CN107312300B - Transparent resin composition with improved fluidity and preparation method thereof - Google Patents
Transparent resin composition with improved fluidity and preparation method thereof Download PDFInfo
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- CN107312300B CN107312300B CN201710517070.8A CN201710517070A CN107312300B CN 107312300 B CN107312300 B CN 107312300B CN 201710517070 A CN201710517070 A CN 201710517070A CN 107312300 B CN107312300 B CN 107312300B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a transparent resin composition with improved fluidity and a preparation method thereof; the composition comprises the following components in parts by weight: 75-90 parts of polycarbonate resin; 8-20 parts of polybutylene terephthalate resin; 1.1-2.1 parts of nano zinc oxide; 0.5-1 part of antioxidant; 0-5 parts of a toughening agent. PC, PBT, nano ZnO, an antioxidant and a toughening agent are premixed in a mixer and then put into a double-screw technology, and the resin composition is obtained through melt extrusion and granulation. The PC/PBT resin composition prepared by the invention not only has excellent transparency, but also has good fluidity and heat resistance. The resin composition prepared by the invention can be used as a transparent substrate of a spraying-free special-effect resin composition.
Description
Technical Field
The invention relates to a transparent resin composition with improved fluidity and a preparation method thereof, belonging to the technical field of high polymer material processing.
Background
Polycarbonate (PC) resin has excellent optical transparency, excellent impact properties and heat resistance, and is one of five most widely used engineering plastics. In recent years, with increasingly higher social importance on environmental protection, the spraying-free aesthetic plastics are gradually led to the market. To maximize special effects (such as pearlescent glitter, jade transparency, etc.) in aesthetic plastics, it is first required that the substrate is a transparent substrate, such as transparent ABS, PC, etc. However, the PC resin has high molecular chain rigidity and melt viscosity and poor processing flowability, and therefore stress concentration is likely to occur during molding, and stress cracking is likely to occur during long-term use. It can be said that internal stress and stress cracking of PC articles are a more prominent problem.
In order to solve this problem, introduction of a polybutylene terephthalate (PBT) resin having a soft molecular chain and good fluidity into a PC resin is one of the feasible methods. However, PBT is a crystalline material, and the transparency of PC resin is affected by the large crystal size of PBT. Thus, there have been reports on the preparation of transparent PC/PBT resin compositions. For example, patent publication No. CN101759985 discloses that a transparent PC/PBT material is prepared by using copolyester as a compatilizer of PC and PBT resin; however, the copolyester has a small source and a high price, and the light transmittance of the prepared resin composition is less than 80%. Patent publication No. CN104710748 discloses the use of a transparent nucleating agent to improve the transparency of PC/PBT resins, which is also expensive, and does not disclose the light transmittance level and processing flowability of the resin composition.
The patent CN103183935A discloses a high-toughness PBT/PC alloy, which is formed by extruding the following components in percentage by mass through a melting reaction: 60-65% of polybutylene terephthalate, 30-35% of polycarbonate, 4-6% of a toughening agent and 0.1-1% of an ester exchange catalyst. By adding a very small amount of ester exchange catalyst into the system, the ester exchange reaction is carried out between PBT and PC and a block copolymer with compatibilization is generated, so that the addition amount of the toughening agent is reduced, the cost is saved, and the high-toughness PBT/PC alloy is obtained. However, in the alloy prepared by the method, the PBT resin is mainly composed of a matrix phase, the transparent PC resin is only a disperse phase, the PBT resin is an opaque crystalline resin, the content of the ester exchange catalyst is low, and the influence on the crystallization capacity of the PBT is small, so that the prepared resin composition is opaque.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing a transparent resin composition having improved flowability and a method for preparing the same. The inventors have made extensive experiments to surprisingly find that addition of an appropriate amount of zinc oxide (ZnO) to a resin composition of PC and PBT can promote transesterification reaction between PC and PBT. The higher the transesterification degree of the PC and the PBT is, the lower the crystallization capacity of the PBT resin is, the smaller the crystal size is, and the better the transparency is; however, if the degree of transesterification is too high, the PC/PBT resin composition is yellowed, and transparency is also affected. The degree of transesterification reaction is thus controlled by controlling the amount of ZnO used; and transparency and light transmittance are controlled by controlling the particle size of ZnO.
The purpose of the invention is realized by the following technical scheme:
the invention provides a transparent resin composition with improved fluidity, which comprises the following components in parts by weight:
preferably, the polycarbonate resin is bisphenol A polycarbonate, and the number average molecular weight is 25,000-30,000 g/mol.
Preferably, the intrinsic viscosity of the polybutylene terephthalate resin is 0.8 to 1.3 dl/g.
Preferably, the transesterification catalyst is nano zinc oxide (ZnO), and the particle size of the zinc oxide is 20-50 nm; the particle size is too large, and the physical property cracking of the composition is remarkably influenced.
Preferably, the antioxidant is a combination of pentaerythritol ester and phosphite ester.
Preferably, the toughening agent is methyl methacrylate-butadiene-styrene copolymer (MBS), the particle size is 100-200nm, and the influence on the transparency of the composition is remarkable if the particle size is too large.
The present invention also provides a method for preparing a transparent resin composition having improved flowability, the method comprising the steps of: and premixing PC, PBT, nano ZnO, an antioxidant and a toughening agent according to a set proportion, and putting the mixture into a double-screw extruder for melt blending to obtain the transparent resin composition.
Preferably, the twin-screw extruder has a screw length/diameter ratio of greater than 50.
Preferably, the barrel temperature of the double-screw extruder from the charging opening to the die is set to be step-shaped, the 1-2 region is set to be 180-.
Compared with the prior art, the invention has the following beneficial effects:
the PC/PBT resin composition prepared by the invention has excellent transparency (light transmittance is more than 80%), and simultaneously has good fluidity and heat resistance. The resin composition prepared by the invention can be used as a transparent substrate of a spraying-free special-effect resin composition.
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.
In the following examples of the present invention, the raw materials used were:
selected PC with a melt index (300 ℃ C. 1.2kg) of 10g/10min, manufactured by Nippon imperial;
the selected PBT has the intrinsic viscosity of 1.0dl/g and is manufactured by chemical fiber characterization;
selected nano ZnO with the purity of 99.7 percent is manufactured by US Zinc;
selected antioxidants IG1010 and IG168, manufactured by basf, germany;
the grain size of the selected MBS toughening agent is 160nm, and the chemical manufacturing of LG is carried out;
examples 1 to 4
Examples 1 to 4 provide a transparent resin composition having improved flowability, comprising the components in parts by weight shown in table 1. The preparation method comprises the following steps:
(1) weighing the raw materials in parts by weight in the table 1;
(2) mixing the raw materials in a high-speed mixer;
(3) all the mixed raw materials are put into a double-screw extruder from a main feeding port at one time, and the composition is obtained through melt extrusion, cooling and granulation;
in the above preparation method, the screw length/diameter ratio of the twin-screw extruder is 50; the barrel temperatures of the extruders were set at 180, 200, 255, 265, 270, 275, 280, 270, 260 ℃ in one to thirteen zones from the feed port to the die, respectively.
Comparative example 1
This comparative example 1 provides a transparent resin composition having improved flowability, the components and parts by weight of which are shown in table 1, wherein ZnO, a transesterification catalyst, is not included, and a preparation method thereof, comprising the steps of:
(1) weighing the raw materials in parts by weight in the table 1;
(2) mixing the raw materials in a high-speed mixer;
(3) and (3) putting all the mixed raw materials into a double-screw extruder from a main feeding port at one time, and carrying out melt extrusion, cooling and granulation to obtain the composition.
In the above preparation method, the screw length/diameter ratio of the twin-screw extruder is 50; the barrel temperatures of the extruders were set at 180, 200, 255, 265, 270, 275, 280, 270, 260 ℃ in one to thirteen zones from the feed port to the die, respectively.
Comparative example 2
This comparative example 1 provides a transparent resin composition having improved flowability, the components and parts by weight of the resin composition are shown in table 1; the length/diameter ratio of the double-screw extruder used in the preparation method is 40, and the method comprises the following steps:
(1) weighing the raw materials in parts by weight in the table 1;
(2) mixing the raw materials in a high-speed mixer;
(3) and (3) putting all the mixed raw materials into a double-screw extruder from a main feeding port at one time, and carrying out melt extrusion, cooling and granulation to obtain the composition.
In the above-mentioned production method, the barrel temperatures of the extruders in the one to thirteen zones from the feed port to the die were set to 180, 200, 255, 265, 270, 275, 280, 270, 260 ℃ respectively.
Comparative examples 3 to 6
Comparative examples 3 to 6 provide a transparent resin composition having improved flowability, the components and parts by weight of which are shown in table 1; the preparation method is the same as the example. Wherein: the transesterification catalyst used in comparative example 3 was nano-magnesia; the transesterification catalyst used in comparative example 4 was micron-sized zinc oxide (ZnO-2); the toughening agent adopted in the comparative example 5 is MBS (MBS-2) with the grain diameter of more than 200 nm; the toughening agent used in comparative example 6 was a core-shell structure elastomer (ACR-MMA) whose core layer was a polyacrylic resin.
Performance testing
The particles of the compositions prepared in examples 1 to 4 and comparative examples 1 to 6 were vacuum-dried at 100 ℃ for 12 hours or more, and then injection-molded into sample bars under the same injection molding conditions according to the ASTM standard, and the physical properties of the respective resin compositions were tested; injection molded into 100mm by 100mm plaques and tested for light transmittance. The test follows the following test method: determining the light transmittance of the sample plate based on the test procedure of ASTM D1003; heat distortion temperature was determined based on the test procedure of ASTM D648 with a load of 0.45 MPa; izod notched impact strength was determined based on the test procedure of ASTM D256, with a sample thickness of 1/8 "; the melt flow rate was determined based on the test procedure of ASTM D1238, under test conditions of 300 ℃ temperature and 1.2kg load.
The results of testing the physical properties of the resin compositions prepared in examples 1 to 4 and comparative examples 1 to 6 are shown in Table 1; comparing the data of examples 1-4 and comparative examples 1-6 in Table 1, it can be seen that the PC/PBT resin composition has excellent light transmittance and good flow property after the nano ZnO is introduced; impact properties can be significantly improved depending on the presence or absence of the toughening agent.
TABLE 1
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (7)
1. A transparent resin composition with improved fluidity is characterized by comprising the following components in parts by weight:
the transesterification catalyst is nano zinc oxide, and the particle size of the zinc oxide is 20-50 nm;
the toughening agent is methyl methacrylate-butadiene-styrene copolymer with the particle size of 100-200 nm.
2. The transparent resin composition with improved flowability as claimed in claim 1, wherein the polycarbonate resin is bisphenol A polycarbonate and has a number average molecular weight of 25,000 to 30,000 g/mol.
3. The transparent resin composition having improved flowability as claimed in claim 1, wherein the intrinsic viscosity of the polybutylene terephthalate resin is 0.8 to 1.3 dl/g.
4. The transparent resin composition with improved flowability as claimed in claim 1, wherein the antioxidant is a combination of pentaerythritol ester and phosphite ester.
5. A method for producing the transparent resin composition having improved flowability according to claim 1, comprising the steps of: and premixing PC, PBT, nano ZnO, an antioxidant and a toughening agent according to a set proportion, and putting the mixture into a double-screw extruder for melt blending to obtain the transparent resin composition.
6. The method for preparing a transparent resin composition having improved flowability as claimed in claim 5, wherein the twin-screw extruder has a screw length/diameter ratio of more than 50.
7. The method as claimed in claim 5, wherein the barrel temperature of the twin-screw extruder from the inlet to the die is set to be stepped, and the 1-2 zone is set to be 180-.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710517070.8A CN107312300B (en) | 2017-06-29 | 2017-06-29 | Transparent resin composition with improved fluidity and preparation method thereof |
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| CN107312300A CN107312300A (en) | 2017-11-03 |
| CN107312300B true CN107312300B (en) | 2020-04-10 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113999513A (en) * | 2021-11-24 | 2022-02-01 | 青岛国恩科技股份有限公司 | PC/PMMA alloy material for LED lampshade and preparation method thereof |
| CN114921078B (en) * | 2022-03-16 | 2023-11-17 | 金发科技股份有限公司 | Transparent PC/PBT alloy and preparation method and application thereof |
| CN115197525B (en) * | 2022-03-29 | 2024-02-23 | 江苏金发科技新材料有限公司 | PC/ABS resin composition for laser welding and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183935A (en) * | 2013-04-08 | 2013-07-03 | 四川大学 | High-ductility PBT/PC (polybutylece terephthalate/polycarbonate) alloy and preparation method thereof |
| CN103289342A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | High heat conduction reinforced PC/PBT alloy |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0774491A3 (en) * | 1995-11-20 | 1997-12-03 | General Electric Company | Films, sheets and molded products made of a polyester/polycarbonate composition |
| JPH1087973A (en) * | 1996-09-11 | 1998-04-07 | Nippon G Ii Plast Kk | Transparent polyester/polycarbonate composition excellent in impact strength and solvent resistance |
| JPWO2007023919A1 (en) * | 2005-08-24 | 2009-02-26 | 株式会社カネカ | Stabilizer composition for synthetic resin |
| CN101089046A (en) * | 2007-06-08 | 2007-12-19 | 深圳市科聚新材料有限公司 | Transparent polycarbonate alloy composite material and its prepn process |
| CN101759985B (en) * | 2008-12-23 | 2012-07-11 | 安徽科聚新材料有限公司 | Transparent polycarbonate/polybutylece terephthalate alloy and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183935A (en) * | 2013-04-08 | 2013-07-03 | 四川大学 | High-ductility PBT/PC (polybutylece terephthalate/polycarbonate) alloy and preparation method thereof |
| CN103289342A (en) * | 2013-06-24 | 2013-09-11 | 苏州新区佳合塑胶有限公司 | High heat conduction reinforced PC/PBT alloy |
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Effective date of registration: 20201019 Address after: 201517 Huadao 1223, Jinshan Second Industrial Zone, Jinshan District, Shanghai Patentee after: SHANGHAI KUMHOSUNNY PLASTICS Co.,Ltd. Address before: 201107, No. 1399, Ji Gao Road, Hua Cao Town, Shanghai, Minhang District Patentee before: SHANGHAI KUMHOSUNNY PLASTICS Co.,Ltd. |
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