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CN110157122B - Extremely-low-temperature fluorine mixed rubber and preparation method thereof - Google Patents

Extremely-low-temperature fluorine mixed rubber and preparation method thereof Download PDF

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Publication number
CN110157122B
CN110157122B CN201910496436.7A CN201910496436A CN110157122B CN 110157122 B CN110157122 B CN 110157122B CN 201910496436 A CN201910496436 A CN 201910496436A CN 110157122 B CN110157122 B CN 110157122B
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rubber
agent
low temperature
parts
bridging agent
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CN110157122A (en
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许茂祥
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Changxin Rubber Industry Shanghai Co ltd
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Changxin Rubber Industry Shanghai Co ltd
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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
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the field of fluororubber, in particular to a very low temperature fluororubber and a preparation method thereof. The invention provides a very low temperature fluorine mixed rubber, which comprises the following raw materials, by weight, 80-110 parts of virgin rubber, 1-5 parts of a co-bridging agent and 0.4-1.2 parts of a bridging agent, wherein the virgin rubber is a tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer.

Description

Extremely-low-temperature fluorine mixed rubber and preparation method thereof
Technical Field
The invention relates to the field of fluororubber, in particular to a very low temperature fluororubber and a preparation method thereof.
Background
The low temperature properties of rubber refer to the ability of the rubber to function properly at low temperatures. When the rubber works under the low temperature condition, the movement among molecules of the rubber is restricted due to low temperature, the movement is inconvenient, if the rubber is crystallized, molecular chain segments of the rubber are frozen when the rubber is crystallized, the rubber cannot normally move, the rubber loses the due elasticity, cannot normally work and loses the use value. At present, various industries are continuously developed, science and technology are also improved, the performance of rubber is required to be higher, for a specific environment, low-temperature-resistant rubber needs to be used, the requirement and the requirement for the low-temperature-resistant rubber are increased, and the rubber needs to have better tensile strength, better tearing strength, smaller compression set, certain impact strength and the like under a low-temperature condition.
Fluororubbers are widely applied to the fields of aviation, aerospace, automobiles, off-road vehicles, oil exploitation, petrochemical industry, industrial pollution control, hydraulic and pneumatic devices and the like due to excellent heat resistance, liquid resistance, oil resistance, electrical insulation and radiation resistance. Particularly, with the expansion of fluororubber application in recent years, the demand for fluororubbers has been increasing, and the existing fluororubber grades have become unable to meet the market, which has stimulated the application market of special fluororubbers. The strength of the conventional ternary fluororubber can only reach 1.6MPa, and the conventional ternary fluororubber can only bear the temperature of minus 30 ℃ and cannot bear the requirements of the harsh environment.
Disclosure of Invention
In order to solve some problems in the prior art, the invention provides a very low temperature fluorine mixed rubber, which is prepared from at least 80-110 parts by weight of raw rubber, 1-5 parts by weight of co-bridging agent and 0.4-1.2 parts by weight of bridging agent, wherein the raw rubber is tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer.
As a preferable technical scheme of the invention, the molar percentage of the tetrafluoroethylene in the virgin rubber is 10-30%, and the molar percentage of the 1, 1-difluoroethylene in the virgin rubber is 40-75%.
In a preferred embodiment of the present invention, the co-bridging agent comprises isocyanurate derivative and silica.
As a preferable technical scheme of the invention, the isocyanurate derivative accounts for 60-80 wt% of the co-bridging agent.
As a preferred technical scheme, the preparation raw materials of the extremely-low-temperature fluorine rubber compound further comprise 2-8 parts of an active agent, 15-30 parts of a reinforcing agent and 0.5-1.5 parts of an auxiliary agent.
As a preferable technical scheme of the invention, the auxiliary agent comprises fatty acid derivatives and wax.
In a preferred embodiment of the present invention, the fatty acid derivative is one or more of potassium stearate, sodium laurate, potassium laurate, sodium palmitate, and potassium palmitate.
In a preferred embodiment of the present invention, the fatty acid derivative includes potassium stearate and sodium stearate.
In a preferred embodiment of the present invention, the wax is polyethylene wax and/or palm wax.
The second aspect of the invention provides a preparation method of the extremely low temperature fluorine mixed rubber, and the preparation method of the extremely low temperature fluorine mixed rubber at least comprises the following steps:
(1) plasticating the virgin rubber;
(2) banburying;
(3) adding the bridging agent and the bridging agent, milling, and forming and obtaining the fluorine rubber compound.
(4) And vulcanizing the fluorine mixed rubber to obtain the ultralow-temperature fluorine mixed rubber.
Compared with the prior art, the invention has the following beneficial effects:
the ultralow-temperature fluorine mixed rubber provided by the invention can resist the low temperature of-40 ℃, has excellent mechanical property and appearance, ensures the normal use of the ultralow-temperature fluorine mixed rubber in an ultralow-temperature environment, and expands the use range.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a very low temperature fluorine mixed rubber, which comprises the following raw materials, by weight, 80-110 parts of raw rubber, 1-5 parts of a co-bridging agent and 0.4-1.2 parts of a bridging agent.
In one embodiment, the preparation raw materials of the extremely low temperature fluorine rubber compound further comprise 2-8 parts of an active agent, 15-30 parts of a reinforcing agent and 0.5-1.5 parts of an auxiliary agent.
Preferably, the preparation raw materials of the extremely-low-temperature fluorine rubber compound at least comprise 95-105 parts of virgin rubber, 2-4 parts of co-bridging agent, 0.5-1 part of bridging agent, 4-6 parts of activator, 15-25 parts of reinforcing agent and 0.7-1.2 parts of auxiliary agent in parts by weight.
More preferably, the preparation raw materials of the extremely low temperature fluorine rubber compound at least comprise 100 parts of virgin rubber, 2.4 parts of co-bridging agent, 0.8 part of bridging agent, 4 parts of activator, 20 parts of reinforcing agent and 1 part of auxiliary agent by weight.
Virgin rubber
The virgin rubber is tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer.
Preferably, the molar percentage of the tetrafluoroethylene in the virgin rubber is 10-30%, and the molar percentage of the 1, 1-difluoroethylene in the virgin rubber is 40-75%; further preferably, the molar percentage of the tetrafluoroethylene in the virgin rubber is 15-25%, and the molar percentage of the 1, 1-difluoroethylene in the virgin rubber is 50-65%; more preferably, the tetrafluoroethylene is 20 mole percent of the virgin rubber, and the 1, 1-difluoroethylene is 57 mole percent of the virgin rubber.
The Applicant has found that the flexibility of the molecular chain segment of the fluororubber is improved when the raw rubber is tetrafluoroethylene, 1-difluoroethylene and trifluoro (trifluoromethoxy) ethylene polymer, and the flexibility of the molecular chain segment is improved because of-OCF3The existence of (2) increases the distance between molecular chain segments, destroys the regularity of the structure, prevents the crystallization tendency of macromolecular chains, and improves the low temperature resistance of the fluororubber, but the improvement of the low temperature resistance of the fluororubber often leads to the reduction of the mechanical property of the rubber. The applicant unexpectedly finds that when the molar percentage of tetrafluoroethylene in the virgin rubber is 10-30% and the molar percentage of 1, 1-difluoroethylene in the virgin rubber is 40-75%, the tensile strength of the fluororubber can be improved, and the probable reason is that the virgin rubber composed of a certain proportion of monomers is crosslinked with other components in a fluororubber system, and on the premise of ensuring the low-temperature resistance, a proper degree of crosslinking bonds are formed at the same time, so that the oriented arrangement and the elongation oriented crystallization of rubber molecular chains are facilitated, and the tensile strength of the fluororubber is improved.
The tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is not particularly limited in its source, and may be purchased or prepared by itself.
The preparation method of the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer at least comprises the following steps:
adding disodium hydrogen phosphate and a sodium perfluorooctanoate aqueous solution into a reaction kettle, introducing tetrafluoroethylene, 1-difluoroethylene and trifluoro (trifluoromethoxy) ethylene, keeping a certain pressure P, stirring and heating; adding 15wt% ammonium persulfate aqueous solution to initiate polymerization reaction, stopping reaction when the pressure of the reaction kettle is reduced by 8%, coagulating with 5wt% calcium chloride aqueous solution, washing with deionized water until the conductivity of water is less than 5 μ s/m, and drying.
Preferably, the weight ratio of the disodium hydrogen phosphate to the sodium perfluorooctanoate to the ammonium persulfate is 1: 1: (5-15); further preferably, the weight ratio of the disodium hydrogen phosphate to the sodium perfluorooctanoate to the ammonium persulfate is 1: 1: (7-12); more preferably, the weight ratio of the disodium hydrogen phosphate, the sodium perfluorooctanoate and the ammonium persulfate is 1: 1: 10.
preferably, the P is 0.3-5 MPa; further preferably, the P is 1.5-2.5 MPa; more preferably, said P is 2 MPa.
Preferably, the stirring speed is 550-1000 r/min; further preferably, the stirring speed is 700-900 r/min; more preferably, the stirring rate is 800 r/min.
Preferably, the temperature is increased to 50-80 ℃; more preferably, the temperature is raised to 60 ℃.
Co-bridging agent
Preferably, the co-bridging agent comprises an isocyanurate derivative and silica.
Further preferably, the isocyanurate derivative is trishydroxyethyl isocyanurate or triallyl isocyanurate; more preferably, the isocyanurate derivative is triallyl isocyanurate.
The triallyl isocyanurate CAS: 1025-15-6; the silica CAS: 14808-60-7.
Preferably, the triallyl isocyanurate accounts for 60-80 wt% of the co-bridging agent; more preferably, the triallyl isocyanurate constitutes 70 wt% of the co-crosslinking agent.
Preferably, the silicon dioxide accounts for 20-40 wt% of the co-bridging agent; further preferably, the silica comprises 30 wt% of the co-bridging agent; more preferably, the particle size of the silicon dioxide is 10-40 nm; more preferably, the silica has a particle size of 30 nm.
The triallyl isocyanurate and silica are not particularly limited by the manufacturer.
In the application, the bridging agent decomposes to generate free radicals, attacks active sites on a crosslinking point monomer and generates macromolecular chain free radicals, and the applicant finds that when the co-bridging agent consists of 60-80% of triallyl isocyanurate and 20-40% of silica by mass, and the particle size of the silica is 10-40 nm, the reaction rate of the co-bridging agent and the macromolecular chain free radicals is greater than the chain scission rate of tetrafluoroethylene, 1-difluoroethylene and trifluoro (trifluoromethoxy) ethylene polymers, free electrons are transferred to the co-bridging agent, the polymer free radical chain scission is avoided, and because the co-bridging agent is connected to a main chain in a side group form, the space probability of forming crosslinking is improved, the highest torque of fluororubber is further improved, and in addition, the co-bridging agent with the silica can form good dispersion in a polymer matrix, physical cross-linking points are formed with rubber molecular chains, and reactive sites are increased, so that the probability of molecular chain cross-linking is increased, and a more compact structure is formed; can realize the perfection of the cross-linked network structure of the fluororubber, and further can optimize the comprehensive performance of the material.
When the content of silica is high or the particle size is large, it may agglomerate during blending or affect the flowability of rubber, thereby affecting the rubber properties.
Bridging agent
The bridging agent has the chemical name of closed water-based curing agent (nonionic cross-linking agent), and is also named as bridging agent, curing agent, cross-linking agent, color fixing agent, adhesive, promoter, reinforcing agent and fastness improver. The main component of the bridging agent is blocked polyisocyanate. The series of curing agents can stably coexist with waterborne resin (waterborne polyurethane, waterborne acrylate, fluorine emulsion, organic silicon emulsion and the like) for a long time at normal temperature, and isocyanate (-NCO) groups released by the curing agents react with hydroxyl, carboxyl, amino and other groups on a molecular chain of the waterborne resin to form a cross-linked structure during heat treatment, so that the performance of the waterborne resin can be obviously improved.
Preferably, the bridging agent is an organic peroxide.
Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, and the like; preferably, the organic peroxide is 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, and the 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane is not particularly limited to the purchasing manufacturer.
Active agent
The activator is a substance that increases the activity of the organic accelerator to bring it into full play, thereby reducing the amount of accelerator used or shortening the vulcanization time.
Examples of the activator include magnesium oxide, calcium oxide, zinc oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and the like; preferably, the active agent is zinc oxide, the zinc oxide CAS: 1314-13-2, and the zinc oxide is not particularly limited to the purchasing manufacturer.
Reinforcing agent
The reinforcing agent is a compounding agent capable of improving the strength of rubber products.
Examples of the reinforcing agent include carbon black, calcium carbonate, white carbon, barium sulfate, calcium fluoride, calcium silicate, aluminum silicate, magnesium silicate, and aluminum borate; preferably, the reinforcing agent is carbon black, which is not particularly limited to the manufacturer.
Auxiliary agent
Preferably, the auxiliaries are fatty acid derivatives and waxes.
In one embodiment, the fatty acid derivative accounts for 40-60 wt% of the auxiliary agent; preferably, the fatty acid derivative constitutes 50 wt% of the adjuvant.
Preferably, the fatty acid derivative is any one or more of potassium stearate, sodium laurate, potassium laurate, sodium palmitate and potassium palmitate; further preferably, the fatty acid derivatives include potassium stearate and sodium stearate.
Preferably, the potassium stearate accounts for 5-15 wt% of the fatty acid derivative; more preferably, the potassium stearate comprises 10 wt% of the fatty acid derivative.
Preferably, the sodium stearate accounts for 85-95 wt% of the fatty acid derivative; more preferably, the sodium stearate constitutes 90 wt% of the fatty acid derivative.
The potassium stearate CAS: 593-29-3; the sodium stearate CAS: 822-16-2.
In one embodiment, the wax is a polyethylene wax and/or a palm wax; further preferably, the wax is a polyethylene wax; more preferably, the relative atomic mass of the polyethylene wax is 1500-2500, and the polyethylene wax is not particularly limited to a purchasing manufacturer.
The fatty acid derivative and the polyethylene wax are synergistic, so that on one hand, the mutual friction between the fluororubber and the molecules in the die is weakened, and the melt flowability of the rubber is improved, on the other hand, the auxiliary agent increases the distance between the molecular chain segments of the rubber, the interaction between the molecular chain segments is reduced, the viscosity of the fluororubber is reduced, the flexibility of the fluororubber is increased, and the processability of the fluororubber is improved.
In one embodiment, the auxiliary agent further comprises a polyglycol ether ester substance; preferably, the polyglycol ether esters include, but are not limited to, polyethylene glycol octyl adipate, polyethylene glycol ether adipate, polyethylene glycol nonyl adipate; further preferably, the polyglycol ether ester substance is polyethylene glycol octyl adipate; further preferably, the polydiethylene glycol octyl adipate accounts for 15-25 wt% of the fatty acid derivative; more preferably, the dioctyl adipate comprises 20 wt% of the fatty acid derivative.
The preparation method of the poly diethylene glycol octyl adipate at least comprises the following steps:
adding adipic acid, n-octanol, diethylene glycol and 20mL of toluene into a three-necked bottle, stirring and heating to T1Reflux t1Adding 0.4 wt% (percentage content of total mass of reaction material) of tetrabutyl titanate, heating to T2Reaction t2Until no more water was produced, the acid value was measured, and when the acid value was less than 10mg KOH/g, distillation under reduced pressure was conducted at 70 ℃.
Preferably, the molar ratio of adipic acid, n-octanol and diethylene glycol is 6: 2: 5.
preferably, said T1170-190 ℃; more preferably, said T1It was 180 ℃.
Preferably, said t1Is 0.5 to 1.5 hours; more preferably, said t1Is 1 h.
Preferably, said T2190 to 230 ℃; more preferably, said T2The temperature was 220 ℃.
PreferablySaid t is2Is 2-4 h; more preferably, said t2Is 3 h.
Preferably, the pressure of the reduced pressure distillation is 0.05-0.15 MPa; more preferably, the pressure of the reduced pressure distillation is 0.1 MPa.
The acid value of the invention is measured by the following steps:
100mL of ethanol was taken, 5 drops of phenolphthalein indicator were added, and the solution was neutralized to pink with 0.02mol/L potassium hydroxide standard solution for use. 1g of the sample is placed in a conical flask, 50mL of ethanol is added, and only 50mL of ethanol is added in another conical flask without the sample to serve as an end-point colorimetric standard. After the sample is completely dissolved, titrating by using 0.02mol/L potassium hydroxide standard solution until the color is the same as the standard color, and keeping the color unchanged for 15s to obtain the end point.
The acid value X (mg KOH/g) was calculated as follows:
X＝(CV*56.11)/m
c: the molar concentration of the potassium hydroxide standard solution is expressed in mol/L.
V: the volume of potassium hydroxide standard solution was consumed in mL.
m: the mass of the sample is weighed in g.
56.11: molar mass of potassium hydroxide.
The poly diethylene glycol octyl adipate is directionally arranged at the polar position of the rubber macromolecule, plays a role in surrounding and isolating the rubber macromolecule chain segment, increases the polar position of the rubber molecule, enables the rubber molecule chain segment to easily slide, and improves the elongation at break of the fluororubber. The applicant has found that the addition of the dioctyl adipate further improves the low temperature resistance of the fluororubber, possibly due to: on one hand, a proper amount of active groups on the poly-diethylene glycol octyl adipate can improve the affinity among particles such as carbon black and an active agent, influence the dispersion condition of the particles in a rubber system and further influence the crystallization performance of the fluororubber at low temperature; on the other hand, the poly diethylene glycol octyl adipate improves the flexibility of molecular chain segments and increases the space between molecular chain segments.
The second aspect of the invention provides a preparation method of the extremely low temperature fluorine mixed rubber, and the preparation method of the extremely low temperature fluorine mixed rubber at least comprises the following steps:
(1) plasticating the virgin rubber;
(2) banburying;
(3) adding the bridging agent and the bridging agent, milling, and forming and obtaining the fluorine rubber compound.
(4) And vulcanizing the fluorine mixed rubber to obtain the ultralow-temperature fluorine mixed rubber.
In one embodiment, the method of preparing the very low temperature fluoro compound comprises at least the following steps:
(1) adjusting the roller spacing of the open mill, and plasticating the original rubber in the open mill;
(2) adding an active agent, a reinforcing agent and an auxiliary agent for banburying;
(3) adjusting the roll gap of the open mill to d1Adding bridging agent and bridging agent, open-milling, regulating the roller spacing of open mill to d2Beating a triangular bag, and adjusting the roller spacing of the open mill to d again3And forming a sheet to obtain the fluorine rubber compound.
(4) And putting the fluorine rubber compound into a vulcanizing tank for secondary vulcanization reaction.
Preferably, the roller spacing of the open mill in the step (1) is 0.1-0.4 mm; more preferably, the roller spacing of the open mill in the step (1) is 0.2 mm.
Preferably, the virgin rubber in the step (1) is plasticated for 5-10 times; more preferably, the virgin rubber is masticated 7 times.
Preferably, the banburying temperature in the step (2) is 50-80 ℃; more preferably, the banburying temperature in the step (2) is 65 ℃.
Preferably, the banburying time in the step (2) is 8-12 min; more preferably, the banburying time in the step (2) is 10 min.
Preferably, said step (3) d10.5-1.5 mm; more preferably, said step (3) d1Is 1 mm.
Preferably, said step (3) d20.1-0.5 mm; more preferably, said step (3) d2Is 0.2 mm.
Preferably, the triangular package in the step (3) is performed for 1-10 times; more preferably, the triangular packaging times in the step (3) are 5 times.
Preferably, said step (3) d31-2 mm; more preferably, said step (3) d3Is 1.6 mm.
Preferably, the pressure of the vulcanizing tank in the step (4) is 0.4-0.6 MPa; more preferably, the pressure of the vulcanizing tank in the step (4) is 0.5 MPa.
Preferably, the first-stage vulcanization temperature in the second-stage vulcanization reaction in the step (4) is 160-180 ℃, and the second-stage vulcanization temperature is 220-250 ℃; more preferably, the temperature of the first-stage vulcanization in the second-stage vulcanization reaction in the step (4) is 170 ℃, and the temperature of the second-stage vulcanization is 235 ℃.
Preferably, the first-stage vulcanization time in the second-stage vulcanization reaction in the step (4) is 5-15 min, and the second-stage vulcanization time is 1-3 h; more preferably, the one-stage vulcanization time in the second-stage vulcanization reaction in the step (4) is 10min, and the second-stage vulcanization time is 2 h.
Examples
Example 1
The embodiment 1 of the invention provides a very-low-temperature fluorine mixed rubber, which is prepared from the raw materials of, by weight, 80 parts of virgin rubber, 1 part of co-bridging agent, 0.4 part of bridging agent, 2 parts of activating agent, 15 parts of reinforcing agent and 0.5 part of auxiliary agent.
The virgin rubber is tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer.
The tetrafluoroethylene accounts for 10 percent of the original rubber in mole percentage; the mol percentage of the 1, 1-difluoroethylene in the virgin rubber is 40%.
The preparation method of the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer comprises the following steps:
adding disodium hydrogen phosphate and a sodium perfluorooctanoate aqueous solution into a reaction kettle, introducing tetrafluoroethylene, 1-difluoroethylene and trifluoro (trifluoromethoxy) ethylene, keeping the pressure at 2MPa, stirring at the speed of 800r/min, and heating to 60 ℃; adding 15wt% ammonium persulfate aqueous solution to initiate polymerization reaction, stopping reaction when the pressure of the reaction kettle is reduced by 8%, coagulating with 5wt% calcium chloride aqueous solution, washing with deionized water until the conductivity of water is less than 5 μ s/m, and drying.
The weight ratio of the disodium hydrogen phosphate to the sodium perfluorooctanoate to the ammonium persulfate is 1: 1: 10.
the co-bridging agent comprises isocyanurate derivatives and silicon dioxide; the isocyanurate derivative is triallyl isocyanurate.
The triallyl isocyanurate accounts for 60wt% of the co-bridging agent, and the silica accounts for 40 wt% of the co-bridging agent.
The particle size of the silicon dioxide is 10nm, and the silicon dioxide is purchased from Shanghai Po micro application materials technology Co.
The bridging agent is organic peroxide; the organic peroxide is 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
The active agent is zinc oxide.
The reinforcing agent is carbon black available from Cancarb, Canada, under the model number N990.
The auxiliary agent is fatty acid derivative and wax.
The fatty acid derivative accounts for 40 wt% of the auxiliary agent; the fatty acid derivative comprises 5wt% of potassium stearate and 95wt% of sodium stearate.
The wax accounts for 60wt% of the additive, is polyethylene wax, is purchased from Gaoyi county Li and chemical industry Co., Ltd, and is PEW.
The preparation method of the extremely low temperature fluorine mixed rubber comprises the following steps:
(1) adjusting the roller spacing of the open mill to be 0.2mm, and plasticating the original rubber in the open mill for 7 times;
(2) adding an active agent, a reinforcing agent and an auxiliary agent, and banburying at 65 ℃ for 10 min;
(3) adjusting the roller spacing of the open mill to be 1mm, adding the common bridging agent and the bridging agent, carrying out open milling, adjusting the roller spacing of the open mill to be 0.2mm again, packaging the mixture for 5 times, adjusting the roller spacing of the open mill to be 1.6mm again, and forming and discharging the sheet to obtain the fluorine rubber compound.
(4) And putting the fluorine rubber compound into a vulcanizing tank, pressurizing the vulcanizing tank to 0.5MPa, and then starting to perform a second-stage vulcanization reaction, wherein the first-stage vulcanization temperature is 170 ℃, the time is 10min, and the second-stage vulcanization temperature is 235 ℃, and the time is 2 h.
Example 2
The embodiment 2 of the invention provides a very-low-temperature fluorine mixed rubber, which is prepared from the following raw materials, by weight, 110 parts of virgin rubber, 5 parts of co-bridging agent, 1.2 parts of bridging agent, 8 parts of activator, 30 parts of reinforcing agent and 1.5 parts of auxiliary agent.
The virgin rubber is tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer.
The tetrafluoroethylene accounts for 30 percent of the original rubber in mole percentage; the mol percentage of the 1, 1-difluoroethylene in the virgin rubber is 65%.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The co-bridging agent comprises isocyanurate derivatives and silicon dioxide; the isocyanurate derivative is triallyl isocyanurate.
The triallyl isocyanurate accounts for 80wt% of the co-bridging agent, and the silica accounts for 20 wt% of the co-bridging agent.
The particle size of the silicon dioxide is 40nm, and the silicon dioxide is purchased from Shanghai Po micro application materials technology Co.
The bridging agent is organic peroxide; the organic peroxide is 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
The active agent is zinc oxide.
The reinforcing agent is carbon black available from Cancarb, Canada, under the model number N990.
The auxiliary agent is fatty acid derivative and wax.
The fatty acid derivative accounts for 60wt% of the auxiliary agent; the fatty acid derivative comprises 15wt% of potassium stearate and 85 wt% of sodium stearate.
The wax accounts for 40 wt% of the auxiliary agent, is polyethylene wax, is purchased from Gaoyi county Li and chemical industry Co., Ltd, and is PEW.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 3
The embodiment 3 of the invention provides a very-low-temperature fluorine mixed rubber, which is prepared from the following raw materials, by weight, 100 parts of virgin rubber, 2.4 parts of co-bridging agent, 0.8 part of bridging agent, 4 parts of activator, 20 parts of reinforcing agent and 1 part of auxiliary agent.
The virgin rubber is tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer.
The tetrafluoroethylene accounts for 20 percent of the original rubber in mole percentage; the mol percentage of the 1, 1-difluoroethylene in the virgin rubber is 57%.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The co-bridging agent comprises isocyanurate derivatives and silicon dioxide; the isocyanurate derivative is triallyl isocyanurate.
The triallyl isocyanurate accounts for 70 wt% of the co-bridging agent, and the silica accounts for 30 wt% of the co-bridging agent.
The particle size of the silicon dioxide is 30nm, and the silicon dioxide is purchased from Shanghai Po micro application materials technology Co.
The bridging agent is organic peroxide; the organic peroxide is 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane.
The active agent is zinc oxide.
The reinforcing agent is carbon black available from Cancarb, Canada, under the model number N990.
The auxiliary agent is fatty acid derivative and wax.
The fatty acid derivative accounts for 50 wt% of the auxiliary agent; the fatty acid derivative comprises 10 wt% of potassium stearate and 90 wt% of sodium stearate.
The wax accounts for 50 wt% of the auxiliary agent, is polyethylene wax, is purchased from Gaoyi county Li and chemical industry Co., Ltd, and is PEW.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 4
The embodiment 4 of the invention provides a very low temperature fluorine rubber compound, which is the same as the embodiment 3 in specific implementation, and is different in that the auxiliary agent further comprises a polyethylene glycol ether ester substance, the polyethylene glycol ether ester substance is polyethylene glycol octyl adipate, and the polyethylene glycol octyl adipate accounts for 20 wt% of the fatty acid derivative.
The preparation method of the poly diethylene glycol octyl adipate comprises the following steps:
adding adipic acid, n-octanol, diethylene glycol and 20mL of toluene into a three-necked bottle, stirring and heating to 180 ℃, refluxing for 1h, adding 0.4 wt% (percentage content of the total mass of the reaction materials) of tetrabutyl titanate, heating to 220 ℃, reacting for 3h until no water is generated, measuring the acid value, and performing reduced pressure distillation operation at 70 ℃ when the acid value is lower than 10mg KOH/g, wherein the pressure of the reduced pressure distillation is 0.1 MPa.
The molar ratio of the adipic acid to the n-octanol to the diethylene glycol is 6: 2: 5.
the specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 5
The embodiment 5 of the invention provides a very low temperature fluorine rubber compound, which has the same specific implementation manner as the embodiment 3, and is characterized in that the auxiliary agent further comprises polyethylene glycol ether ester substances, wherein the polyethylene glycol ether ester substances are polyethylene glycol octyl adipate, and the polyethylene glycol octyl adipate accounts for 20 wt% of the fatty acid derivatives.
The preparation method of the polyethylene glycol octyl adipate comprises the following steps:
adding adipic acid, n-octanol, polyethylene glycol 200 and 20mL of toluene into a three-necked bottle, stirring and heating to 180 ℃, refluxing for 1h, adding 0.4 wt% (percentage content of the total mass of the reaction materials) of tetrabutyl titanate, heating to 220 ℃, reacting for 3h until no water is generated, measuring the acid value, and performing reduced pressure distillation operation at 70 ℃ when the acid value is lower than 10mg KOH/g, wherein the pressure of the reduced pressure distillation is 0.1 MPa.
The molar ratio of the adipic acid to the n-octanol to the polyethylene glycol 200 is 6: 2: 5.
the polyethylene glycol 200 is purchased from West Long chemical plant Shantou.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 6
Example 6 of the present invention provides a very low temperature fluorine compounded rubber, which is the same as example 3 except that the virgin rubber is purchased from SOLVAY (SOLVAY) group and has a model number of P757.
The specific embodiment of the preparation method of the very low temperature fluorine compound is the same as that of example 1.
Example 7
Example 7 of the present invention provides a very low temperature fluorine rubber compound, which is the same as example 1 in the specific embodiment, except that the tetrafluoroethylene accounts for 50 mol% of the virgin rubber, and the 1, 1-difluoroethylene accounts for 40 mol% of the virgin rubber.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 8
The embodiment 8 of the invention provides a very low temperature fluorine rubber compound, which is the same as the embodiment 1 in the specific implementation mode, and is characterized in that the tetrafluoroethylene accounts for 2 mol% of the virgin rubber, and the 1, 1-difluoroethylene accounts for 30 mol% of the virgin rubber.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 9
Example 9 of the present invention provides a very low temperature fluorine rubber compound, which is the same as example 3 in the following description, except that the co-crosslinking agent comprises trimethylolpropane trimethacrylate; the trialkyl methacrylate accounts for 70 wt% of the co-bridging agent; the co-bridging agent is purchased from first-benefit international trade (Shanghai) Co., Ltd, and is in the model of Actigran 70.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 10
The embodiment 10 of the invention provides a very low temperature fluorine rubber compound, which has the same specific implementation manner as the embodiment 3, and is characterized in that the co-bridging agent comprises polybutadiene resin and calcium silicate; the co-crosslinking agent is purchased from Yupont rubber science and technology Limited of Dongguan and has the model of RICON 153D.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 11
The embodiment 11 of the invention provides a very low temperature fluorine rubber compound, which has the same specific implementation manner as the embodiment 3, and is characterized in that the co-bridging agent comprises triallyl cyanurate and silicon dioxide; the triallyl cyanurate accounts for 70 wt% of the co-bridging agent; the co-bridging agent is purchased from St.Lai chemical technology Co., Ltd, Pingxiang, and is of the type TAC 70.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 12
Example 12 of the present invention provides a very low temperature fluoro compound, the specific embodiment of which is the same as example 3, except that the triallyl isocyanurate makes up 40 wt% of the co-bridging agent.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 13
Example 13 of the present invention provides a very low temperature fluoro compound, the specific embodiment of which is the same as example 3, except that the triallyl isocyanurate constitutes 90 wt% of the co-bridging agent.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 14
Example 14 of the present invention provides a very low temperature fluorine compounded rubber, which is the same as example 3 except that the silica particle size is 200 mesh, which is obtained from Guangzhou tide chemical Co., Ltd.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Example 15
Example 15 of the present invention provides a very low temperature fluoro compound, which is a specific embodiment of the same as example 3, except that the adjuvant comprises a fatty acid derivative and a wax, the wax being a montan wax, the adjuvant being available from DOG corporation as model D-400.
The specific embodiment of the method for preparing the tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer is the same as that of example 1.
The specific embodiment of the preparation method of the extremely low temperature fluorine mixed rubber is the same as that of example 1.
Performance evaluation
1.100% tensile modulus test: the 100% tensile modulus of the very low temperature fluoro compounds prepared in examples 1 to 15 were tested according to ASTM D412.
2. And (3) testing the maximum torque: the maximum torque of the very low temperature fluoro compounds prepared in examples 1 to 15 was tested according to ISO 4664-2-2006 standard.
3. And (3) low temperature resistance test: the low temperature resistance of the very low temperature fluoro compounds prepared in examples 1 to 15 was tested according to ASTM D2137.
4. And (3) appearance testing: the appearance of the very low temperature fluoro compounds prepared in examples 1 to 15 was judged by the smoothness of the surface and the presence or absence of white matter.
Table 1 results of performance testing
Figure BDA0002088755220000151
Figure BDA0002088755220000161
The test results in table 1 show that the ultralow-temperature fluorine rubber compound provided by the invention has excellent 100% tensile modulus, torque, low-temperature resistance and appearance, and ensures that the fluorine rubber compound is normally used in the ultralow-temperature environment.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (2)

1. The extremely low temperature fluorine mixed rubber is characterized in that the preparation raw materials of the extremely low temperature fluorine mixed rubber at least comprise 80-110 parts of virgin rubber, 1-5 parts of co-bridging agent and 0.4-1.2 parts of bridging agent by weight, wherein the virgin rubber is tetrafluoroethylene-1, 1-difluoroethylene-trifluoro (trifluoromethoxy) ethylene copolymer;
the co-bridging agent comprises isocyanurate derivatives and silicon dioxide;
the bridging agent is organic peroxide;
the isocyanurate derivative accounts for 60-80 wt% of the co-bridging agent;
the molar percentage of the tetrafluoroethylene in the virgin rubber is 10-30%, and the molar percentage of the 1, 1-difluoroethylene in the virgin rubber is 40-75%;
the preparation raw materials of the extremely-low-temperature fluorine rubber compound also comprise 2-8 parts of an active agent, 15-30 parts of a reinforcing agent and 0.5-1.5 parts of an auxiliary agent;
the auxiliary agent comprises fatty acid derivatives and wax;
the fatty acid derivative accounts for 40-60 wt% of the auxiliary agent;
the fatty acid derivatives include potassium stearate and sodium stearate;
the potassium stearate accounts for 5-15 wt% of the fatty acid derivative;
the sodium stearate accounts for 85-95 wt% of the fatty acid derivative;
the wax is polyethylene wax; the relative molecular mass of the polyethylene wax is 1500-2500.
2. A method for preparing a very low temperature fluoro compound as claimed in claim 1, characterized in that said method for preparing a very low temperature fluoro compound comprises at least the following steps:
the preparation method of the extremely low temperature fluorine mixed rubber at least comprises the following steps:
(1) adjusting the roller spacing of the open mill, and plasticating the original rubber in the open mill;
(2) adding an active agent, a reinforcing agent and an auxiliary agent for banburying;
(3) adjusting the roll gap of the open mill to d1Adding bridging agent and bridging agent, open-milling, regulating the roller spacing of open mill to d2Beating a triangular bag, and adjusting the roller spacing of the open mill to d again3Molding and forming a sheet to obtain the fluorine rubber compound;
(4) putting the fluorine rubber compound into a vulcanizing tank for a second-stage vulcanization reaction;
the roller spacing of the open mill in the step (1) is 0.1-0.4 mm;
said step (3) d10.5-1.5 mm;
said step (3) d20.1-0.5 mm;
said step (3) d3Is 1-2 mm.
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