CN112724561A - Low-shrinkage thermoplastic fluoroplastic alloy and preparation method thereof - Google Patents
Low-shrinkage thermoplastic fluoroplastic alloy and preparation method thereof Download PDFInfo
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Abstract
The invention provides a low-shrinkage thermoplastic fluoroplastic alloy, which comprises the following components in parts by weight: 20-60 parts of plastic fluoroplastic, 5-25 parts of polyaryletherketone, 5-25 parts of polyphenylene sulfide, 1-4 parts of silicone oil, 0.5-3 parts of coupling agent, 5-10 parts of nano stiffening agent and 0.5-3 parts of antioxidant; the polyaryletherketone is any one of PEEK, PEKK and PEEKK; d50 of the polyphenylene sulfide linear high molecular weight micro powder is less than 30 μm; the nano stiffening agent is sheet or spherical silicon dioxide micropowder with the diameter of 200nm-800 nm. The preparation process is simple, and the thermoplastic fluoroplastic alloy with high heat resistance, corrosion resistance, high toughness, high rigidity and shrinkage of less than 2.5% can be produced in a large amount in an industrialized mode. When the fluoroplastic alloy is used for preparing a product with high precision requirement, higher matching degree with the size of a die can be obtained; meanwhile, the fluoroplastic alloy can be used for preparing large-size long straight tubular materials.
Description
Technical Field
The invention relates to the field of engineering plastics, in particular to a thermoplastic fluoroplastic alloy and a preparation method thereof.
Background
Fluorine materials are a class of directly-linked alkane polymers in which some or all of the hydrogen atoms are replaced with fluorine atoms, the most common being Polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), depending on the amount of hydrogen atoms replaced. Fluorine atoms have extremely strong electronegativity, so that polytetrafluoroethylene has extremely strong crystallization property, and fluorine plastics such as high temperature resistance, corrosion resistance and excellent mechanical properties are endowed with fluorine plastics. But the extremely strong crystallization property reduces the processing property of the fluoroplastic, the polytetrafluoroethylene cannot be processed and molded by melting, and then the tetrafluoroethylene is copolymerized to prepare a plurality of fluorine-containing block copolymers, such as perfluoroethylene propylene copolymer (FEP), polyperfluoroalkoxy resin (PFA), ethylene-chlorotrifluoroethylene copolymer (ECTFE), ethylene-tetrafluoroethylene copolymer (ETFE) and the like, so that the processing property of the fluoroplastic is greatly improved on the basis of keeping the original excellent property of the fluoroplastic. However, as the thermal expansion coefficient of the fluoroplastic is generally large, the volume shrinkage rate of the fluoroplastic product is high in the cooling and curing process after demolding, so that the matching degree of the cooled product and a mold is generally low, the mold design of the fluoroplastic product with large size and high precision requirement is very complex, the yield of the finished product is low, and particularly, the situations of poor section roundness, straight pipe bending and the like of a tubular sample after cooling are often caused, so that the quality of the product and the application range of the fluoroplastic are greatly reduced.
Polyaryletherketones are semi-crystalline polymers formed by connecting phenylene rings through ether bonds and carbonyl groups (ketones), and can form a plurality of different polymers according to different connection sequences and proportions of ether bonds, ketone groups and benzene rings in molecular chains, wherein the different polymers comprise Polyetheretherketone (PEEK), Polyetherketone (PEK), Polyetherketoneketone (PEKK), Polyetheretherketoneketone (PEEKK), Polyetherketoneketone (PEKEKK) and the like. Polyphenylene Sulfide (PPS) is also a similar type of semi-crystalline polymer material having a benzene ring in the main chain. The polymers have higher rigidity and heat resistance due to the rigidity of benzene rings in the main chain. Although relatively low in toughness, these materials possess low shrinkage. Meanwhile, phase separation can be generated when the polyaryletherketone and the polyphenylene sulfide are blended with the fluoroplastic, so that the blending alloy of the polyaryletherketone and the fluoroplastic can obtain excellent performance by adjusting the phase region morphology.
The silicon dioxide micro-nano powder is a rigid nano material, and can improve the rigidity of the material. Due to the function of interface energy, the silicon dioxide micro-nano powder tends to be distributed at the phase interface of the high polymer material. For the polymer alloy, the orientation of the silicon dioxide micro-nano powder can be regulated and controlled to be distributed at a multiphase interface through proper process conditions. The rigid continuous structure of the silicon dioxide obtained in the way can greatly inhibit the contraction phenomenon of the fluoroplastic in the cooling process, thereby reducing the contraction rate of the fluoroplastic.
Disclosure of Invention
The invention provides a thermoplastic fluoroplastic alloy and a preparation method thereof, aiming at overcoming the defects in the prior art and solving the disadvantage of higher shrinkage of the existing fluoroplastic.
In order to solve the technical problems, the invention adopts the technical scheme that: a low-shrinkage thermoplastic fluoroplastic alloy is characterized by comprising the following components in parts by weight: 20-60 parts of plastic fluoroplastic, 5-25 parts of polyaryletherketone, 5-25 parts of polyphenylene sulfide, 1-4 parts of silicone oil, 0.5-3 parts of coupling agent, 5-10 parts of nano stiffening agent and 0.5-3 parts of antioxidant;
the polyaryletherketone is any one of PEEK, PEKK and PEEKK; the polyphenylene sulfideIs composed ofPowderBodyD50 is less than 30 μm; the nano stiffening agent is sheet or spherical silicon dioxide micropowder with the diameter of 200nm-800 nm.
Further, the thermoplastic fluoroplastic is one or more of PVDF, FEP, PFA, ETFE and PCTFF.
Further, the coupling agent is a composite coupling agent of a titanate coupling agent and a silane coupling agent; the titanate coupling agent comprises: a monoalkoxy titanate coupling agent, a monoalkoxy pyrophosphate titanate coupling agent, an integrated titanate coupling agent and a ligand titanate coupling agent; the silane coupling agent includes: epoxy group-containing alkoxysilane compounds such as 3- (2, 3-glycidoxy) propyltriethoxysilane and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.
The paint further comprises a functional filler, wherein the addition amount of the functional filler is not more than 5 parts, and the functional filler comprises a coloring agent, an ultraviolet-resistant absorbent, a release agent and a nucleating agent.
In order to solve the technical problem, the invention adopts another technical scheme that: a preparation method of a thermoplastic fluoroplastic alloy with low shrinkage rate is characterized by comprising the following steps:
s1, adding the thermoplastic fluoroplastic, the polyaryletherketone, the polyphenylene sulfide, the coupling agent and the antioxidant into a stirring kettle, and stirring to obtain a blend A, wherein the rotating speed of the stirring kettle is 500-1000 r/min, and the stirring time is 5-10 min;
s2, adding silicone oil and a nano stiffening agent into the blend A, and then arranging a stirring kettle 1500 r/min-2500 r/min for stirring for 5 r/min-10 min until the surface temperature of a sample is 70-80 ℃, so as to obtain a blend B;
s3, carrying out dry heat treatment on the blend B until the moisture content is lower than 0.02% to obtain a blend C;
and S4, adding the blend C into a double-screw extruder for melt blending granulation to obtain the fluoroplastic alloy product.
Further, the treatment temperature in the step S3 is 120-180 ℃, and the treatment time is 1-5 h.
Further, the ratio of the length to the diameter of the screw of the twin-screw extruder in the S4 is more than 35, and the twin-screw extruder at least comprises 2 shearing modules, wherein at least one shearing module has a 90-degree rotation angle.
Furthermore, the temperature of each zone of the double-screw extruder is 280-400 ℃, the current of a main machine is 0.5-1.2A, and the rotating speed of the main machine is 100-500 rpm.
Furthermore, the continuous working temperature of the thermoplastic fluoroplastic alloy is not lower than 220 ℃, the shrinkage rate is less than 2.5%, and the thermoplastic fluoroplastic alloy has good corrosion resistance and electrical insulation property.
Compared with the prior art, the invention has the beneficial effects that: the preparation process is simple, and the thermoplastic fluoroplastic alloy with high heat resistance, high corrosion resistance, high toughness, high rigidity and shrinkage of less than 2.5% can be produced in a large amount in an industrialized mode. When the fluoroplastic alloy is used for preparing a product with high precision requirement, higher matching degree with the size of a die can be obtained; meanwhile, the fluoroplastic alloy can be used for preparing large-size long straight tubular materials.
Detailed Description
It is easily understood that according to the technical solution of the present invention, a person skilled in the art can propose various alternative structures and implementation ways without changing the spirit of the present invention. Therefore, the following detailed description is merely illustrative of the technical solutions of the present invention, and should not be construed as being all of the present invention or limiting or restricting the technical solutions of the present invention.
A low-shrinkage thermoplastic fluoroplastic alloy comprises the following components in parts by weight: 20-60 parts of thermoplastic fluoroplastic, 5-25 parts of polyaryletherketone, 5-25 parts of polyphenylene sulfide, 1-4 parts of silicone oil, 0.5-3 parts of coupling agent, 5-10 parts of nano stiffening agent and 0.5-3 parts of antioxidant.
The thermoplastic fluoroplastic is at least one of polyvinylidene fluoride (PVDF), perfluoroethylene propylene copolymer (FEP), polyperfluoroalkoxy resin (PFA), ethylene-tetrafluoroethylene copolymer (ETFE) and Polychlorotrifluoroethylene (PCTFF), and can be adjusted according to the use temperature of the product. If a continuous 250 ℃ service temperature is desired, PFA is preferred; if a continuous use temperature of less than 180 ℃ is desired, PVDF is preferred.
The polyaryletherketone is Polyetheretherketone (PEEK); polyether ketone (PEKK) and polyether ether ketone (PEEKK).
In order to improve the dispersibility of polyphenylene sulfide (PPS), thermoplastic fluoroplastic and polyaryletherketone and the phase region distribution after blending, the polyphenylene sulfide (PBS) is linear high molecular weight superfine powder, and the D50 size is less than 30 microns.
The coupling agent is a composite coupling agent of titanate coupling agent and silane coupling agent. Wherein the titanate coupling agent comprises: a monoalkoxy titanate coupling agent, a monoalkoxy pyrophosphate titanate coupling agent, an integrated titanate coupling agent and a ligand titanate coupling agent. The silane coupling agent includes: epoxy group-containing alkoxysilane compounds such as 3- (2, 3-glycidoxy) propyltriethoxysilane and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.
The nano stiffening agent is flake or spherical silicon dioxide micropowder with the size of 200-800 nm. The surface of the micro powder is grafted with short-chain high molecules so as to improve the compatibility with the fluoroplastic alloy.
Aiming at different application requirements, other functional fillers can be added into the polymer alloy, and the specific steps are as follows: coloring agent, ultraviolet-resistant absorbent, mold release agent and nucleating agent. The addition amount of the functional filler is controlled within 5 parts.
In order to further improve the rigidity of the material and reduce the heat shrinkage ratio, other rigid fillers can be added in proper amount, including: micro-nano fillers such as graphene, carbon nanotubes, carbon fibers, calcium oxide, talcum powder, silicate, calcium carbonate, calcium hydroxide and magnesium hydroxide, and fibrous fillers such as glass fibers and ceramic fibers.
In order to reduce the shrinkage rate of the fluoroplastic alloy, each phase region in the fluoroplastic alloy should have a specific domain structure, which is as follows: the blend shows a double-wiring phase separation mechanism by adjusting the proportion of the polymer, and the post-annealing temperature is controlled to be higher than the double-wiring temperature, so that the fluoroplastic alloy shows a phase structure of a double-continuous phase. Ensuring that the thermoplastic fluoroplastic has an island phase structure and the polyaryletherketone and the polyphenylene sulfide have a bicontinuous phase. And the silicon dioxide micro-nano powder is distributed at the phase interface of a bicontinuous phase and an island-shaped phase structure and forms continuous orientation arrangement. Therefore, on the basis of keeping excellent heat resistance, corrosion resistance, excellent toughness and antistatic performance of the fluoroplastic, the rigidity of the material is improved, and the shrinkage rate is greatly reduced.
The following is a description of specific examples of the present invention. The examples are only for the understanding of the present invention, and the scope of the present invention is not limited thereto, and any non-original formulation or process modification made by the study of the invention and the technical scope of the present invention by those skilled in the art should be covered by the scope of the present invention.
The first embodiment is as follows:
the formula adopted by the embodiment comprises the following components in parts by weight: 40 parts of polyperfluoroalkoxy resin, 25 parts of polyether-ether-ketone, 15 parts of polyphenylene sulfide powder, 10 parts of silicon dioxide sheet-shaped nano stiffening agent, 3 parts of monoalkoxy pyrophosphate titanate coupling agent, 3 parts of antioxidant and 4 parts of silicone oil.
The preparation method adopted in this example is as follows:
(1) adding polyperfluoroalkoxy resin, polyether-ether-ketone, polyphenylene sulfide powder, monoalkoxy pyrophosphate titanate coupling agent and antioxidant into a stirring kettle, and stirring at the rotating speed of 1000 rpm for 5min to obtain a blend A.
(2) Adding silicone oil and silicon dioxide flaky nano stiffening agent into the blend A, and stirring at a high speed of 2000 r/min for 10min until the surface temperature of the sample reaches 70-80 ℃ to obtain a blend B.
(3) And carrying out dry heat treatment on the blend B until the moisture content is lower than 0.02 percent to obtain a blend C.
(4) And adding the blend C into a double-screw extruder for melt blending granulation, wherein the length-diameter ratio of the double-screw extruder is 52, the temperature of each area from a feeding port to a discharging port is 380 ℃, 390 ℃, 380 ℃, 370 ℃, 380 ℃, 385 ℃, 390 ℃, and the main machine rotation speed is 400rpm, and the mixture is subjected to melt mixing and granulation to obtain granules.
(5) And placing the prepared granules in an oven at 180 ℃ for 6 hours to obtain the fluoroplastic alloy with low shrinkage.
Example two:
the formula adopted by the embodiment comprises the following components in parts by weight: 45 parts of polyethylene-tetrafluoroethylene copolymer, 20 parts of polyether-ether-ketone, 15 parts of polyphenylene sulfide powder, 9 parts of silicon dioxide sheet-shaped nano stiffening agent, 2 parts of monoalkoxy pyrophosphate titanate coupling agent, 2 parts of 3- (2, 3-epoxypropoxy) propyl triethoxysilane coupling agent, 3 parts of antioxidant and 4 parts of silicone oil.
The preparation method adopted in this example is as follows:
(1) adding ethylene-tetrafluoroethylene copolymer, polyether ketone, polyphenylene sulfide powder, monoalkoxy pyrophosphate titanate coupling agent, 3- (2, 3-epoxypropoxy) propyl triethoxysilane coupling agent and antioxidant into a stirring kettle, stirring, wherein the rotating speed of the stirring kettle is 1000 rpm, and the stirring time is 5min to obtain a blend A.
(2) Adding silicone oil and silicon dioxide flaky nano stiffening agent into the blend A, and stirring at a high speed of 2000 r/min for 10min until the surface temperature of the sample reaches 70-80 ℃ to obtain a blend B.
(3) And carrying out dry heat treatment on the blend B until the moisture content is lower than 0.02 percent to obtain a blend C.
(4) And adding the blend C into a double-screw extruder for melt blending granulation, wherein the length-diameter ratio of the double-screw extruder is 52, the temperature of each area from a feeding port to a discharging port is 370 ℃, 380 ℃, 360 ℃, 350 ℃, 360 ℃, 370 ℃, 365 ℃, 380 ℃ and the rotation speed of a main machine is 400rpm, and the mixture is melted, mixed and granulated to obtain granules.
(5) And placing the prepared granules in an oven at 170 ℃ for 7 hours to obtain the fluoroplastic alloy with low shrinkage.
Example three:
the formula adopted by the embodiment comprises the following components in parts by weight: 55 parts of perfluoroethylene propylene copolymer, 20 parts of polyether-ether-ketone, 10 parts of polyphenylene sulfide powder, 7 parts of silicon dioxide sheet-shaped nano stiffening agent, 2 parts of monoalkoxy pyrophosphate titanate coupling agent, 2 parts of 3- (2, 3-epoxypropoxy) propyl triethoxysilane coupling agent, 2 parts of antioxidant and 2 parts of silicone oil.
The preparation method adopted in this example is as follows:
(1) adding a perfluoroethylene propylene copolymer, polyether-ether-ketone, polyphenylene sulfide powder, a monoalkoxy pyrophosphate titanate coupling agent, a 3- (2, 3-epoxypropoxy) propyltriethoxysilane coupling agent and an antioxidant into a stirring kettle, stirring at the rotating speed of 1000 rpm for 5min to obtain a blend A.
(2) Adding silicone oil and silicon dioxide flaky nano stiffening agent into the blend A, and stirring at a high speed of 2000 r/min for 10min until the surface temperature of the sample reaches 70-80 ℃ to obtain a blend B.
(3) And carrying out dry heat treatment on the blend B until the moisture content is lower than 0.02 percent to obtain a blend C.
(4) And adding the blend C into a double-screw extruder for melt blending granulation, wherein the length-diameter ratio of the double-screw extruder is 52, the temperature of each area from a feeding port to a discharging port is 380 ℃, 390 ℃, 370 ℃, 380 ℃, 385 ℃, 380 ℃ and 390 ℃, the main machine rotation speed is 400rpm, and the mixture is subjected to melt mixing and granulation to obtain granules.
(5) The prepared granules are placed in an oven at 160 ℃ for 7 hours to obtain the fluoroplastic alloy with low shrinkage.
Example four:
the formula adopted by the embodiment comprises the following components in parts by weight: 60 parts of polychlorotrifluoroethylene, 10 parts of polyether-ether-ketone, 17 parts of polyphenylene sulfide powder, 5 parts of silicon dioxide sheet-shaped nano stiffening agent, 3 parts of 3- (2, 3-epoxypropoxy) propyl triethoxysilane coupling agent, 2 parts of antioxidant and 3 parts of silicone oil.
The preparation method adopted in this example is as follows:
(1) adding polychlorotrifluoroethylene, polyether ketone, polyphenylene sulfide powder, 3- (2, 3-epoxypropoxy) propyl triethoxysilane coupling agent and antioxidant into a stirring kettle for stirring, wherein the rotating speed of the stirring kettle is 1000r/min, and the stirring time is 5min, thus obtaining the blend A.
(2) Adding silicone oil and silicon dioxide flaky nano stiffening agent into the blend A, and stirring at a high speed of 2000 r/min for 10min until the surface temperature of the sample reaches 70-80 ℃ to obtain a blend B.
(3) And carrying out dry heat treatment on the blend B until the moisture content is lower than 0.02 percent to obtain a blend C.
(4) And adding the blend C into a double-screw extruder for melt blending granulation, wherein the length-diameter ratio of the double-screw extruder is 52, the temperature of each area from a feeding port to a discharging port is 360 ℃, 370 ℃, 360 ℃, 365 ℃, 370 ℃ and the rotation speed of a main machine is 300rpm, and the mixture is melted, mixed and granulated to obtain granules.
(5) And placing the prepared granules in an oven at 150 ℃ for 8 hours to obtain the fluoroplastic alloy with low shrinkage.
Sample shrinkage data fluoroplastic alloys were prepared into strip samples using a Haitian MARS molding machine and tested using ASTM D955 test method, the following table being a recipe and test data table.
Comparative example one is the polyperfluoroalkoxy resin of example one;
comparative example two is the polyethylene-tetrafluoroethylene copolymer resin of example two;
comparative example three is the perfluoroethylene propylene copolymer resin of example three;
comparative example four the polychlorotrifluoroethylene resin of example four;
the preparation process is simple, and the thermoplastic fluoroplastic alloy with high heat resistance, high corrosion resistance, high toughness, high rigidity and shrinkage of less than 2.5% can be produced in a large amount in an industrialized mode. When the fluoroplastic alloy is used for preparing a product with high precision requirement, higher matching degree with the size of a die can be obtained; meanwhile, the fluoroplastic alloy can be used for preparing large-size long straight tubular materials.
The technical scope of the present invention is not limited to the above description, and those skilled in the art can make various changes and modifications to the above-described embodiments without departing from the technical spirit of the present invention, and such changes and modifications should fall within the protective scope of the present invention.
Claims (10)
1. A low-shrinkage thermoplastic fluoroplastic alloy is characterized by comprising the following components in parts by weight: 20-60 parts of plastic fluoroplastic, 5-25 parts of polyaryletherketone, 5-25 parts of polyphenylene sulfide, 1-4 parts of silicone oil, 0.5-3 parts of coupling agent, 5-10 parts of nano stiffening agent and 0.5-3 parts of antioxidant;
the polyaryletherketone is any one of PEEK, PEKK and PEEKK; d50 of the polyphenylene sulfide linear high molecular weight micro powder is less than 30 μm; the nano stiffening agent is sheet or spherical silicon dioxide micropowder with the diameter of 200nm-800 nm.
2. A low shrinkage thermoplastic fluoroplastic alloy according to claim 1 wherein said thermoplastic fluoroplastic is one or more of PVDF, FEP, PFA, ETFE, PCTFF.
3. A low shrinkage thermoplastic fluoroplastic alloy according to claim 1 wherein said coupling agent is a composite coupling agent of a titanate coupling agent and a silane coupling agent; the titanate coupling agent comprises: a monoalkoxy titanate coupling agent, a monoalkoxy pyrophosphate titanate coupling agent, an integrated titanate coupling agent and a ligand titanate coupling agent; the silane coupling agent includes: epoxy group-containing alkoxysilane compounds such as 3- (2, 3-glycidoxy) propyltriethoxysilane and β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.
4. A low shrinkage thermoplastic fluoroplastic alloy according to claim 1 comprising, in parts by weight: 45 parts of thermoplastic fluoroplastic, 25 parts of polyaryletherketone, 15 parts of polyphenylene sulfide, 7 parts of nano-reinforcing agent, 3 parts of coupling agent, 3 parts of antioxidant and 2 parts of silicone oil.
5. A low shrinkage thermoplastic fluoroplastic alloy according to claim 1 further comprising a functional filler present in an amount of no greater than 5 parts, said functional filler comprising a colorant, an ultraviolet light absorber, a mold release agent, and a nucleating agent.
6. A preparation method of a thermoplastic fluoroplastic alloy with low shrinkage rate is characterized by comprising the following steps:
s1, adding the thermoplastic fluoroplastic, the polyaryletherketone, the polyphenylene sulfide, the coupling agent and the antioxidant into a stirring kettle, and stirring to obtain a blend A, wherein the rotating speed of the stirring kettle is 500-1000 r/min, and the stirring time is 5-10 min;
s2, adding silicone oil and a nano stiffening agent into the blend A, and then arranging a stirring kettle 1500 r/min-2500 r/min for stirring for 5 r/min-10 min until the surface temperature of a sample is 70-80 ℃, so as to obtain a blend B;
s3, carrying out dry heat treatment on the blend B until the moisture content is lower than 0.02% to obtain a blend C;
and S4, adding the blend C into a double-screw extruder for melt blending granulation to obtain the fluoroplastic alloy product.
7. A process for preparing a thermoplastic fluoroplastic alloy according to claim 6 wherein said treatment in S3 is carried out at a temperature of from 120 ℃ to 180 ℃ for a period of from 1 hour to 5 hours.
8. A method of preparing a thermoplastic fluoroplastic alloy according to claim 6 wherein said twin screw extruder at S4 has a screw length to diameter ratio of greater than 35 and at least 2 shear modules, at least one 90 ° degree corner shear block.
9. A process for preparing a thermoplastic fluoroplastic alloy according to claim 8 wherein the temperatures in the zones of said twin screw extruder are between 280 ℃ and 400 ℃, the host current is between 0.5A and 1.2A, and the host speed is between 100rpm and 500 rpm.
10. A thermoplastic fluoroplastic alloy according to any one of claims 1 to 9 wherein said thermoplastic fluoroplastic alloy has a continuous operating temperature of not less than 220 ℃ and a shrinkage of less than 2.5%, and exhibits good corrosion resistance and electrical insulation properties.
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