CN112538240B - polycarbonate/PCT polyester composition and preparation method and application thereof - Google Patents
polycarbonate/PCT polyester composition and preparation method and application thereof Download PDFInfo
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- CN112538240B CN112538240B CN202011371298.9A CN202011371298A CN112538240B CN 112538240 B CN112538240 B CN 112538240B CN 202011371298 A CN202011371298 A CN 202011371298A CN 112538240 B CN112538240 B CN 112538240B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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Abstract
The invention discloses a polycarbonate/PCT polyester composition which comprises the following components in parts by weight: 100 parts of PCT resin; 10-50 parts of polycarbonate resin; 0.05-1 part of hyperbranched polyester, wherein the molecular weight is 1000-11000g/mol, and the number of carboxyl groups is 4-48/mol. The polycarbonate/PCT polyester composition provided by the invention overcomes the technical defect of poor mechanical property of PCT resin, and also overcomes the defect of poor UV resistance of PCT resin and PC resin compositions.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polycarbonate/PCT polyester composition and a preparation method and application thereof.
Background
The advent of Light Emitting Diodes (LEDs) has brought the lighting industry into the semiconductor lighting era. The LED light source has the advantages of high reliability, high luminous power, low power consumption, high corresponding speed, long service life, low price, rich colors and the like. Following gas lighting, incandescent lamps and fluorescent lamps, LEDs are becoming a new generation of mainstream lighting technology. With the development of the times and the progress of science and technology, LEDs have been widely used in various fields such as street lamps, indoor lighting, backlight display screens, automobile headlamps, landscape lamps, and the like. The LED bracket is used as a chip carrier, has both the electric conduction function and the heat conduction function, and is an indispensable key auxiliary material for LED devices. The materials used as LED support are mainly high temperature resistant polyamide (PPA) and high temperature resistant polyester (polycyclohexylenedimethylene terephthalamide, PCT). The high-temperature resistant polyamide (mainly comprising PA46, PA6T and PA 9T) has high initial whiteness, good heat resistance, high fluidity, suitability for injection molding process and low cost, and is the mainstream material of the LED bracket at present. However, the photo-thermal aging of the PPA material is relatively fast, and the PPA material can only be used for low-power products at present. With the introduction of high-voltage LEDs, PCT has great advantages in application to medium and high power LED supports due to excellent high-temperature discoloration resistance.
Chinese patent applications 202010426329X and 202010452425.1 disclose the use of hyperbranched polyester resins in PCT resin compositions, which can improve the binding force between molded articles made from the polyester resin compositions and silica gel, so that the molded articles are not easily separated from silica gel, and have high reflectance after the addition of white pigment. However, the above two PCT resin compositions have poor mechanical properties, and require the addition of a large amount of reinforcing materials, such as glass fibers, wollastonite, potassium titanate whiskers, kaolin, talc or mica, which tend to lower the light transmittance of the PCT resin compositions.
Disclosure of Invention
The invention aims to provide a polycarbonate/PCT polyester composition which has the technical advantages of good mechanical property and UV aging resistance.
Another object of the present invention is to provide a process for the preparation and use of the polycarbonate/PCT polyester compositions.
The invention is realized by the following technical scheme:
a polycarbonate/PCT polyester composition comprises the following components in parts by weight:
100 parts of PCT resin;
10-50 parts of polycarbonate resin;
0.05 to 1 portion of hyperbranched polyester,
wherein the molecular weight is 1000-11000g/mol, and the number of carboxyl groups is 4-48/mol.
Preferably, 0.3 to 0.6 part of hyperbranched polyester.
The intrinsic viscosity of the PCT resin is 0.6-0.8 dL/g.
Preferably, the polycarbonate resin has a melt mass flow rate of 10 to 30g/10min, under the conditions of 300 ℃ and 1.20 kgf.
Preferably, the molecular weight of the hyperbranched polyester is 2000-10000g/mol, and the number of carboxyl groups is 12-48/mol.
The hydroxyl-terminated hyperbranched polyester can be carboxyl-terminated aliphatic hyperbranched polyester and/or carboxyl-terminated aromatic hyperbranched polyester. The hyperbranched polyesters used herein are commercially available.
In order to further improve the mechanical property, the material also comprises 0 to 20 parts of reinforcing material by weight; the reinforcing material is at least one of glass fiber, wollastonite, potassium titanate whisker, kaolin, talc and mica.
The polycarbonate/PCT polyester composition of the present invention may further contain additives such as antioxidants, impact modifiers, flame retardants, optical brighteners, lubricants, plasticizers, thickeners, antistatic agents, nucleating agents, UV stabilizers, mold release agents, dyes, etc., as needed.
The preparation method of the polycarbonate/PCT polyester composition comprises the following steps: uniformly mixing the PCT resin, the polycarbonate resin and the reinforcing material, then carrying out melt blending on the mixture and the hyperbranched polyester through a double-screw extruder, and carrying out extrusion granulation to obtain the polyester resin composition, wherein the temperature of the double-screw extruder is set to be 230-300 ℃.
The polycarbonate/PCT polyester composition is used for preparing an LED reflecting plate.
The invention has the following beneficial effects:
according to the invention, a certain amount of PC resin is added into the PCT resin, so that the mechanical property can be improved. But because the compatibility of the PCT resin and the PC resin is poor, the compatibility problem is solved by adding a certain amount of hyperbranched polyester with specific parameters. It has been unexpectedly found that the resistance of the PCT resin/PC resin composition to ultraviolet light is improved by adding the hyperbranched polyester. This was analyzed because the molecular chains of PC and PCT were partially broken when PCT was extruded in a blend with PC. The hyperbranched polyester contains a large amount of carboxyl, and can react with end groups generated by the fracture of PCT resin and PC resin to link two molecules through chemical bonds. Thus, the cyclohexyl groups in the PCT molecular chain will be evenly distributed in the composition. In this case, higher energy is required for the transition of the cyclohexyl electron to the transition state, the molecular chain stability is better under UV irradiation, and the UV resistance of the composition is higher.
Detailed Description
The present invention will be further illustrated by the following specific examples and comparative examples, which are preferred embodiments of the present invention, but the present invention is not limited to the following examples, and is not particularly limited to the types of raw materials of the components used in the following specific examples.
The following examples and comparative examples use starting materials derived from commercially available products.
PCT resin-A: the intrinsic viscosity was: 0.719dL/g, Istman Chemical Products, Inc. (Eastman Chemical Products), PCT 36296;
PCT resin-B: the intrinsic viscosity is: 0.65dL/g, SK chemistry (SK Chemicals), 0302;
PCT resin-C: the intrinsic viscosity was: 0.75dL/g, SK chemistry (SK Chemicals), 0502;
PC resin-A: the melt mass flow rate is 15 g/10min, from Mitsubishi engineering plastics, S-3000R, and the melt mass flow rate test temperature is 300oC, the load is 1.20 kgf;
PC resin-B: the melt mass flow rate was 7.5 g/10min from Mitsubishi engineering plastics, S-1000R, and the melt mass flow rate test temperature was 300oC, the load is 1.20 kgf;
PC resin-C: melt mass flow rate of 63 g/10min from Mitsubishi engineering plastics, H-4000, melt mass flow rate test temperature of 300oC, the load is 1.20 kgf;
hyperbranched polyester-A: molecular weight is 2100g/mol, carboxyl number is 12/mol, Wuhan hyperbranched resin science and technology Limited;
hyperbranched polyester-B: molecular weight of 5200g/mol, carboxyl number of 24/mol, Wuhan hyperbranched resins science and technology Limited;
hyperbranched polyester-C: molecular weight of 9800g/mol, carboxyl number of 48/mol, Wuhan super-branched resin science and technology Limited;
hyperbranched polyester-D: molecular weight of 1200g/mol, number of carboxyl groups of 4/mol, Wuhan hyperbranched resin science and technology Limited;
hyperbranched polyester-E: molecular weight of 950 g/mol, number of carboxyl groups of 6/mol, Wuhan hyperbranched resins science and technology Limited;
hyperbranched polyester-F: molecular weight is 12000g/mol, carboxyl number is 48/mol, Wuhan hyperbranched resin science and technology Limited;
glass fiber: f7x 28: NITTO BOSEKI, Japan; the glass fiber consists of short glass fiber CSG3PA-820, silica 60-67 wt% and alumina 33-40 wt%, wherein the short glass fiber CSG comprises E-glass with the length of 3mm, the main cross section axis of 28 microns, the auxiliary cross section axis of 7 microns and the axial ratio of 4 (non-circular cross section).
Examples and comparative examples preparation method of polyester resin composition: uniformly mixing PCT resin, polycarbonate resin and glass fiber, then carrying out melt blending with hyperbranched polyester through a double-screw extruder, and carrying out extrusion granulation to obtain the polyester resin composition, wherein the temperature of the double-screw extruder is set to be 230-300 ℃.
The performance test method comprises the following steps:
(1) and (3) testing mechanical properties: the tensile strength is tested according to GB/T1447-2005 tensile property test method for fiber reinforced plastics, and the bending strength is tested according to GB/T1449-2005 bending property test method for fiber reinforced plastics.
(2) UV resistance: the light transmittance of the sample was measured on the sample after irradiating the sample with an LED light source at a wavelength of 460nm for 500 hours in a constant temperature oven at 85 ℃ and 85% RH.
Table 1: EXAMPLES 1-9 polycarbonate/PCT polyester compositions the amounts of the ingredients (parts by weight) and the results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Example 9 | |
| PCT resin-A | 100 | 100 | 100 | 100 | 100 | 100 | 100 | ||
| PCT resin-B | 100 | ||||||||
| PCT resin-C | 100 | ||||||||
| PC resin-A | 12 | 25 | 25 | 25 | 40 | 50 | 50 | 50 | 50 |
| Hyperbranched polyester-A | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.1 | 0.3 | 1 |
| Glass fiber | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Tensile strength/MPa | 41 | 51 | 50 | 54 | 56 | 61 | 59 | 60 | 58 |
| Flexural Strength/MPa | 59 | 70 | 70 | 72 | 73 | 77 | 75 | 77 | 74 |
| UV aged transmittance,% | 74.5 | 73.4 | 73.6 | 73.1 | 72.1 | 71.5 | 70.1 | 73.9 | 70.8 |
As can be seen from examples 2 to 4, the technical solution of the present application is applicable to the existing PCT resin that can be applied to LED holders.
From example 1/2/5/6, it is clear that the polycarbonate content is increased. Tensile strength and flexural strength increase, but UV aging resistance decreases. Referring again to example 7/8/9, it can be seen that the preferred amount of hyperbranched polyester added further inhibits UV aging.
Table 2: EXAMPLES 10-15 polycarbonate/PCT polyester compositions the amounts of the ingredients (parts by weight) and the results
| Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | |
| PCT resin-A | 100 | 100 | 100 | 100 | 100 | 100 |
| PC resin-A | 25 | 25 | 25 | 25 | ||
| PC resin-B | 25 | |||||
| PC resin-C | 25 | |||||
| Content of hyperbranched polyester | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 | 0.6 |
| Hyperbranched polyester type | A | A | B | C | D | A |
| Glass fiber | 5 | 5 | 5 | 5 | 5 | |
| Tensile strength/MPa | 54 | 48 | 50 | 48 | 47 | 44 |
| Flexural Strength/MPa | 73 | 66 | 71 | 68 | 67 | 62 |
| UV aged transmittance% | 73.3 | 70.4 | 73.5 | 70.3 | 71.0 | 76.5 |
As is clear from example 2/10/11, the polycarbonate preferably has a melt mass flow rate of 10 to 30g/10min under the conditions of 300 ℃ and 1.20 kgf.
From example 2/12/13/14, it is preferable that the molecular weight is 2000-10000g/mol and the number of carboxyl groups is 12-48/mol.
Table 3: comparative polycarbonate/PCT polyester composition the amounts of the ingredients (parts by weight) and the results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| PCT resin-A | 100 | 100 | 100 | 100 | 100 | 100 |
| PC resin-C | 25 | 25 | 25 | 25 | 80 | |
| Content of hyperbranched polyester | 0.6 | 0.6 | 2 | 1 | ||
| Hyperbranched polyester species | E | F | A | A | A | |
| Glass fiber | 5 | 5 | 5 | 5 | 5 | 5 |
| Tensile strength/MPa | 40 | 37 | 30 | 34 | 66 | 33 |
| Flexural Strength/MPa | 52 | 49 | 41 | 46 | 82 | 45 |
| UV aged transmittance,% | 67.5 | 68.1 | 66.2 | 65.2 | 63.1 | 63.5 |
It is understood from comparative example 1/2 that the improvement of UV aging performance is not significant when the molecular weight and the number of carboxyl groups of the hyperbranched polyester are not within the ranges defined in the present application.
From comparative example 3/4, it is clear that too high a content of hyperbranched polyester would on the contrary reduce the mechanical properties.
From comparative example 5, it is clear that too high a content of polycarbonate, although improving the mechanical properties of the composition, further reduces the UV aging resistance.
Claims (8)
1. A polycarbonate/PCT polyester composition is characterized by comprising the following components in parts by weight:
100 parts of PCT resin;
10-50 parts of polycarbonate resin;
0.05 to 1 portion of hyperbranched polyester,
wherein the molecular weight of the hyperbranched polyester is 1000-11000g/mol, and the number of carboxyl groups is 4-48/mol.
2. The polycarbonate/PCT polyester composition of claim 1, wherein the hyperbranched polyester is 0.3 to 0.6 parts.
3. The polycarbonate/PCT polyester composition of claim 1, wherein said PCT resin has an intrinsic viscosity of 0.65 to 0.75 dL/g.
4. The polycarbonate/PCT polyester composition of claim 1 or 2, wherein said polycarbonate resin has a melt mass flow rate of 10 to 30g/10min, at 300 ℃ and 1.20 kgf.
5. polycarbonate/PCT polyester composition according to claim 1 or 2, characterized in that the hyperbranched polyester has a molecular weight of 2000-10000g/mol and a number of carboxylic groups of 12-48/mol.
6. The polycarbonate/PCT polyester composition according to claim 1 or 2, further comprising 0 to 20 parts by weight of a reinforcing material; the reinforcing material is at least one selected from glass fiber, wollastonite, potassium titanate whisker, kaolin, talc and mica.
7. A method of making a polycarbonate/PCT polyester composition according to any of claims 1-6, comprising the steps of: uniformly mixing the PCT resin, the polycarbonate resin and an optional reinforcing material, then carrying out melt blending and extrusion granulation on the mixture and the hyperbranched polyester through a double-screw extruder to obtain the polycarbonate/PCT polyester composition, wherein the temperature of the double-screw extruder is set to be 230-300 ℃.
8. Use of the polycarbonate/PCT polyester composition according to any one of claims 1 to 6, for the preparation of LED reflectors.
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| CN202011371298.9A CN112538240B (en) | 2020-11-30 | 2020-11-30 | polycarbonate/PCT polyester composition and preparation method and application thereof |
| PCT/CN2021/119396 WO2022111007A1 (en) | 2020-11-30 | 2021-09-18 | Polycarbonate/pct polyester composition, preparation method therefor and application thereof |
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| CN111732819A (en) * | 2020-05-26 | 2020-10-02 | 金发科技股份有限公司 | Polyester resin composition and preparation method and application thereof |
| CN111763408A (en) * | 2020-05-19 | 2020-10-13 | 金发科技股份有限公司 | Polyester resin composition and preparation method and application thereof |
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| DE102005002044A1 (en) * | 2005-01-14 | 2006-07-20 | Basf Ag | Flowable polyesters with hydrolysis protection |
| US20110147998A1 (en) * | 2009-12-17 | 2011-06-23 | E.I. Du Pont De Nemours And Company | Polyester Compositions with Good Melt Rheological Properties |
| WO2011159377A1 (en) * | 2010-06-14 | 2011-12-22 | E. I. Du Pont De Nemours And Company | Long-term outdoor exposure resistant polyester composite structures and processes for their preparation |
| CN101906244A (en) * | 2010-08-12 | 2010-12-08 | 东莞市信诺橡塑工业有限公司 | Polycarbonate combination and preparation method thereof |
| CN103865246B (en) * | 2012-12-14 | 2016-08-10 | 苏州汉扬精密电子有限公司 | A kind of glass fiber-reinforced resin composition |
| CN111117192A (en) * | 2019-12-28 | 2020-05-08 | 会通新材料股份有限公司 | Polycarbonate/polyester alloy with high CTI value, high glow wire and low hot ball indentation and preparation method thereof |
| CN112538240B (en) * | 2020-11-30 | 2022-07-19 | 金发科技股份有限公司 | polycarbonate/PCT polyester composition and preparation method and application thereof |
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| CN111763408A (en) * | 2020-05-19 | 2020-10-13 | 金发科技股份有限公司 | Polyester resin composition and preparation method and application thereof |
| CN111732819A (en) * | 2020-05-26 | 2020-10-02 | 金发科技股份有限公司 | Polyester resin composition and preparation method and application thereof |
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| "Polyester-based Blends";Daniela Rusu;《ResearchGate》;20161201;第247-283页 * |
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