CN115386187A - Cycloolefin copolymer composite material with adjustable glass transition temperature and preparation method thereof - Google Patents
Cycloolefin copolymer composite material with adjustable glass transition temperature and preparation method thereof Download PDFInfo
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- CN115386187A CN115386187A CN202211078239.1A CN202211078239A CN115386187A CN 115386187 A CN115386187 A CN 115386187A CN 202211078239 A CN202211078239 A CN 202211078239A CN 115386187 A CN115386187 A CN 115386187A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/12—Syndiotactic polypropylene
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Abstract
The invention discloses a cycloolefin copolymer composite material with adjustable glass transition temperature and a preparation method thereof; the composite material comprises the following components in parts by mass: 51.1 to 59.3 parts by mass of cycloolefin copolymer; 24.0 to 48.9 parts by mass of petroleum resin; 0-7.1 parts by mass of syndiotactic polypropylene; 0 to 16.6 parts by mass of polystyrene; 0 to 16.1 parts of toughening agent. And mixing, extruding and granulating the components by a double-screw extruder to obtain the cyclic olefin copolymer composite material. The glass transition temperature of the obtained composite material is obviously reduced, and the composite material can be regulated and controlled according to processing requirements, so that the problems of difficult secondary processing, high processing cost and the like caused by the higher glass transition temperature of the cycloolefin copolymer can be solved, and the wide application of the cycloolefin copolymer in the fields of high-precision processing of microfluidic chips and the like is promoted.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a cycloolefin copolymer composite material with adjustable glass transition temperature and a preparation method thereof.
Background
Cycloolefin copolymers (hereinafter abbreviated as COC) are amorphous polymers prepared by copolymerizing norbornene or its derivatives with ethylene. The COC contains rigid groups in the main chain, and has excellent mechanical properties, high transparency, low dielectric loss, low hygroscopicity, good solvent resistance, high heat resistance and excellent dimensional stability. COCs have numerous applications in the packaging, optical and medical fields. The excellent optical characteristics of COC are particularly suitable for manufacturing components of microfluidic equipment, and some products need to be subjected to secondary processing by using COC plates to produce microfluidic products. The main reason is that the production efficiency of the secondary processing is high, and the product precision meets the application requirement of the microfluidic technology. Commercial COC has a glass transition temperature (Tg) in the range of 30 to 180 ℃ depending on the norbornene content. However, COC with high glass transition temperature and high strength is usually accompanied with the problems of poor toughness, high secondary processing temperature, difficult processing, high production cost and the like, and the application and popularization of products are greatly influenced.
The factors influencing the glass transition temperature of plastics are very complex, with the molecular chain structure playing a major role. At present, most of adjusting methods for the glass transition temperature are to introduce additives such as plasticizers, but low-molecular plasticizers influence the mechanical properties of materials and are more likely to cause that the materials cannot be applied to medical instruments due to the problem of biological safety. Therefore, by blending COC with other olefin polymers, the influence on mechanical properties is minimized while improving processability, which will promote the wide application and further development of cyclic olefin polymers.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned disadvantages and drawbacks of the prior art and providing a cyclic olefin copolymer composite material having an adjustable glass transition temperature and a method for preparing the same.
The invention is realized by the following technical scheme:
a cyclic olefin copolymer composite material with adjustable glass transition temperature comprises the following components:
51.1 to 59.3 parts by mass of cycloolefin copolymer;
24.0 to 48.9 parts by mass of petroleum resin;
0-7.1 parts by mass of syndiotactic polypropylene;
0-16.6 parts of polystyrene;
0 to 16.1 parts of toughening agent.
The cycloolefin copolymer is cycloolefin copolymer plastic with the norbornene content of more than 70 percent, preferably 5013L-10 produced by TOPAS Advanced Polymers in Germany, the glass transition temperature of the cycloolefin copolymer is 134 ℃ (DSC method, the heating rate is 10 ℃/min), and the Vicat softening point is 133 ℃ (50N, the heating rate is 50 ℃/h).
The petroleum resin is aromatic hydrocarbon modified alicyclic hydrogenated resin with very light color, preferably Escorez 5600 series petroleum resin produced by Exxon Mobil chemical industry Co., ltd, and has a glass transition temperature of 55 deg.C (ETM 300-90).
The syndiotactic polypropylene is polypropylene resin with the syndiotactic degree of more than 80 percent catalyzed by metallocene, and the melt flow rate (230 ℃,2.16 kg) is 5 to 20g/10min; the mPP6006 produced by the institute of petrochemical engineering preferably has a melt flow rate (230 ℃ C., 2.16 kg) of 5-8 g/10min.
The polystyrene is homopolymerized polystyrene with the polystyrene content of more than 95 percent, preferably GPPS-PG33 produced by Jiangsu Zhenjiangqi beautifying chemical company Limited, and the Vicat softening point of the polystyrene is 94 ℃ (50N, the heating rate is 50 ℃/h).
The toughening agent is a polypropylene elastomer with the propylene content of more than 80 percent, preferably Vistamaxx6102 produced by exxonmobil chemical company in the United states, and the melt flow rate of the toughening agent is 3g/10min (the test temperature is 230 ℃ C., and the load is 2.16 kg).
A method for preparing a glass transition temperature-adjustable cyclic olefin copolymer composite material, comprising the steps of:
1) Mixing: adding the cycloolefin copolymer, the petroleum resin, the syndiotactic polypropylene, the polystyrene and the toughening agent into a high-speed mixer in sequence for premixing, wherein the mixing temperature is 20-40 ℃, the rotating speed is 200-400 r/min, and the mixing time is 3-5 min, so as to obtain the premix of the cycloolefin copolymer composite material.
(2) And (3) extruding and granulating by using double screws: the premix of the cycloolefin copolymer composite material was extruded and pelletized by a parallel co-rotating twin-screw extruder having a length-diameter ratio of 40. The rotating speed of the feeder is set to be 10-50 r/min, the rotating speed of the screw is set to be 200-600 r/min, and the temperature of each section of the extruder is set to be 160-200 ℃, so as to obtain the compound of the cycloolefin copolymer composite material.
The principle of the invention is as follows: the aromatic petroleum resin has similarity with the structure of the cycloolefin copolymer, has excellent compatibility when being blended with the cycloolefin copolymer, can achieve the compatibility of molecular level, and can adjust the viscosity of the cycloolefin copolymer. The polystyrene has certain compatibility with cycloolefin copolymer due to the aromatic ring structure of the polystyrene. The glass transition temperature of the cycloolefin copolymer and the modified cycloolefin copolymer is lower than that of the cycloolefin copolymer, and the good compatibility realizes the aim of adjusting the glass transition temperature of the blends of the cycloolefin copolymer and the modified cycloolefin copolymer, thereby improving the processability of the cycloolefin copolymer composite. Syndiotactic polypropylene and propylene-based elastomers may improve the toughness of the composite.
Compared with the prior art, the invention has the following advantages and effects:
(1) The petroleum resin has good compatibility with COC, the glass transition temperature of the cycloolefin copolymer can be effectively reduced after the COC is added, the adjustability of the glass transition temperature within the range of 90-130 ℃ is realized, and the processing cost is reduced. Meanwhile, the method is also beneficial to the molding of the cycloolefin copolymer composite material in a microfluidic device, and the adaptability of the material to various processing technologies is improved.
(2) The structure of the polystyrene has certain similarity with the structure of the cycloolefin copolymer, and the interfacial interaction of the cycloolefin copolymer and the petroleum resin can be improved. The polystyrene has a compatibilization effect on the mixture of the polystyrene and the cycloolefin copolymer to a certain extent, and is favorable for exerting the regulation and control effect of the petroleum resin on the performance of the cycloolefin copolymer.
(3) The addition of syndiotactic polypropylene and polypropylene elastomer (toughening agent) improves the toughness of the cycloolefin copolymer to a certain extent and makes up for short plates with higher brittleness of the cycloolefin copolymer. The two materials enhance the mechanical property of the composite material and reduce the influence of petroleum resin on the mechanical property of the cycloolefin copolymer.
(4) The preparation method is simple, the raw materials are easy to obtain, the cost is lower, the large-scale production is easy, and a new way is provided for the application of the high added value of the cycloolefin copolymer plastic.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In inventive examples 1 to 5, the cycloolefin copolymer was 5013L-10, manufactured by TOPAS advanced polymers, germany, and had a glass transition temperature of 134 deg.C (10 deg.C/min).
The petroleum resin is Escorez 5600 series petroleum resin produced by Exxon Mobil chemical industry Co., USA, and the glass transition temperature of the petroleum resin is 55 ℃ (ETM 300-90).
The syndiotactic polypropylene is the syndiotactic polypropylene which is produced by mPP6006 of the institute of petroleum and chemical engineering and has the melt flow rate (230, 2.16kg at the temperature of between 5 and 8g/10min.
The polystyrene is GPPS-PG33 produced by Jiangsu Zhenjiangqi beautification chemical company Limited, and the Vicat softening point of the polystyrene is 94 ℃ (50N, and the heating rate is 50 ℃). H
The toughening agent is a propylene-based elastomer Vistamaxx6102 produced by Exxon Mobil chemical Co., ltd., U.S. with a melt flow rate of 3g/10min (test temperature 230 ℃ C., load 2.16 kg).
The test results for glass transition in the examples of the invention and the comparative examples are from a relaxation-resistant DSC214 differential calorimeter, test conditions: 20-200 ℃, the heating rate is 10 ℃/min, and the atmosphere is nitrogen.
Example 1
Weighing the following raw materials in proportion: 59.3 parts by mass of cycloolefin copolymer, 24.6 parts by mass of petroleum resin and 16.1 parts by mass of toughening agent. The cycloolefin copolymer, the petroleum resin and the toughening agent are premixed at a mixing temperature of 30 ℃ and a rotation speed of 200 revolutions per minute for 4 minutes. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeding machine, and is subjected to melt extrusion granulation. The process conditions are set as follows: the rotating speed of the feeding machine is 10 r/min, the rotating speed of the screw is 200 r/min, and the temperature of each section of the extruding machine is 160-200 ℃. And (5) pulling strips, and carrying out water granulation.
And (3) carrying out DSC test on the dried cycloolefin copolymer composite material, wherein all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating and cooling rates are 10K/min. The test results are shown in Table 1.
Example 2
Weighing the following raw materials in proportion: 56.9 parts by mass of a cycloolefin copolymer, 26.5 parts by mass of a petroleum resin, and 16.6 parts by mass of polystyrene. The cycloolefin copolymer, the petroleum resin and the polystyrene were premixed at a mixing temperature of 30 ℃ and a rotation speed of 200 rpm for 4 minutes. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeding machine, and is subjected to melt extrusion granulation. The process conditions were set as follows: the rotating speed of the feeding machine is 20 r/min, the rotating speed of the screw is 300 r/min, and the temperature of each section of the extruding machine is 160-200 ℃. And (5) pulling strips, and carrying out water granulation.
And (3) carrying out DSC test on the dried cycloolefin copolymer composite material, wherein all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating and cooling rates are 10K/min. The test results are shown in Table 1.
Example 3
Weighing the following raw materials in proportion: 51.1 parts by mass of cycloolefin copolymer, 25.0 parts by mass of petroleum resin, 7.1 parts by mass of syndiotactic polypropylene, 8.6 parts by mass of polystyrene and 8.2 parts by mass of toughening agent. The cycloolefin copolymer, the petroleum resin, the syndiotactic polypropylene, the polystyrene and the toughening agent are premixed for 5 minutes at a mixing temperature of 30 ℃ and a rotation speed of 200 revolutions per minute. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeder, and is subjected to melt extrusion granulation. The process conditions were set as follows: the rotating speed of the feeding machine is 30 revolutions per minute, the rotating speed of the screw is 400 revolutions per minute, and the temperature of each section of the extruding machine is 160-200 ℃. And (5) drawing strips, watering and granulating.
And (3) carrying out DSC test on the dried cycloolefin copolymer composite material, wherein all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating and cooling rates are 10K/min. The test results are shown in Table 1.
Example 4
Weighing the following raw materials in proportion: 52.3 parts by mass of cycloolefin copolymer, 24.0 parts by mass of petroleum resin, 16.1 parts by mass of polystyrene and 7.5 parts by mass of toughening agent. The cycloolefin copolymer, the petroleum resin, the polystyrene and the toughening agent were premixed at a mixing temperature of 30 ℃ and a rotation speed of 200 rpm for 5 minutes. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeding machine, and is subjected to melt extrusion granulation. The process conditions were set as follows: the rotating speed of the feeding machine is 40 r/min, the rotating speed of the screw is 500 r/min, and the temperature of each section of the extruding machine is 160-200 ℃. And (5) pulling strips, and carrying out water granulation.
And (3) carrying out DSC test on the dried cycloolefin copolymer composite material, wherein all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating and cooling rates are 10K/min. The test results are shown in Table 1.
Example 5
Weighing the following raw materials in proportion: the amount of the cycloolefin copolymer was 51.1 parts by mass, and the amount of the petroleum resin was 48.9 parts by mass. The cycloolefin copolymer and the petroleum resin were premixed at a mixing temperature of 20 ℃ and a rotation speed of 200 rpm for 3 minutes. Then, the premixed material is added into a co-rotating parallel double-screw extruder from a feeding machine, and is subjected to melt extrusion granulation. The process conditions were set as follows: the rotating speed of the feeding machine is 50 r/min, the rotating speed of the screw is 600 r/min, and the temperature of each section of the extruding machine is 160-200 ℃. And (5) drawing strips, watering and granulating.
And (3) carrying out DSC test on the dried cycloolefin copolymer composite material, wherein all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating and cooling rates are 10K/min. The test results are shown in Table 1.
Comparative example 1
DSC test is carried out on a cycloolefin copolymer sample, all experiments are carried out in a nitrogen atmosphere, the mass of the sample is 5-8mg, and the heating and cooling rates are 10K/min. The test results are shown in Table 1.
TABLE 1 thermal Properties of composites obtained in examples and comparative examples
| Raw materials | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example |
| COC | 59.3 | 56.9 | 51.1 | 52.4 | 51.1 | 100 |
| Petroleum resin | 24.6 | 26.5 | 25.0 | 24.0 | 48.9 | 0 |
| sPP | 0 | 0 | 7.1 | 0 | 0 | 0 |
| PS | 0 | 16.6 | 8.6 | 16.1 | 0 | 0 |
| Toughening agent | 16.1 | 0 | 8.2 | 7.5 | 0 | 0 |
| Performance of | ||||||
| Composite Tg/. Degree.C | 112.4 | 92.1 | 113.5 | 92.7 | 101.6 | 132.3 |
As described above, the present invention can be preferably realized.
The glass transition temperature of the composite material obtained by the invention is obviously reduced, and the composite material can be regulated and controlled according to the processing requirement, so that the problems of difficult secondary processing, high processing cost and the like caused by the higher glass transition temperature of the cycloolefin copolymer can be solved, and the wide application of the composite material in the fields of high-precision processing of microfluidic chips and the like is promoted.
The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and fall within the scope of the present invention.
Claims (7)
1. A glass transition temperature adjustable cyclic olefin copolymer composite comprising the following components:
51.1 to 59.3 parts by mass of cycloolefin copolymer;
24.0 to 48.9 parts by mass of petroleum resin;
0-7.1 parts by mass of syndiotactic polypropylene;
0 to 16.6 parts by mass of polystyrene;
0 to 16.1 parts of toughening agent.
2. The glass transition temperature-adjustable cycloolefin copolymer composite according to claim 1, characterized in that the glass transition temperature of the cycloolefin copolymer is 130 ℃ or higher.
3. The glass transition temperature-adjustable cycloolefin copolymer composite according to claim 2, wherein the petroleum resin is an aromatic hydrocarbon-modified alicyclic hydrogenated resin having a glass transition temperature of 40 ℃ or more.
4. The cyclic olefin copolymer composite with adjustable glass transition temperature of claim 3, wherein the syndiotactic polypropylene has a syndiotacticity of 80% or more and a melt flow rate of 5 to 20g/10min.
5. The glass transition temperature-adjustable cycloolefin copolymer composite according to claim 4, wherein the polystyrene homopolymer has a Vicat softening point of 94 ℃.
6. The glass transition temperature adjustable cyclic olefin copolymer composite as claimed in claim 5, wherein the toughening agent is a polypropylene elastomer having a melt flow rate of 2 to 20g/10min.
7. A method for preparing the glass transition temperature-adjustable cyclic olefin copolymer composite according to any one of claims 1 to 6, comprising the steps of:
(1) Mixing: sequentially adding the cycloolefin copolymer, the petroleum resin, the syndiotactic polypropylene, the polystyrene and the toughening agent into a high-speed mixer for premixing, wherein the mixing temperature is 20-40 ℃, the rotating speed is 200-400 r/min, and the mixing time is 3-5 min, so as to obtain a premix of the cycloolefin copolymer composite material;
(2) And (3) double-screw extrusion granulation: extruding and granulating the premix obtained in the step (1) by using a parallel co-rotating double-screw extruder with the length-diameter ratio of 40; the rotating speed of the feeder is set to be 10-50 revolutions per minute, and the rotating speed of the screw is set to be 200-600 revolutions per minute; the temperature of each section of the extruder is 160-200 ℃, and the cycloolefin copolymer composite material is obtained.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116574391A (en) * | 2023-04-14 | 2023-08-11 | 湖南映宏新材料股份有限公司 | Method for manufacturing wood-plastic composite material by using waste circuit board resin powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09221577A (en) * | 1996-02-13 | 1997-08-26 | Japan Synthetic Rubber Co Ltd | Resin composition |
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2022
- 2022-09-05 CN CN202211078239.1A patent/CN115386187A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09221577A (en) * | 1996-02-13 | 1997-08-26 | Japan Synthetic Rubber Co Ltd | Resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116574391A (en) * | 2023-04-14 | 2023-08-11 | 湖南映宏新材料股份有限公司 | Method for manufacturing wood-plastic composite material by using waste circuit board resin powder |
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