A kind of fluororesin alloy and preparation method thereof
Technical field
The present invention relates to fluororesin modified field, in particular to a kind of fluororesin alloy.
Background technique
Melt-Processable Polytetrafluoroethylene (PFA) full name perfluorinated alkoxy vinyl ether polymer, with excellent resistance to
Hot, chemical reagent resistance and electrical resistance, continuous maximum operation (service) temperature reach 250 DEG C, and melt-processable can be used for producing height
Warm communication cable, obturator, wear part etc..
Since PFA melt viscosity is higher, it is easy to appear form phenomena such as bad in production.In order to improve productivity ratio and drop
Low production cost improves melt fracture phenomena and improves critical extruded velocity, in patent 200680013865.5, using 0.1-
Perfluoroethylene-propylene (FEP) aqueous liquid dispersion of 3% mass parts aqueous dispersion of polytetrafluoroethyland and 1 00%-97% mass parts
Condensation after mixing, then carry out melting extrusion after the drying and be made, preparation method is cumbersome and just for fluororesin aqueous liquid dispersion, skill
Art difficulty is big.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of fluororesin alloy, which is keeping original resin
On the basis of physical property, melt viscosity and processing temperature are advantageously reduced, reduces the fraction defective in following process forming process.
In order to solve the above-mentioned technical problem, the technical scheme is that a kind of fluororesin alloy, including following weight hundred
Divide the component of ratio:
PFA resin 1-90%
FEP resin 1-90%
Composite nucleating agent 5-10%,
The composite nucleating agent is rubber or PPS, inorganic rigid particle, organic phosphate nucleating agent 4-8 in mass ratio:
1-2:1-2 is mixed, the inorganic rigid particle be selected from mica powder, talcum powder, kaolin, wollastonite, calcium carbonate and
One of barium sulfate, rubber or PPS, which are surrounded on outside inorganic rigid particle, organic phosphate nucleating agent, forms shell-core structure.
Preferably, composite nucleating agent the preparation method comprises the following steps: inorganic rigid particle is mixed with organic phosphate first,
Then it places it in rubber or PPS forms slurries, composite nucleating agent powder is formed by spray drying process again after mixing evenly.
Preferably, the average grain diameter of the composite nucleating agent powder is 150~300nm.
Preferably, the average grain diameter of the inorganic rigid particle is 20~80nm.
Preferably, the perfluorinated stable processing of the FEP resin.
Preferably, a kind of fluororesin alloy, including following weight percentage components:
PFA resin 90%
FEP resin 5%
Composite nucleating agent 5%
The composite nucleating agent is rubber, inorganic rigid particle, organic phosphate nucleating agent 4:2:1 in mass ratio progress
Mixing.
Preferably, a kind of fluororesin alloy, including following weight percentage components:
PFA resin 80%
FEP resin 10%
Composite nucleating agent 10%
The composite nucleating agent is rubber, inorganic rigid particle, organic phosphate nucleating agent 4:1:1 in mass ratio progress
Mixing.
Preferably, a kind of fluororesin alloy, including following weight percentage components:
PFA resin 70%
FEP resin 26%
Composite nucleating agent 4%
The composite nucleating agent is rubber, inorganic rigid particle, organic phosphate nucleating agent 6:1:1 in mass ratio progress
Mixing.
A kind of preparation method of fluororesin alloy, comprising the following steps:
S1: by formula by the PFA resin, FEP resin, composite nucleating agent 110 DEG C at a temperature of in mixed grain machine
Middle stirring 30min is uniformly mixed, obtains the mixed material of PFA and FEP;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
305-315 DEG C, two area's temperature be 315-325 DEG C, three area's temperature are 325-335 DEG C, four area's temperature are 335-345 DEG C, five Qu Wen
Degree is 345-355 DEG C, six area's temperature are 345-355 DEG C;
Preferably, screw speed is 35~55r/min, compression section screw rod pressure when screw extruding in the double screw extruder
Contracting is than being 2.5:1.
By adopting the above technical scheme, since FEP and PFA are the modified polymer of tetrafluoroethene, compatibility is fine, wherein
FEP resin can serve as the lubricant of PFA melt-processed, reduce the melt viscosity and processing temperature of PFA, improve the molding of PFA
Fraction defective.Meanwhile FEP is also the polymer with suitable molecular weight, it is small on the influence of the physical property of PFA resin itself, and lead to
The addition of composite nucleating agent is crossed, rubber or PPS, inorganic rigid particle, organic phosphate in composite nucleating agent, i.e., by inorganic rigid
Particle, organic phosphate nucleating agent are wrapped up by rubber or PPS, form nucleocapsid structure, even if nucleating agent partial size be nanoscale
Agglomeration is less likely to occur, to guarantee the dispersibility of nucleating agent, further decreases whole system melt viscosity and processing temperature
Degree, while also whole system can be made to be balanced between rigidity and toughness by inorganic rigid particle, organic phosphate.
Tensile strength of the invention is 273-285MPa, elongation at break 345-361%, and intensity is remaining after environmental stress resistance
Rate 54-68/% melt index is 15.1-16.5 (g/10min).
Specific embodiment
Specific embodiments of the present invention will be further explained below.It should be noted that for these implementations
The explanation of mode is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, invention described below
Technical characteristic involved in each embodiment can be combined with each other as long as they do not conflict with each other.
The preparation method of composite nucleating agent in following embodiment is equal are as follows: first by inorganic rigid particle and organic phosphate
It is mixed, then places it in rubber or PPS forms slurries, compound nucleation is formed by spray drying process again after mixing evenly
Agent powder.
Embodiment 1
The fluororesin alloy of the present embodiment, including following weight percentage components:
PFA resin 90%
FEP resin 5%
Composite nucleating agent 5%
Wherein, composite nucleating agent is made of rubber, mica powder (20nm), NA-11 by weight 4:2:1, and obtained answers
Synthetic kernel agent is in powdery, average grain diameter 300nm
Preparation method, comprising the following steps:
S1: by formula by the PFA resin, FEP resin, composite nucleating agent 110 DEG C at a temperature of in mixed grain machine
Middle stirring 30min is uniformly mixed, obtains mixed material;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
305 DEG C, two area's temperature be 315 DEG C, three area's temperature are 325 DEG C, four area's temperature are 335 DEG C, five area's temperature are 345 DEG C, six Qu Wen
Degree is 345 DEG C;Screw speed is 35r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain novel fluororesin alloy particle through double screw extruder.
Embodiment 2
The fluororesin alloy of the present embodiment, including following weight percentage components:
PFA resin 80%
FEP resin 10%
Composite nucleating agent 10%
Wherein, composite nucleating agent is made of PPS, talcum powder (50nm), NA-11 by weight 4:1:1, and obtained is compound
Nucleating agent is in powdery, average grain diameter 150nm
Preparation method, comprising the following steps:
S1: by formula by the PFA resin, FEP resin, composite nucleating agent 110 DEG C at a temperature of in mixed grain machine
Middle stirring 30min is uniformly mixed, obtains mixed material;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
310 DEG C, two area's temperature be 320 DEG C, three area's temperature are 330 DEG C, four area's temperature are 340 DEG C, five area's temperature are 350 DEG C, six Qu Wen
Degree is 350 DEG C;Screw speed is 40r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain novel fluororesin alloy particle through double screw extruder.
Embodiment 3
The fluororesin alloy of the present embodiment, including following weight percentage components:
PFA resin 70%
FEP resin 25%
Composite nucleating agent 5%
Wherein, composite nucleating agent is made of rubber, kaolin (60nm), NA-11 by weight 6:1:1, and obtained answers
Synthetic kernel agent is in powdery, average grain diameter 200nm
Preparation method, comprising the following steps:
S1: by formula by the PFA resin, FEP resin, composite nucleating agent 110 DEG C at a temperature of in mixed grain machine
Middle stirring 30min is uniformly mixed, obtains mixed material;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
315 DEG C, two area's temperature be 325 DEG C, three area's temperature are 335 DEG C, four area's temperature are 345 DEG C, five area's temperature are 355 DEG C, six Qu Wen
Degree is 355 DEG C;Screw speed is 55r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain novel fluororesin alloy particle through double screw extruder.
Embodiment 4
The fluororesin alloy of the present embodiment, including following weight percentage components:
PFA resin 50%
FEP resin 40%
Composite nucleating agent 10%
Wherein, composite nucleating agent is made of PPS, wollastonite (80nm), NA-11 by weight 4:2:1, and obtained is compound
Nucleating agent is in powdery, average grain diameter 250nm
Preparation method, comprising the following steps:
S1: by formula by the PFA resin, FEP resin, composite nucleating agent 110 DEG C at a temperature of in mixed grain machine
Middle stirring 30min is uniformly mixed, obtains mixed material;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
315 DEG C, two area's temperature be 325 DEG C, three area's temperature are 335 DEG C, four area's temperature are 345 DEG C, five area's temperature are 355 DEG C, six Qu Wen
Degree is 355 DEG C;Screw speed is 55r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain novel fluororesin alloy particle through double screw extruder.
Embodiment 5
The fluororesin alloy of the present embodiment, including following weight percentage components:
PFA resin 40%
FEP resin 55%
Composite nucleating agent 5%
Wherein, composite nucleating agent is made of rubber, calcium carbonate (30nm), NA-11 by weight 6:2:2, and obtained answers
Synthetic kernel agent is in powdery, average grain diameter 150nm
Preparation method, comprising the following steps:
S1: by formula by the PFA resin, FEP resin, composite nucleating agent 110 DEG C at a temperature of in mixed grain machine
Middle stirring 30min is uniformly mixed, obtains mixed material;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
310 DEG C, two area's temperature be 320 DEG C, three area's temperature are 330 DEG C, four area's temperature are 340 DEG C, five area's temperature are 350 DEG C, six Qu Wen
Degree is 350 DEG C;Screw speed is 40r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain novel fluororesin alloy particle through double screw extruder.
Embodiment 6
The fluororesin alloy of the present embodiment, including following weight percentage components:
PFA resin 30%
FEP resin 60%
Composite nucleating agent 10%
Wherein, composite nucleating agent is made of PPS, barium sulfate (40nm), NA-13 by weight 7:2:1, and obtained is compound
Nucleating agent is in powdery, average grain diameter 200nm
Preparation method, comprising the following steps:
S1: by formula by the PFA resin, FEP resin, composite nucleating agent 110 DEG C at a temperature of in mixed grain machine
Middle stirring 30min is uniformly mixed, obtains mixed material;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
310 DEG C, two area's temperature be 320 DEG C, three area's temperature are 330 DEG C, four area's temperature are 340 DEG C, five area's temperature are 350 DEG C, six Qu Wen
Degree is 350 DEG C;Screw speed is 40r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain novel fluororesin alloy particle through double screw extruder.
Embodiment 7
The fluororesin alloy of the present embodiment, including following weight percentage components:
PFA resin 20%
FEP resin 72%
Composite nucleating agent 8%
Wherein, composite nucleating agent is made of PPS, barium sulfate (40nm), NA-13 by weight 8:1:1, and obtained is compound
Nucleating agent is in powdery, and average grain diameter 200nm, FEP resin is the resin for stablizing processing by fluorination.
Processing is stablized in the fluorination of FEP resin: processing is stablized in the fluorination of FEP resin can be in improved bi-conical mixer
It carries out, mixer is provided with air inlet/outlet and electric mantle, rotates fluorination reaction with the speed of 5r/min and heats, and fills after taking out air to the greatest extent
Enter the F2 that volume ratio is 1:3, N2 gaseous mixture terminates fluorination reaction after stopping heating after a certain period of time.Remove F2 in fluorination reaction
Method is to be filled with a large amount of N2 to be cleaned.
The FEP resin of perfluorinated processing can avoid generating corrosive gas and bubble during melting, cause into
Contain bubble in product, influences performance.
Preparation method, comprising the following steps:
S1: by formula by the PFA resin, FEP resin, composite nucleating agent 110 DEG C at a temperature of in mixed grain machine
Middle stirring 30min is uniformly mixed, obtains mixed material;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
310 DEG C, two area's temperature be 320 DEG C, three area's temperature are 330 DEG C, four area's temperature are 340 DEG C, five area's temperature are 350 DEG C, six Qu Wen
Degree is 350 DEG C;Screw speed is 40r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain novel fluororesin alloy particle through double screw extruder.
Embodiment 8
The fluororesin alloy of the present embodiment, including following weight percentage components:
PFA resin 10%
FEP resin 84%
Composite nucleating agent 6%
Wherein, composite nucleating agent is made of rubber, calcium carbonate (50nm), NA-13 by weight 7:1:2, and obtained answers
Synthetic kernel agent is in powdery, and average grain diameter 300nm, FEP resin is the resin for stablizing processing by fluorination, is fluorinated and stablizes processing
Method is the same as embodiment 7.
Preparation method, comprising the following steps:
S1: by formula by the PFA resin, FEP resin, composite nucleating agent 110 DEG C at a temperature of in mixed grain machine
Middle stirring 30min is uniformly mixed, obtains mixed material;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
310 DEG C, two area's temperature be 320 DEG C, three area's temperature are 330 DEG C, four area's temperature are 340 DEG C, five area's temperature are 350 DEG C, six Qu Wen
Degree is 350 DEG C;Screw speed is 40r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain novel fluororesin alloy particle through double screw extruder.
Embodiment 9
The fluororesin alloy of the present embodiment, including following weight percentage components:
PFA resin 1%
FEP resin 90%
Composite nucleating agent 9%
Wherein, composite nucleating agent is made of PPS, calcium carbonate (50nm), NA-13 by weight 4:1:2, and obtained is compound
Nucleating agent is in powdery, average grain diameter 200nm
Preparation method, comprising the following steps:
S1: by formula by the PFA resin, FEP resin, composite nucleating agent 110 DEG C at a temperature of in mixed grain machine
Middle stirring 30min is uniformly mixed, obtains mixed material;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
310 DEG C, two area's temperature be 320 DEG C, three area's temperature are 330 DEG C, four area's temperature are 340 DEG C, five area's temperature are 350 DEG C, six Qu Wen
Degree is 350 DEG C;Screw speed is 40r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain novel fluororesin alloy particle through double screw extruder.
Comparative example 1
PFA resin 100%
Preparation method, comprising the following steps:
S1: by PFA resin 110 DEG C at a temperature of in mixed grain machine stir 30min, be uniformly mixed, obtain mixed material;
S2: by PFA resin by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
310 DEG C, two area's temperature be 320 DEG C, three area's temperature are 330 DEG C, four area's temperature are 340 DEG C, five area's temperature are 350 DEG C, six Qu Wen
Degree is 350 DEG C;Screw speed is 40r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain PFA resin particle through double screw extruder.
Comparative example 2
PFA resin 95%
Composite nucleating agent 5%
Preparation method, comprising the following steps:
S1: by formula by the PFA resin, composite nucleating agent 110 DEG C at a temperature of stir in the mixed grain machine
30min is uniformly mixed, obtains mixed material;
S2: by mixed material by double screw extruder, melt extruder includes six heating zones, and Zhong-1 block temperature is
320 DEG C, two area's temperature be 330 DEG C, three area's temperature are 340 DEG C, four area's temperature are 350 DEG C, five area's temperature are 360 DEG C, six Qu Wen
Degree is 350 DEG C;Screw speed is 40r/min when screw extruding in the double screw extruder, screw compression ratio in compression section is
2.5:1。
Under the above conditions, it squeezes out to obtain novel fluororesin alloy particle through double screw extruder.
Intensity is remaining after carrying out tensile strength, elongation at break, thermal stress cracking, environmental stress resistance to above-described embodiment
The test of rate index, test result is as follows:
|
Tensile strength/MPa |
Elongation at break/% |
Intensity remnants rate/% after environmental stress resistance |
Melt index g/10min |
Embodiment 1 |
27.6 |
356 |
56 |
15.5 |
Embodiment 2 |
27.5 |
349 |
61 |
15.7 |
Embodiment 3 |
28.4 |
357 |
58 |
15.4 |
Embodiment 4 |
27.7 |
361 |
54 |
15.9 |
Embodiment 5 |
27.3 |
352 |
57 |
16.0 |
Embodiment 6 |
27.4 |
348 |
62 |
15.1 |
Embodiment 7 |
28.5 |
357 |
63 |
16.5 |
Embodiment 8 |
27.8 |
345 |
68 |
15.9 |
Embodiment 9 |
27.3 |
352 |
65 |
16.1 |
Comparative example 1 |
24 |
350 |
50 |
15.4 |
Comparative example 2 |
26 |
320 |
55 |
15.1 |
Tensile strength of the invention is 273-285MPa, elongation at break 345-361%, and intensity is remaining after environmental stress resistance
Rate 54-68/% melt index is 15.1-16.5 (g/10min), compared with comparative example, in situation similar in melt index, other
Performance be substantially higher in comparative example.
Above the embodiments of the present invention are described in detail, but the present invention is not limited to described embodiments.It is right
For those skilled in the art, in the case where not departing from the principle of the invention and spirit, these embodiments are carried out more
Kind change, modification, replacement and modification, still fall in protection scope of the present invention.