CN112552624A - Method for improving processability of polychlorotrifluoroethylene resin and mechanical toughness of product thereof - Google Patents
Method for improving processability of polychlorotrifluoroethylene resin and mechanical toughness of product thereof Download PDFInfo
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- CN112552624A CN112552624A CN202011459844.4A CN202011459844A CN112552624A CN 112552624 A CN112552624 A CN 112552624A CN 202011459844 A CN202011459844 A CN 202011459844A CN 112552624 A CN112552624 A CN 112552624A
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- copolymer
- chlorotrifluoroethylene
- pctfe
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of a product thereof, which comprises the following steps: s1, preparing materials; s2, mixing; s3, putting the mixed materials into an extruder for melt blending extrusion; s4, granulating the blended extrudate obtained in the step S3 by a granulator to obtain PCTFE modified master batches; s5, processing, namely modifying the processability and mechanical toughness of the PCTFE by adopting a chlorotrifluoroethylene copolymer, wherein the interaction between the chlorotrifluoroethylene copolymer and PCTFE molecules can be improved due to the chlorotrifluoroethylene chain segment contained in the copolymer; the copolymer also has higher fluorine content, and can keep high corrosion resistance and low-temperature toughness; the performance of the composite system can be regulated and controlled by the addition amount of the copolymer and the proportion of each block in the copolymer.
Description
Technical Field
The invention relates to the field of materials science, in particular to a method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of a product thereof.
Background
The molecular chain of Polychlorotrifluoroethylene (PCTFE) is composed of carbon atoms, fluorine atoms and chlorine atoms, and does not contain hydrogen atoms. Because the carbon skeleton is tightly wrapped by fluorine atoms and chlorine atoms, the carbon skeleton is effectively prevented from being exposed, and the molecular structure is regular, the PCTFE has good chemical corrosion resistance and low-temperature (<0 ℃) mechanical toughness, so that the PCTFE is commonly used in the fields with large temperature change and corrosion prevention requirements. On the other hand, PCTFE has high viscosity in a molten state, a narrow processing temperature window, low heat conduction efficiency, high crystallization rate during cooling and high heat shrinkage, so that the thermoplastic molding processability is poor, and a product has high brittleness at normal temperature, thereby limiting the application of the product in many fields.
Currently, the studies on modification of PCTFE are largely divided into chemical modification and physical modification. The chemical modification is mainly that chlorotrifluoroethylene monomer and ethylene, vinylidene fluoride and other monomers are subjected to copolymerization reaction to destroy the molecular regularity and intermolecular force, thereby reducing the crystallinity and improving the processability and mechanical toughness. The modification is complex in technology and remarkable in product cost improvement, and with the introduction of a copolymerization chain segment, the use temperature range of PCTFE becomes narrow, and the heat distortion temperature and the low-temperature toughness can be remarkably reduced. The physical modification is mainly to introduce the modifying component by means of blending. For example, Li Quer et al [ synthetic resins and plastics, 2015,32(3):40-43 ] reported that melt blending PCTFE with a core-shell acrylate copolymer can shorten the plasticizing time, reduce crystallinity, and improve mechanical toughness. Von Na et al [ plastics science and technology, 2014,42(6): 109-112.) use rare earth composite stabilizer to improve the processing stability of PCTFE by melt blending, and research shows that the dynamic thermal stability of PCTFE is firstly increased and then decreased with the increase of the dosage of the rare earth stabilizer. When the rare earth stabilizer reaches 6phr, the effect is most obvious, the mechanical property of the material is correspondingly improved, and the addition of the rare earth composite stabilizer reduces the plasticizing time of PCTFE and improves the processing fluidity of the material. However, the physical modification techniques disclosed so far add components mostly free of fluorine, resulting in a decrease in corrosion resistance of the whole system, and do not involve the influence of low temperature (<0 ℃) mechanical toughness of the material, thus limiting the application fields of PCTFE.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of a product thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of its products comprises the following steps:
s1, weighing the copolymer of the PCTFE resin and the chlorotrifluoroethylene and an auxiliary agent according to the mass ratio;
s2, physically mixing the copolymer of PCTFE resin and chlorotrifluoroethylene, a stabilizer and a lubricant by using a high-speed mixer to obtain a mixed material;
s3, putting the mixed materials into an extruder for melt blending extrusion;
s4, granulating the blended extrudate obtained in the step S3 by a granulator to obtain PCTFE modified master batches;
and S5, processing the PCTFE modified master batch to obtain the required product.
Further, the copolymer of the chlorotrifluoroethylene comprises a copolymer of the chlorotrifluoroethylene and the vinylidene fluoride or a copolymer of the chlorotrifluoroethylene, the vinylidene fluoride and the trifluoroethylene, the addition amount of the copolymer of the chlorotrifluoroethylene accounts for not more than 20% of the total material amount by mass, and the addition amount of the auxiliary agent accounts for not more than 2% of the total material amount by mass.
Further, in the step S3, the temperature in the extruder is 200 ℃ to 320 ℃.
Further, in step S5, the forming process is one or more of hot pressing, injection molding, extrusion, casting, double drawing, blow molding, and 3D printing.
Further, the shape of the product in the step S5 is block, tube, film, fiber, or profile.
Further, the auxiliary agent is a stabilizer and a lubricant, wherein the mass fraction of the lubricant is not more than 1% of the total mass of the materials.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the processability and normal-temperature mechanical toughness of the resin are improved, and the original corrosion resistance and low-temperature toughness of the PCTFE are maintained.
2. The performance of the composite system can be regulated and controlled by the addition amount of the copolymer and the proportion of each block in the copolymer.
3. The processing performance is adjustable, so that various processing modes such as hot pressing, injection molding, extrusion, tape casting, double drawing, blow molding and the like can be met, the shape of the product is various, the requirements of more application fields can be met, meanwhile, the continuous and large-scale production is easy, and the service performance of the product is stable and reliable.
4. The modification method is simple and easy to implement, the product prepared by the modified material has excellent comprehensive performance, is easy for continuous and large-scale production, and the product has stable and reliable service performance for a long time.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific embodiments as follows:
therefore, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention, and all other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without inventive efforts shall fall within the scope of the present invention.
In the description of the present invention, it should also be noted that, unless otherwise explicitly specified or limited, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; the two elements can be directly connected or indirectly connected through an intermediate medium, and the two elements can be communicated with each other, so that the specific meaning of the terms in the invention can be understood by those skilled in the art.
Example 1:
a method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of its products comprises the following steps:
s1, weighing the copolymer of the PCTFE resin and the chlorotrifluoroethylene and an auxiliary agent according to the mass ratio;
s2, physically mixing the copolymer of PCTFE resin and chlorotrifluoroethylene, a stabilizer and a lubricant by using a high-speed mixer to obtain a mixed material;
s3, putting the mixed materials into an extruder for melt blending extrusion;
s4, granulating the blended extrudate obtained in the step S3 by a granulator to obtain PCTFE modified master batches;
and S5, processing the PCTFE modified master batch to obtain the required product.
In this embodiment, the copolymer of chlorotrifluoroethylene includes a copolymer of chlorotrifluoroethylene and vinylidene fluoride or a copolymer of chlorotrifluoroethylene, vinylidene fluoride and trifluoroethylene, the addition amount of the copolymer of chlorotrifluoroethylene accounts for 10% by mass of the total amount of the materials, and the addition amount of the auxiliary agent accounts for 1% by mass of the total amount of the materials.
In this embodiment, in the step S3, the temperature in the extruder is 200 ℃ to 320 ℃.
In this embodiment, in the step S5, the forming process is one or more of hot pressing, injection molding, extrusion, casting, double drawing, blow molding, and 3D printing.
In this embodiment, the shape of the product in step S5 is block, tube, film, fiber, or irregular material.
In this embodiment, the auxiliary agent is a stabilizer and a lubricant, wherein the mass fraction of the lubricant is not more than 1% of the total mass of the material.
Example 2:
a method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of its products comprises the following steps:
s1, weighing the copolymer of the PCTFE resin and the chlorotrifluoroethylene and an auxiliary agent according to the mass ratio;
s2, physically mixing the copolymer of PCTFE resin and chlorotrifluoroethylene, a stabilizer and a lubricant by using a high-speed mixer to obtain a mixed material;
s3, putting the mixed materials into an extruder for melt blending extrusion;
s4, granulating the blended extrudate obtained in the step S3 by a granulator to obtain PCTFE modified master batches;
and S5, processing the PCTFE modified master batch to obtain the required product.
In this embodiment, the copolymer of chlorotrifluoroethylene includes a copolymer of chlorotrifluoroethylene and vinylidene fluoride or a copolymer of chlorotrifluoroethylene, vinylidene fluoride and trifluoroethylene, the addition amount of the copolymer of chlorotrifluoroethylene accounts for 15% by mass of the total amount of the materials, and the addition amount of the auxiliary agent accounts for 1.5% by mass of the total amount of the materials.
In this embodiment, in the step S3, the temperature in the extruder is 200 ℃ to 320 ℃.
In this embodiment, in the step S5, the forming process is one or more of hot pressing, injection molding, extrusion, casting, double drawing, blow molding, and 3D printing.
In this embodiment, the shape of the product in step S5 is block, tube, film, fiber, or irregular material.
In this embodiment, the auxiliary agent is a stabilizer and a lubricant, wherein the mass fraction of the lubricant is not more than 1% of the total mass of the material.
Example 3:
a method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of its products comprises the following steps:
s1, weighing the copolymer of the PCTFE resin and the chlorotrifluoroethylene and an auxiliary agent according to the mass ratio;
s2, physically mixing the copolymer of PCTFE resin and chlorotrifluoroethylene, a stabilizer and a lubricant by using a high-speed mixer to obtain a mixed material;
s3, putting the mixed materials into an extruder for melt blending extrusion;
s4, granulating the blended extrudate obtained in the step S3 by a granulator to obtain PCTFE modified master batches;
and S5, processing the PCTFE modified master batch to obtain the required product.
In this embodiment, the copolymer of chlorotrifluoroethylene includes a copolymer of chlorotrifluoroethylene and vinylidene fluoride or a copolymer of chlorotrifluoroethylene, vinylidene fluoride and trifluoroethylene, the addition amount of the copolymer of chlorotrifluoroethylene accounts for 18% by mass of the total amount of the materials, and the addition amount of the auxiliary agent accounts for 1% by mass of the total amount of the materials.
In this embodiment, in the step S3, the temperature in the extruder is 200 ℃ to 320 ℃.
In this embodiment, in the step S5, the forming process is one or more of hot pressing, injection molding, extrusion, casting, double drawing, blow molding, and 3D printing.
In this embodiment, the shape of the product in step S5 is block, tube, film, fiber, or irregular material.
In this embodiment, the auxiliary agent is a stabilizer and a lubricant, wherein the mass fraction of the lubricant is not more than 1% of the total mass of the material.
The processability and mechanical toughness of PCTFE are modified by adopting the chlorotrifluoroethylene copolymer, and the interaction between the chlorotrifluoroethylene copolymer and PCTFE molecules can be improved due to the chlorotrifluoroethylene chain segment contained in the copolymer; the copolymer also has higher fluorine content, and can keep high corrosion resistance and low-temperature toughness; the performance of the composite system can be regulated and controlled by the addition amount of the copolymer and the proportion of each block in the copolymer.
The above embodiments are not intended to limit the shape, material, structure, etc. of the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (6)
1. A method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of a product thereof is characterized by comprising the following steps:
s1, weighing the copolymer of the PCTFE resin and the chlorotrifluoroethylene and an auxiliary agent according to the mass ratio;
s2, physically mixing the copolymer of PCTFE resin and chlorotrifluoroethylene, a stabilizer and a lubricant by using a high-speed mixer to obtain a mixed material;
s3, putting the mixed materials into an extruder for melt blending extrusion;
s4, granulating the blended extrudate obtained in the step S3 by a granulator to obtain PCTFE modified master batches;
and S5, processing the PCTFE modified master batch to obtain the required product.
2. The method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of its products according to claim 1, wherein the copolymer of chlorotrifluoroethylene comprises a copolymer of chlorotrifluoroethylene and vinylidene fluoride or a copolymer of chlorotrifluoroethylene, vinylidene fluoride and trifluoroethylene, the copolymer of chlorotrifluoroethylene is added in an amount of not more than 20% by mass of the total amount of materials, and the additive is added in an amount of not more than 2% by mass of the total amount of materials.
3. The method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of its product according to claim 1, wherein in the step S3, the temperature in the extruder is 200 ℃ to 320 ℃.
4. The method of claim 1, wherein in step S5, the shaping process is one or more selected from hot pressing, injection molding, extrusion, casting, double drawing, blow molding, and 3D printing.
5. The method of claim 1, wherein the product of step S5 is in the shape of block, tube, film, fiber, or profile.
6. The method for improving the processability of polychlorotrifluoroethylene resin and the mechanical toughness of its products according to claim 1, wherein the auxiliary agent is stabilizer, lubricant, wherein the mass fraction of lubricant is not more than 1% of the total mass of the materials.
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| CN202011459844.4A CN112552624A (en) | 2020-12-11 | 2020-12-11 | Method for improving processability of polychlorotrifluoroethylene resin and mechanical toughness of product thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113444330A (en) * | 2021-06-28 | 2021-09-28 | 浙江巨化技术中心有限公司 | Polychlorotrifluoroethylene resin composition |
| CN113461953A (en) * | 2021-06-16 | 2021-10-01 | 济南大学 | Preparation method of polychlorotrifluoroethylene resin |
| CN115386183A (en) * | 2022-09-28 | 2022-11-25 | 四川大学 | High-performance polytrifluorochloroethylene water-blocking material and preparation method and application thereof |
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| WO2007113424A1 (en) * | 2006-04-05 | 2007-10-11 | Arkema France | Pvdf-based extrusion-aiding agent |
| CN107163460A (en) * | 2017-07-19 | 2017-09-15 | 日氟荣高分子材料(上海)有限公司 | A kind of coloured fluorine resin film of high temperature resistant, preparation method and the usage |
| CN111961298A (en) * | 2020-08-31 | 2020-11-20 | 四川大学 | Low dielectric loss high water resistance transparent film and preparation method thereof |
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2020
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2007113424A1 (en) * | 2006-04-05 | 2007-10-11 | Arkema France | Pvdf-based extrusion-aiding agent |
| CN107163460A (en) * | 2017-07-19 | 2017-09-15 | 日氟荣高分子材料(上海)有限公司 | A kind of coloured fluorine resin film of high temperature resistant, preparation method and the usage |
| CN111961298A (en) * | 2020-08-31 | 2020-11-20 | 四川大学 | Low dielectric loss high water resistance transparent film and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113461953A (en) * | 2021-06-16 | 2021-10-01 | 济南大学 | Preparation method of polychlorotrifluoroethylene resin |
| CN113444330A (en) * | 2021-06-28 | 2021-09-28 | 浙江巨化技术中心有限公司 | Polychlorotrifluoroethylene resin composition |
| CN113444330B (en) * | 2021-06-28 | 2023-01-24 | 浙江巨化技术中心有限公司 | Polychlorotrifluoroethylene resin composition |
| CN115386183A (en) * | 2022-09-28 | 2022-11-25 | 四川大学 | High-performance polytrifluorochloroethylene water-blocking material and preparation method and application thereof |
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Application publication date: 20210326 |