CN110885468B - Method for reducing internal stress of polycarbonate and modified product thereof - Google Patents
Method for reducing internal stress of polycarbonate and modified product thereof Download PDFInfo
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- CN110885468B CN110885468B CN201911164903.2A CN201911164903A CN110885468B CN 110885468 B CN110885468 B CN 110885468B CN 201911164903 A CN201911164903 A CN 201911164903A CN 110885468 B CN110885468 B CN 110885468B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a method for reducing internal stress of polycarbonate and a modified product thereof, which comprises the following steps: soaking the polycarbonate or the modified product workpiece thereof in an alcohol solution for 0.1-2 h at 0-50 ℃. The research of the invention finds that the low-concentration micromolecular alcohol solution can promote the molecular chain rearrangement of the stress concentration point of the polycarbonate and the modified product thereof, further reduce the internal stress of the polycarbonate and the modified product thereof, be beneficial to improving the internal stress of the product under the condition of not influencing the dimensional stability of the finished piece, and prevent the phenomena of warping deformation, silver streaks, weak impact resistance and the like of the product caused by large internal stress.
Description
Technical Field
The invention relates to an internal stress treatment method, in particular to a method for reducing the internal stress of polycarbonate and a modified product thereof, belonging to the technical field of polycarbonate materials.
Background
Polycarbonate and a modified product thereof mean a composition containing polycarbonate as a main component, and are very common materials in daily life. Because of good mechanical property, heat resistance, appearance property and excellent processing property, the polycarbonate and the modified products thereof are widely applied to the fields of automobiles, electronic and electrical equipment, illumination, medical appliances, national defense industry and the like.
However, because the polycarbonate molecular chain has high rigidity, the products of the polycarbonate and the modified products thereof are easy to have relatively large internal stress. These internal stresses can cause undesirable phenomena such as warping, deformation, crazing and the like in the use process of the polycarbonate and the modified product thereof in the future. Especially, under the impact of external force, the polycarbonate and the modified products thereof are easy to crack, break and other failure behaviors.
The main method for eliminating the internal stress of polycarbonate plastic products is annealing, in particular, polycarbonate and modified products thereof are placed in a higher temperature environment for a period of time and then are controlled to cool at a proper speed. Publication CN106832377A describes a method for preparing a polycarbonate optical spherical cap, which reduces the internal stress of the product by heat treatment. The patent publication CN108016023A describes a preparation method of polylactic acid and a copolymer stent thereof, and the internal stress of a tube can be effectively released by placing the tube after inflation at an annealing temperature for annealing for 5-30 minutes, so that the shelf life of the stent can be prolonged.
Although the annealing process can reduce the internal stress of polycarbonate and modified products thereof at present, the heat treatment of workpieces can cause the defect of changing the size of products, which cannot meet the application requirements in the field with higher requirements on the size of the products.
Disclosure of Invention
The invention aims to provide a method for reducing internal stress of polycarbonate and a modified product thereof, and the internal stress of the product can be obviously reduced under the condition of no size change of the polycarbonate and the modified product thereof treated by the method, thereby being beneficial to prolonging the service life and the application range of the product.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for reducing the internal stress of polycarbonate and modified products thereof, comprising the steps of: soaking the polycarbonate or the modified product workpiece thereof in an alcohol solution for 0.1-2 h at 0-50 ℃.
Further, the alcohol solution is an aqueous solution with the alcohol content of 0.5-10 wt%, and preferably an aqueous solution with the alcohol content of 0.8-5 wt%.
Further, the alcohol in the alcohol solution is C1-3 small molecular monohydric alcohol and/or polyhydric alcohol.
Further, the alcohol in the alcohol solution is monohydric alcohol and/or polyhydric alcohol with the hydroxyl number less than or equal to 3.
Further, the alcohol in the alcohol solution is one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, 1, 2-propanediol, 1, 3-propanediol and glycerol.
Further, the alcoholic solution soaking treatment time is 0.3-1.5 h.
Further, the temperature of the alcoholic solution soaking treatment is 10-45 ℃.
Further, the polycarbonate is pure polycarbonate with a melt flow index of 3-65 g/10min, preferably 5-50 g/10min, and more preferably 7-35 g/10min at 300 ℃ and 1.2 kg.
Further, the polycarbonate modified product comprises polycarbonate/ABS alloy, polycarbonate/PBT alloy, polycarbonate/PET alloy, polycarbonate/ASA alloy and polycarbonate toughening product.
Further, the polycarbonate/ABS alloy comprises a product with the following information of product sale brand: vanhua chemical CA1356, CA1450, CA1510PG, CA1560, CA1630, CA1660, CA1730, golden hair MAC301, MAC451, MAC501, MAC601, MAC701, MAC751, Taiwan chemical AC2000, AC2300, AC2500, AC3100, Qimei PC-330, PC-345, PC-365, PC-385, Corsaikosa T45PG, T50XF, T65XF, T65PG, T85XF, T90XF, Pridel CB1230, CB2340, Letian GW-1014, HA-1011, HP-1000H, HP-1000P, Sabike C1200HF, SCY620S, SCY630, MC 1300; LG chemical HR5007A, GP5006B, GP5008A, HG5000S, HI5002A, HR5007AT, NS 5000;
preferably, the polycarbonate/PBT alloy comprises a product having a product sales designation of: wanhua chemical CB1221, CB1321, CB3250, CB, Corsichu UT5205, UT4045G, UT6007, S7916, Saebik 5720U, X5600WX, X4820, X4830, X4850, 1670E, 6370, V3900W, Jinhui Nieli HCB9230, HCB9240, HCB9310G, LG chemical TE5011, 5011M, Jinfa Lonoy 1200 and Lonoy 1600.
Preferably, the polycarbonate/PET alloy comprises a product sold under the following information: wanhua chemical CE1631, CE1820, CE6820, Corsaikoku DP7645, DP7665, UT203, UT305, UT403, UT408, EL700, EL703, sabick X2300UV, X2500UV, XL1339, X5630Q, Jinhuilanli HTC6060, KCA9360, KCA9362, KCA9341, and Jinfa lonoy 2100 LT.
Preferably, the polycarbonate/ASA alloy comprises the following information on the product sale: wanhua chemical CS1530, CS1730, Saebick HRA222, XP4025, XP4034, XP7550, XP7560, Jinhuili HSC7045, HSC7060, HSC7079 and HSC 7079Z.
Preferably, the polycarbonate toughened product comprises a product having a product sales designation of: wanhua chemical CR1821, CR1840, Letian CF-1070, LG chemical SC 1004A.
The forming method of the polycarbonate and the modified product thereof comprises but is not limited to injection molding, extrusion, blow molding, casting, pressing, 3D printing and the like.
The research of the invention finds that the low-concentration micromolecular alcohol solution can promote the molecular chain rearrangement of the stress concentration point of the polycarbonate and the modified product thereof, further reduce the internal stress of the polycarbonate and the modified product thereof, be beneficial to improving the internal stress of the product under the condition of not influencing the dimensional stability of the finished piece, and prevent the phenomena of warping deformation, silver streaks, weak impact resistance and the like of the product caused by large internal stress.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The raw materials and sources of the product are as follows:
a1105, pure polycarbonate product, melt flow index 10g/10min (test conditions 300 ℃, 1.2kg), Vanhua chemical group GmbH;
CA1560, polycarbonate/ABS products, Vanhua chemical group, Inc.;
CB1221, polycarbonate/PBT products, Vanhua chemical group, Inc.;
CE1631, polycarbonate/PET products, Vanhua chemical group, Inc.;
CS1530, polycarbonate/ASA products, Vanhua chemical group, Inc.;
CR1840, polycarbonate toughened products, Vanhua chemical group, Inc.
The polycarbonate and the modified product thereof are used for preparing tensile sample strips and square plate sample strips by injection molding. Wherein tensile bars are used to test internal stresses and have dimensions in accordance with ASTM D638; the square plate bars were used to test the dimensional stability and had dimensions of 365mm by 100mm by 3 mm.
(1) The concrete operation steps of soaking the sample strips by the alcohol solution are as follows:
and (3) pouring the alcohol solution with the specific solubility into a beaker, placing the beaker into a water bath kettle, and regulating the temperature of the alcohol solution through the water bath kettle. The stretched and square plate bars were placed in an alcohol solution to completely submerge all bars. After a specified time of soaking, all the strips were removed from the alcohol solution and rinsed in running water for 2 minutes and then wiped dry with a paper towel.
(2) The specific operation steps for processing the sample strip by annealing are as follows:
and putting the stretched sample strips and the square plate sample strips into an oven, heating at a specific temperature for a specific time, taking all the sample strips out of the oven, and naturally cooling for later use.
(3) Internal stress testing method
And bending the treated tensile sample strip along the arc curved surface, so that the whole sample strip is tightly attached to the arc curved surface and fixed. And selecting a proper arc surface to ensure that the bending deformation of the tensile sample strip reaches 1.5 percent. The middle part of the tensile sample strip was wiped with absorbent cotton stained with carbon tetrachloride, and the time at which the tensile sample strip cracked was observed and recorded. Longer times represent less internal stress.
(4) Dimensional stability test method
The dimensions of the long side of the square plate bar before and after the treatment were recorded, and the amount of change was calculated.
Examples 1 to 12 were set up according to method (1) except that the polycarbonate samples shown in Table 1 were immersed in an alcohol solution, and the difference in treatment temperature and time was observed;
comparative examples 1 to 6 were set according to the method (2) except for differences in heat treatment temperature, time of the polycarbonate samples shown in Table 1;
the samples without any treatment were designated as comparative examples 7 to 12, respectively, differing only in the polycarbonate samples shown in Table 1.
TABLE 1 Distinguishing parameters in the examples and comparative examples
The samples of the examples and comparative examples were tested for internal stress and dimensional stability according to the methods of (3) and (4), and the test results are shown in table 2:
table 2 results of performance testing
Note: the size change value is a positive number, which indicates that the size becomes larger; the dimensional change value is negative, indicating a decrease in size.
By comparing examples 1-12 with comparative examples 7-12, it can be seen that, after the treatment of soaking in an alcohol solution, whether pure polycarbonate or various polycarbonate-modified products, the time for cracks to appear in the tensile bar stress test is obviously increased, which indicates that the internal stress of the products is obviously reduced, and proves that the treatment of an alcohol aqueous solution is an effective method for reducing the internal stress of the polycarbonate and the modified products thereof.
As can be seen from the comparison of examples 1 to 12 with comparative examples 1 to 6, the polycarbonate and the modified product thereof underwent annealing treatment, and although the time for occurrence of cracks became long, the square plate bars correspondingly underwent a large change in size, indicating that the heat treatment deteriorated the dimensional stability of the polycarbonate and the modified product thereof. After the polycarbonate and the modified product thereof are soaked in the alcohol solution, not only the internal stress is reduced, but also the size of the sample strip is almost unchanged, which shows that compared with the traditional annealing treatment method, the solution soaking method has the advantage of not influencing the dimensional stability of the polycarbonate and the modified product thereof, and is suitable for large-scale popularization and application.
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 (16)
1. A method for reducing the internal stress of polycarbonate and modified products thereof, which is characterized by comprising the following steps: soaking a polycarbonate or a modified product of the polycarbonate in an alcohol solution for 0.1-2 h at 0-50 ℃; the alcohol solution is an aqueous solution with the alcohol content of 0.5-10 wt%.
2. The method for reducing the internal stress of polycarbonate and modified products thereof as claimed in claim 1, wherein the alcohol solution is an aqueous solution with an alcohol content of 0.8-5 wt%.
3. The method for reducing the internal stress of the polycarbonate and the modified product thereof according to claim 1, wherein the alcohol in the alcohol solution is a C1-3 small-molecule monohydric alcohol and/or polyhydric alcohol.
4. The method for reducing the internal stress of polycarbonate and modified products thereof as claimed in claim 3, wherein the alcohol in the alcohol solution is monohydric alcohol and/or polyhydric alcohol with hydroxyl number less than or equal to 3.
5. The method for reducing the internal stress of polycarbonate and modified products thereof as claimed in claim 4, wherein the alcohol in the alcohol solution is one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, 1, 2-propanediol, 1, 3-propanediol and glycerol.
6. The method for reducing the internal stress of the polycarbonate and the modified product thereof according to any one of claims 1 to 5, wherein the soaking treatment time of the alcoholic solution is 0.3 to 1.5 hours.
7. The method for reducing the internal stress of the polycarbonate and the modified product thereof according to any one of claims 1 to 5, wherein the temperature of the alcoholic solution soaking treatment is 10 to 45 ℃.
8. The method for reducing the internal stress of polycarbonate and modified products thereof according to any one of claims 1 to 5, wherein the polycarbonate has a melt flow index of 3 to 65g/10min at 300 ℃ and 1.2 kg.
9. The method for reducing the internal stress of polycarbonate and modified products thereof as claimed in claim 8, wherein the polycarbonate has a melt flow index of 5-50 g/10min at 300 ℃ and 1.2 kg.
10. The method for reducing the internal stress of polycarbonate and modified products thereof according to claim 9, wherein the polycarbonate is pure polycarbonate with a melt flow index of 7-35 g/10min at 300 ℃ and 1.2 kg.
11. The method for reducing the internal stress of the polycarbonate and the modified product thereof as claimed in any one of claims 1 to 5, wherein the polycarbonate modified product comprises polycarbonate/ABS alloy, polycarbonate/PBT alloy, polycarbonate/PET alloy, polycarbonate/ASA alloy and polycarbonate toughening product.
12. The method of reducing the internal stress of polycarbonates and their modified products as claimed in claim 11, wherein said polycarbonate/ABS alloy comprises wanhua chemical CA1356, CA1450, CA1510PG, CA1560, CA1630, CA1660, CA1730, blonde MAC301, MAC451, MAC501, MAC601, MAC701, MAC751, platformized AC2000, AC2300, AC2500, AC3100, qimei PC-330, PC-345, PC-365, PC-385, kesikogaku T45PG, T50XF, T1014 65XF, T65PG, T85XF, T90XF, priatecb 1230, 234cb 0, lentian GW-1011, HA-1011, HP-1000H, HP-1000P, sabick C1200HF, SCY620S, SCY630, MC 1300; LG chemistry HR5007A, GP5006B, GP5008A, HG5000S, HI5002A, HR5007AT, NS 5000.
13. The method of reducing the internal stress of polycarbonates and their modified products as claimed in claim 12, wherein said polycarbonate/PBT alloys include wanhua chemical CB1221, CB1321, CB3250, CB, koshiwa UT5205, UT4045G, UT6007, S7916, sabick 5720U, X5600WX, X4820, X4830, X4850, 1670E, 6370, V3900W, jin lake zuri HCB9230, HCB9240, HCB9310G, LG chemical TE5011, TE5011M, jinfa loney 1200, loney 1600.
14. The method of reducing the internal stress of polycarbonates and their modified products according to claim 12, wherein said polycarbonate/PET alloys comprise warfarin chemical CE1631, CE1820, CE6820, koshichu DP7645, DP7665, UT203, UT305, UT403, UT408, EL700, EL703, sabic X2300UV, X2500UV, XL1339, X5630Q, brocade lake flory HTC6060, KCA9360, KCA9362, KCA9341, jindo 2100 LT.
15. The method of reducing the internal stress of polycarbonate and modified products thereof of claim 12, wherein the polycarbonate/ASA alloy comprises wanhua chemical CS1530, CS1730, sabik HRA222, XP4025, XP4034, XP7550, XP7560, jinhu rai HSC7045, HSC7060, HSC 7079Z.
16. The method for reducing the internal stress of polycarbonate and modified products thereof as claimed in claim 12, wherein the polycarbonate toughening products comprise Wanhua chemical CR1821, CR1840, Letian CF-1070, LG chemical SC 1004A.
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| CN113956522B (en) * | 2021-11-10 | 2023-06-02 | 长春工业大学 | Preparation method of high-strength polyurethane product |
| CN114507435A (en) * | 2022-01-20 | 2022-05-17 | 浙江海圣医疗器械股份有限公司 | Medical chemical-resistant transparent polycarbonate composition and preparation method thereof |
| CN114953523B (en) * | 2022-05-23 | 2023-10-13 | 湖北工业大学 | Method for reducing internal stress of polymer product |
| CN116712601B (en) * | 2022-12-23 | 2023-12-26 | 杭州启明医疗器械股份有限公司 | Implantable material, artificial prosthesis, artificial heart valve and preparation method |
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| JP2017065172A (en) * | 2015-09-30 | 2017-04-06 | 大日本印刷株式会社 | Method for producing polycarbonate molded product with hard coat layer |
| CN109897356A (en) * | 2017-12-08 | 2019-06-18 | 万华化学集团股份有限公司 | A kind of polycarbonate compositions of high heat resistance and preparation method thereof |
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| CN1338488A (en) * | 2000-08-18 | 2002-03-06 | 苏峰白 | Refractory high-molecular polymer composition able to quickly release internal stress and its preparing process |
| CN102532570A (en) * | 2010-12-08 | 2012-07-04 | 比亚迪股份有限公司 | Stress relieving method of polycarbonate material |
| JP2017065172A (en) * | 2015-09-30 | 2017-04-06 | 大日本印刷株式会社 | Method for producing polycarbonate molded product with hard coat layer |
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