CN112280273A - PMMA/ionomer/PC ternary alloy and preparation method thereof - Google Patents
PMMA/ionomer/PC ternary alloy and preparation method thereof Download PDFInfo
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- CN112280273A CN112280273A CN202011111379.5A CN202011111379A CN112280273A CN 112280273 A CN112280273 A CN 112280273A CN 202011111379 A CN202011111379 A CN 202011111379A CN 112280273 A CN112280273 A CN 112280273A
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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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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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a PMMA/ionomer/PC ternary alloy which comprises the following components in parts by weight: 5-60 parts of carboxylic acid ionomer; 5-95 parts of polycarbonate; and 1-35 parts of PMMA. Through the compounding of the three resins, the pearlescent defect of the PMMA/PC alloy can be obviously improved, and the ternary alloy has the advantage of low forming stress, thereby being beneficial to preparing high-toughness products with complex structures.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a PMMA/ionomer/PC ternary alloy and a preparation method thereof.
Background
Polycarbonates (PC for short) are high molecular polymers containing carbonate groups in the molecular chain, and are classified into various types, such as aliphatic, aromatic, aliphatic-aromatic, and the like, depending on the structure of the ester group. Due to the structural particularity of polycarbonate, the polycarbonate is the universal engineering plastic with the highest growth speed in five engineering plastics. Polycarbonate is a synthetic material that has begun to develop in the late fifties. The polycarbonate resin has outstanding impact resistance, creep resistance and dimensional stability, is widely applied to the fields of electronic and electric appliances, rail transit and aerospace, and has a dosage exceeding nylon in recent years, thereby jumping the leading position.
However, polycarbonate also has the defects of surface gloss, surface scratch resistance, insufficient strength and the like, and the common solution is to blend with PMMA (polymethyl methacrylate) to form a PMMA/PC alloy. However, since the refractive indices of the two resin matrices of PMMA/PC are different, light is refracted in the resin matrices to generate a pearl effect. The Chinese patent application 2018108054686 discloses a PC/PMMA composite material, wherein the difference of the glossiness of the PC/PMMA composite material is utilized to generate the pearlescent effect, so that the problem that the surface of a product is easy to form flow marks or weld marks due to the addition of aluminum powder or pearl powder in the conventional silver pearlescent spraying-free material is avoided. Chinese patent application 2016104106339 discloses a transparent scratch-resistant PC/PMMA alloy, which can solve the problems of pearlescence, yellowing and the like in the prior art when preparing a transparent scratch-resistant PC resin composition by adopting a metal organic compound stabilizer A and a phosphorus compound stabilizer B and adding the stabilizer B into a melting system in a side feeding manner. Chinese patent application 2018106764638 discloses a transparent high-hardness PC composition, which solves the problems of poor compatibility, poor toughness, opaqueness and pearlescence of PC and PMMA alloy in the prior art by adopting a polyester copolymer, a styrene copolymer and PC for blending.
Regarding the molding stress, the polycarbonate molecular main chain has strong rigidity, and the molecular chain adjustment is relatively slow in the injection molding process, so that the molding stress is high. Generally, the following 3 methods are mainly used for reducing the stress: 1. the viscosity of the polycarbonate is reduced, but the mechanical property is greatly reduced; 2. reducing stress by adjusting molding parameters during molding; 3. ABS resin is introduced to prepare PC/ABS alloy, but the surface hardness of the alloy is low, and the scratch resistance is poor.
Disclosure of Invention
The invention aims to overcome the technical defects and provide the PMMA/ionomer/PC ternary alloy which can greatly improve the pearl effect, has the advantage of low forming stress and is beneficial to preparing high-toughness products with complex structures.
The invention also aims to provide a preparation method of the ternary alloy.
The invention is realized by the following technical scheme:
a PMMA/ionomer/PC ternary alloy comprises the following components in parts by weight:
5-60 parts of carboxylic acid ionomer;
5-95 parts of polycarbonate;
1-35 parts of PMMA.
Preferably, the composition comprises the following components in parts by weight:
15-35 parts of carboxylic acid ionomer;
25-75 parts of polycarbonate;
10-25 parts of PMMA.
The carboxylic acid group ionomer is an ethylene/methacrylic acid copolymer, wherein 40mol% to 90mol% of the carboxylic groups of the methacrylic acid units are neutralized by metal ions.
The metal ions are selected from at least one of sodium ions, zinc ions, magnesium ions and potassium ions.
The melt index of the carboxylic acid-based ionomer is 0.5-5g/10min, and the test conditions are 190 ℃ and 2.16 kg.
The melt index of PMMA is between 12 and 22g/10min, and the test conditions are 230 ℃ and 3.8 kg.
The polycarbonate has a melt index of 3-22g/10min, and the test conditions are 300 ℃ and 1.2 kg.
Polycarbonates, which are branched thermoplastic polymers or copolymers obtained by reaction of dihydroxy compounds or their mixtures with small amounts of polyhydroxy compounds and phosgene (phosgene) or carbonic acid diesters. The polycarbonate resin can be produced by a phosgene method (interfacial polymerization method) or a melt method (transesterification method). The polycarbonate resin is also provided by subjecting a polycarbonate resin produced by a melt process to a post-treatment for adjusting the amount of terminal hydroxyl groups.
In the polycarbonate segment obtained by the phosgene method reaction, the repeating unit is formed by the reaction of bisphenol A and phosgene. In the polycarbonate segment obtained by the transesterification process, the repeating units are formed by reacting diphenyl carbonate with bisphenol A.
In order to improve the melt processing performance, 0 to 3 parts by weight of lubricant can be added.
The lubricant is at least one selected from stearate lubricant, fatty acid lubricant and stearate lubricant; the stearate lubricant is at least one selected from calcium stearate, magnesium stearate and zinc stearate; the fatty acid lubricant is at least one selected from fatty acid, fatty acid derivative and fatty acid ester; the stearate lubricant is at least one selected from glyceryl monostearate and pentaerythritol stearate.
The preparation method of the PMMA/ionomer/PC ternary alloy comprises the following steps: according to the proportion, after the components are uniformly mixed, the mixture is extruded and granulated by a double-screw extruder, the temperature range of the screw is 200-270 ℃, and the rotating speed range is 180-500r/min, so that the PMMA/ionomer/PC ternary alloy is obtained.
The PMMA/ionomer/PC ternary alloy is applied to preparing a scratch-resistant and high-gloss workpiece.
The invention has the following beneficial effects:
the PMMA/ionomer/PC ternary alloy obviously improves the pearlescent defect of the PMMA/PC binary alloy. By introducing the carboxylic acid group ionomer with a flexible molecular chain, the stress generated in the forming process can be reduced after the carboxylic acid group ionomer is alloyed with PC/PMMA, and the surface hardness of the ternary alloy can be improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the invention are as follows:
carboxylic acid group ionomer a: the main chain is ethylene/methacrylic acid copolymer, the melt index is 3.5g/10min, the test condition is 190 ℃, 2.16kg, and 78mol percent of carboxyl of methacrylic acid unit is neutralized by sodium ion.
Carboxylic acid group ionomer B: the main chain is ethylene/methacrylic acid copolymer, the melt index is 1.4g/10min, the test condition is 190 ℃, 2.16kg, and 45mol percent of carboxyl of methacrylic acid unit is neutralized by zinc ions.
Carboxylic acid group ionomer C: the main chain is ethylene/methacrylic acid copolymer, the melt index is 5.9g/10min, the test condition is 190 ℃, 2.16kg, 26mol percent of carboxyl of methacrylic acid unit is neutralized by zinc ion.
Polycarbonate (C): the trade name is TRIREX 3025PJ, the melt index is 10g/10min, the test conditions are 300 ℃, 1.2 kg;
PMMA: the trade name of PMMA LG, the melt index is 9g/10min, the test condition is 230 ℃, 3.8 kg;
zinc stearate: ZINC STEARATE (BS-2818), commercially available, added as a lubricant;
the performance test method comprises the following steps:
(1) and (4) internal stress testing: ISO527.2-2012 tensile bars were fixed on a jig with a curvature of 1.0, coated with toluene: ethanol =1:3 solvent, and the specimens were observed for cracking time and cracking morphology. The fracture within 1h after solvent coating is marked as grade 1, the fracture within 1-4h is marked as grade 2, the fracture within 4-12h is marked as grade 3, the fracture within 12-24h is marked as grade 4, and the fracture exceeding 24h is marked as grade 5. The cracking forms are divided into two forms, namely microcracks and macrocracks.
(2) Surface hardness test: the pencil hardness method was used for evaluation and the test was carried out with reference to ASTM D3363-2005, with a test weight of 750 g. The evaluation grades are divided into: 6B, 5B, 4B, 3B, 2B, HB, F, H, 2H, 3H, 4H, 5H, 6H.
(3) The pearl effect is as follows: and (4) observing whether the pearly-lustre effect exists or not (observing whether the color lines can be seen or not under a side light source, and calculating the generation area of the pearly-lustre effect in a unit area).
Examples and comparative examples preparation of PMMA ionomer PC ternary alloys: according to the proportion, after all the components are uniformly mixed, the mixture is extruded and granulated by a double-screw extruder, the temperature range of the screw is 200-400 ℃ and the rotating speed range is 360-400r/min, and the alloy is obtained.
Table 1: example 1-6 alloy composition ratios and performance test results
From example 1/3/5, it is understood that although the surface hardness is theoretically higher as the content of PMMA is higher, the advantage of PMMA in increasing the surface hardness is hardly exhibited if the resin composition such as ternary alloy is out of the preferable range of the present invention.
From examples 1-6, it can be seen that the preferred ternary alloy ratio range has at least two of the three properties being better.
Table 2: example 7-9 alloy composition ratios and Performance test results
Table 3: proportioning of each component of comparative example alloy and each performance test result
Since comparative example 1 has no PMMA, there is no pearl effect; however, the surface hardness is low and stress cracking is liable to occur.
As can be seen from comparative examples 2 to 4, no carboxylic acid-based ionomer was added or the amount of addition was insufficient, the pearlescence was remarkable, and it was shown that the hardness was low and stress cracking was liable.
As can be seen from comparative example 5, the carboxylic acid-based ionomer is added in too large an amount, the pearlescence of the material cannot be eliminated, and the modulus of the material is reduced.
Claims (10)
1. The PMMA/ionomer/PC ternary alloy is characterized by comprising the following components in parts by weight:
5-60 parts of carboxylic acid ionomer;
5-95 parts of polycarbonate;
1-35 parts of PMMA.
2. The PMMA/ionomer/PC ternary alloy of claim 1, comprising the following components in parts by weight:
15-35 parts of carboxylic acid ionomer;
25-75 parts of polycarbonate;
10-25 parts of PMMA.
3. The PMMA/ionomer/PC ternary alloy of claim 1, wherein the carboxylic acid group ionomer is an ethylene/methacrylic acid copolymer, wherein 40mol% to 90mol% of the carboxylic groups in the methacrylic acid units are neutralized by metal ions.
4. The PMMA/ionomer/PC ternary alloy of claim 3, wherein the metal ion is selected from at least one of sodium ion, zinc ion, magnesium ion and potassium ion.
5. The PMMA/ionomer/PC ternary alloy according to any one of claims 1 to 4, wherein the carboxylic acid based ionomer has a melt index between 0.5 and 5g/10min, measured at 190 ℃ and 2.16 kg.
6. The ternary PMMA/ionomer/PC alloy according to claim 1, characterized in that the PMMA melt index is comprised between 12 and 22g/10min, the test conditions are 230 ℃ and 3.8 kg.
7. The PMMA/ionomer/PC ternary alloy of claim 1, wherein the polycarbonate has a melt index of 3-22g/10min, and the test conditions are 300 ℃ and 1.2 kg.
8. The PMMA/ionomer/PC ternary alloy of claim 1, further comprising 0-3 parts by weight of a lubricant.
9. Method for the preparation of a PMMA/ionomer/PC ternary alloy according to any one of claims 1 to 8, characterized in that it comprises the following steps: according to the proportion, after the components are uniformly mixed, the mixture is extruded and granulated by a double-screw extruder, the temperature range of the screw is 200-270 ℃, and the rotating speed range is 180-500r/min, so that the PMMA/ionomer/PC ternary alloy is obtained.
10. Use of a PMMA/ionomer/PC ternary alloy according to any of claims 1 to 8, characterized in that it is used for the preparation of scratch-resistant, high-gloss articles.
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| CN202011111379.5A CN112280273B (en) | 2020-10-16 | 2020-10-16 | PMMA/ionomer/PC ternary alloy and preparation method thereof |
| PCT/CN2021/082013 WO2022077862A1 (en) | 2020-10-16 | 2021-03-22 | Pmma/ionomer/pc ternary alloy and preparation method therefor |
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| WO2022077862A1 (en) * | 2020-10-16 | 2022-04-21 | 金发科技股份有限公司 | Pmma/ionomer/pc ternary alloy and preparation method therefor |
| WO2022242289A1 (en) * | 2021-05-17 | 2022-11-24 | 金发科技股份有限公司 | Antistatic masterbatch, preparation method therefor and use thereof |
| WO2022242290A1 (en) * | 2021-05-17 | 2022-11-24 | 金发科技股份有限公司 | Antistatic masterbatch, preparation method therefor and use thereof |
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| US5344883A (en) * | 1992-10-05 | 1994-09-06 | Alliedsignal Inc. | Polymeric powder coating compositions comprising low molecular weight copolymer or terpolymer salts of α-olefins and α,β-ethylenically unsaturated carboxylic acids |
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| KR20100049362A (en) * | 2008-11-03 | 2010-05-12 | 주식회사 이폴리머 | Thermoplastics/ionomer blend resin composition or reaction product |
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| CN110218432A (en) * | 2019-06-14 | 2019-09-10 | 广东聚钛新材料有限公司 | A kind of high tenacity PC/PMMA alloy material and preparation method thereof |
| CN111534074A (en) * | 2020-05-20 | 2020-08-14 | 新阳荣乐(上海)汽车电子有限公司 | Application of PMMA-PC composite material |
| CN112280273B (en) * | 2020-10-16 | 2021-12-10 | 金发科技股份有限公司 | PMMA/ionomer/PC ternary alloy and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109367161A (en) * | 2018-12-18 | 2019-02-22 | 上海亮籽智能科技有限公司 | A kind of complex layered materials and its preparation method and application |
| CN110041683A (en) * | 2019-04-25 | 2019-07-23 | 金旸（厦门）新材料科技有限公司 | A kind of PC/PMMA material and preparation method thereof for luggage shell |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022077862A1 (en) * | 2020-10-16 | 2022-04-21 | 金发科技股份有限公司 | Pmma/ionomer/pc ternary alloy and preparation method therefor |
| WO2022242289A1 (en) * | 2021-05-17 | 2022-11-24 | 金发科技股份有限公司 | Antistatic masterbatch, preparation method therefor and use thereof |
| WO2022242290A1 (en) * | 2021-05-17 | 2022-11-24 | 金发科技股份有限公司 | Antistatic masterbatch, preparation method therefor and use thereof |
| CN115368721B (en) * | 2021-05-17 | 2023-09-19 | 金发科技股份有限公司 | Antistatic master batch and preparation method and application thereof |
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Effective date of registration: 20211213 Address after: 510663 Guangzhou science and Technology Development Zone, Guangdong, China, 33 Patentee after: KINGFA SCI. & TECH. Co.,Ltd. Patentee after: Liaoning Baolai New Material Co.,Ltd. Address before: 510663 Guangzhou science and Technology Development Zone, Guangdong, China, 33 Patentee before: KINGFA SCI. & TECH. Co.,Ltd. |
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Address after: 510663 Guangzhou science and Technology Development Zone, Guangdong, China, 33 Patentee after: KINGFA SCI. & TECH. Co.,Ltd. Patentee after: Liaoning Jinfa Technology Co.,Ltd. Address before: 510663 Guangzhou science and Technology Development Zone, Guangdong, China, 33 Patentee before: KINGFA SCI. & TECH. Co.,Ltd. Patentee before: Liaoning Baolai New Material Co.,Ltd. |