A high temperature resistant perfluoroether rubber composition and preparation method thereof

Abstract

The invention discloses a high-temperature resistant perfluoroether rubber composition and a preparation method thereof, belonging to the technical field of rubber compositions. The composition comprises perfluoroether rubber raw rubber, 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, graphene oxide and carbon nanotubes, wherein 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane are used as vulcanizing agents to enable the perfluoroether rubber product to resist a high temperature of 300 DEG C and superheated water vapor, wherein graphene oxide and carbon nanotubes are used as functional fillers to enable the perfluoroether rubber to have a small permanent deformation under high-temperature compression and have excellent free radical scavenging ability, can preferentially capture free radicals generated by thermal decomposition of the perfluoroether rubber, delay the decomposition of the perfluoroether rubber, and significantly improve the temperature resistance of the perfluoroether rubber.

Description

Technical Field

[0001] The invention relates to the technical field of rubber compositions, and in particular to a high-temperature resistant perfluoroether rubber composition and a preparation method thereof. Background Art

[0002] Perfluoroether rubber (FFKM) is a type of fluororubber and has the best comprehensive performance among all synthetic rubbers. It has excellent physical and mechanical properties, heat resistance, chemical resistance, radiation resistance, electrical insulation, oxidation resistance, low permeability, flame retardancy, vacuum resistance and other advantages. However, it also has the disadvantages of a large thermal expansion coefficient, sensitivity to certain polar molecules and high price. Summary of the invention

[0003] Based on the above problems, the present invention provides a high temperature resistant perfluoroether rubber composition and a preparation method thereof. The perfluoroether rubber has a relatively small thermal expansion coefficient and strong high temperature resistance. The contents of the present invention are as follows:

[0004] The first object of the present invention is to provide a high temperature resistant perfluoroether rubber composition, which technical point is that, in terms of weight parts, it includes 90-110 weight parts of perfluoroether rubber raw rubber, 0.5-1 weight parts of 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane, 1-1.5 weight parts of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1-2 weight parts of graphene oxide and 1-2 weight parts of carbon nanotubes.

[0005] In order to better realize the above technical solution, the perfluoroether rubber raw rubber in the high temperature resistant perfluoroether rubber composition formula system of the present invention includes tetrafluoroethylene, perfluoroalkyl vinyl ether and a third monomer.

[0006] In order to better realize the above technical scheme, the third monomer in the high temperature resistant perfluoroether rubber composition formula system of the present invention is at least one of perfluoro-4-carboxymethylbutyl vinyl ether, perfluoro-4-cyanobutyl vinyl ether, perfluoro-2-phenoxypropyl vinyl ether and perfluoro-3-phenoxypropyl vinyl ether.

[0007] In order to better realize the above technical solution, the median particle size of graphene oxide in the high temperature resistant perfluoroether rubber composition formulation system of the present invention is 0.5-3.5 μm.

[0008] In order to better realize the above technical scheme, the carbon nanotubes in the high temperature resistant perfluoroether rubber composition formula system of the present invention are array-type carbon nanotubes, wherein the average tube diameter is ≤2.0nm, the average length is >5μm, and the specific surface area is ≥300m 2 / g.

[0009] The second object of the present invention is to provide a method for preparing high temperature resistant perfluoroether rubber, the technical point of which is that it comprises the following steps:

[0010] Step 1, reducing the raw perfluoroether rubber, 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane in one step to synthesize an elastomer embryo;

[0011] Step 2: placing the elastomer embryo, graphene oxide and carbon nanotubes on an open mill for calendering and softening, and rolling them with a roller, and mixing them evenly to obtain a high-temperature resistant perfluoroether rubber.

[0012] In order to better realize the above technical scheme, in the step 1 of the preparation method of high temperature resistant perfluoroether rubber of the present invention, the temperature of the one-step reduction is 60-85° C. and the pressure is 1.6-4.0 MPa.

[0013] In order to better realize the above technical scheme, in step 2 of the method for preparing high temperature resistant perfluoroether rubber of the present invention, the mixing temperature is 40-270° C. and the mixing time is 3-4 hours.

[0014] Compared with the prior art, the high temperature resistant perfluoroether rubber composition and the preparation method thereof of the present invention can achieve the following beneficial effects:

[0015] The invention discloses a high-temperature resistant perfluoroether rubber composition comprising perfluoroether rubber raw rubber, 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, graphene oxide and carbon nanotubes, wherein 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane are used as vulcanizing agents to enable the perfluoroether rubber product to resist a high temperature of 300 DEG C and superheated water vapor, wherein graphene oxide and carbon nanotubes are used as functional fillers to enable the perfluoroether rubber to have a small permanent deformation under high-temperature compression and have excellent free radical scavenging ability, can preferentially capture free radicals generated by thermal decomposition of the perfluoroether rubber, delay the decomposition of the perfluoroether rubber, and significantly improve the temperature resistance of the perfluoroether rubber. DETAILED DESCRIPTION

[0016] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0017] Example 1

[0018] A high temperature resistant perfluoroether rubber composition comprises 100 kg of perfluoroether rubber raw rubber, 0.75 kg of 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane, 2.25 kg of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.5 kg of graphene oxide and 1.5 kg of carbon nanotubes.

[0019] Furthermore, in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment, the perfluoroether rubber raw rubber includes tetrafluoroethylene, perfluoroalkyl vinyl ether and a third monomer.

[0020] Furthermore, the third monomer in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment is perfluoro-4-carboxymethylbutyl vinyl ether.

[0021] Furthermore, the median particle size of graphene oxide in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment is 2 μm.

[0022] Furthermore, the carbon nanotubes in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment are array-type carbon nanotubes, wherein the average tube diameter is ≤2.0nm, the average length is >5μm, and the specific surface area is ≥300m 2 / g.

[0023] According to the above formula, a method for preparing a high temperature resistant perfluoroether rubber in this embodiment comprises the following steps:

[0024] Step 1, reducing the raw perfluoroether rubber, 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane in one step to synthesize an elastomer embryo;

[0025] Step 2: placing the elastomer embryo, graphene oxide and carbon nanotubes on an open mill for calendering and softening, and rolling them with a roller, and mixing them evenly to obtain a high-temperature resistant perfluoroether rubber.

[0026] Furthermore, in step 1 of the method for preparing high-temperature resistant perfluoroether rubber of this embodiment, the temperature of the one-step reduction is 75° C. and the pressure is 2.8 MPa.

[0027] Furthermore, in step 2 of the method for preparing high temperature resistant perfluoroether rubber of this embodiment, the mixing temperature is 150° C. and the mixing time is 3.5 h.

[0028] Example 2

[0029] A high temperature resistant perfluoroether rubber composition comprises 90 kg of perfluoroether rubber raw rubber, 0.5 kg of 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane, 1 kg of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1 kg of graphene oxide and 1 kg of carbon nanotubes.

[0030] Furthermore, in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment, the perfluoroether rubber raw rubber includes tetrafluoroethylene, perfluoroalkyl vinyl ether and a third monomer.

[0031] Furthermore, the third monomer in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment is perfluoro-4-cyanobutyl vinyl ether.

[0032] Furthermore, the median particle size of graphene oxide in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment is 0.5 μm.

[0033] Furthermore, the carbon nanotubes in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment are array-type carbon nanotubes, wherein the average tube diameter is ≤2.0nm, the average length is >5μm, and the specific surface area is ≥300m 2 / g.

[0034] According to the above formula, a method for preparing a high temperature resistant perfluoroether rubber in this embodiment comprises the following steps:

[0035] Step 1, reducing the raw perfluoroether rubber, 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane in one step to synthesize an elastomer embryo;

[0036] Step 2: placing the elastomer embryo, graphene oxide and carbon nanotubes on an open mill for calendering and softening, and rolling them with a roller, and mixing them evenly to obtain a high-temperature resistant perfluoroether rubber.

[0037] Furthermore, in step 1 of the method for preparing high-temperature resistant perfluoroether rubber of this embodiment, the temperature of the reduction step is 60° C. and the pressure is 4.0 MPa.

[0038] Furthermore, in step 2 of the method for preparing high temperature resistant perfluoroether rubber of this embodiment, the mixing temperature is 40° C. and the mixing time is 4 hours.

[0039] Example 3

[0040] A high temperature resistant perfluoroether rubber composition comprises 110 kg of perfluoroether rubber raw rubber, 1 kg of 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane, 1.5 kg of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2 kg of graphene oxide and 2 kg of carbon nanotubes.

[0041] Furthermore, in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment, the perfluoroether rubber raw rubber includes tetrafluoroethylene, perfluoroalkyl vinyl ether and a third monomer.

[0042] Furthermore, the third monomer in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment is perfluoro-2-phenoxypropyl vinyl ether.

[0043] Furthermore, the median particle size of graphene oxide in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment is 3.5 μm.

[0044] Furthermore, the carbon nanotubes in the high temperature resistant perfluoroether rubber composition formulation system of this embodiment are array-type carbon nanotubes, wherein the average tube diameter is ≤2.0nm, the average length is >5μm, and the specific surface area is ≥300m 2 / g.

[0045] According to the above formula, a method for preparing a high temperature resistant perfluoroether rubber in this embodiment comprises the following steps:

[0046] Step 1, reducing the raw perfluoroether rubber, 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane in one step to synthesize an elastomer embryo;

[0047] Step 2: placing the elastomer embryo, graphene oxide and carbon nanotubes on an open mill for calendering and softening, and rolling them with a roller, and mixing them evenly to obtain a high-temperature resistant perfluoroether rubber.

[0048] Furthermore, in step 1 of the method for preparing high-temperature resistant perfluoroether rubber of this embodiment, the temperature of the one-step reduction is 85° C. and the pressure is 1.6 MPa.

[0049] Furthermore, in step 2 of the method for preparing high temperature resistant perfluoroether rubber of this embodiment, the mixing temperature is 270° C. and the mixing time is 3 hours.

[0050] Comparative Example 1

[0051] The "100 kg of perfluoroether rubber raw rubber, 0.75 kg of 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane, 2.25 kg of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.5 kg of graphene oxide and 1.5 kg of carbon nanotubes" in Example 1 are changed to "100 kg of perfluoroether rubber raw rubber, 3 kg of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3 kg of graphene oxide", and the remaining operations are the same as Example 1.

[0052] Comparative Example 2

[0053] The "100 kg of perfluoroether rubber raw rubber, 0.75 kg of 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane, 2.25 kg of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.5 kg of graphene oxide and 1.5 kg of carbon nanotubes" in Example 1 are changed to "100 kg of perfluoroether rubber raw rubber, 3 kg of 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane and 3 kg of graphene oxide", and the remaining operations are the same as in Example 1.

[0054] Test example

[0055] The high temperature resistant perfluoroether rubber prepared in Example 1-3 and Comparative Example 1-2 was tested for performance according to GB / T528-1998 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber" and GB7759-87 "Physical test methods for vulcanized rubber". The test results are shown in Table 1:

[0056] Table 1

[0057]

[0058] The above description is only an embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A high temperature resistant perfluoroether rubber composition, characterized in that: The invention comprises, by weight, 90-110 parts of perfluoroether rubber raw rubber, 0.5-1 parts of 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane, 1-1.5 parts of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1-2 parts of graphene oxide and 1-2 parts of carbon nanotubes; The perfluoroether rubber raw rubber is obtained by copolymerizing tetrafluoroethylene, perfluoroalkyl vinyl ether and a third monomer; The third monomer is at least one of perfluoro-4-carboxymethylbutyl vinyl ether, perfluoro-4-cyanobutyl vinyl ether, perfluoro-2-phenoxypropyl vinyl ether and perfluoro-3-phenoxypropyl vinyl ether; The median particle size of the graphene oxide is 0.5-3.5 μm; The carbon nanotubes are array-type carbon nanotubes, wherein the average tube diameter is ≤2.0nm, the average length is >5μm, and the specific surface area is ≥300m 2 / g; The preparation method of the high temperature resistant perfluoroether rubber composition comprises the following steps: Step 1, reducing the raw perfluoroether rubber, 1,6-bis[4-(trifluorovinyl)phenyl]dodecafluorohexane and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane in one step to synthesize an elastomer embryo; Step 2, placing the elastomer embryo, graphene oxide and carbon nanotubes on an open mill for calendering and softening, and rolling them with a roller, and mixing them evenly to obtain a high temperature resistant perfluoroether rubber; The temperature of the one-step reduction in step 1 is 60-85° C. and the pressure is 1.6-4.0 MPa; The mixing temperature in step 2 is 40-270° C., and the mixing time is 3-4 hours.

Images