the removed solvent is condensed and recovered.
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| CN107674322A (en) * | 2017-10-19 | 2018-02-09 | 中广核俊尔（上海）新材料有限公司 | Thermoplastic resin heat oxygen aging resistance master batch and preparation method thereof |
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| JPS5247844A (en) * | 1975-10-15 | 1977-04-16 | Ube Ind Ltd | Elastomer compositions |
| CN1355821A (en) * | 1999-06-11 | 2002-06-26 | 通用电气公司 | Polycarbonate production method |
| CN103709442A (en) * | 2013-11-21 | 2014-04-09 | 双键化工（上海）有限公司 | Stabilizer and composition comprising the same |
| CN104629347A (en) * | 2015-01-30 | 2015-05-20 | 上海日之升新技术发展有限公司 | Metal ageing resisting type enhanced nylon material and preparation method thereof |
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