CN108017811B - Damping rubber and preparation method thereof - Google Patents
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Abstract
The invention relates to a damping rubber and a preparation method thereof, wherein the damping rubber is obtained by plasticating and mixing rubber and modified aramid fiber.
Description
Technical Field
The invention relates to a damping rubber and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
Aramid fibers were successfully developed by the U.S. dupont company in the last 60 s and commercialized in the 70 s, and due to the advantages of high strength, high modulus and the like, aramid fibers are applied to the fields of bulletproof vests, fire-fighting uniforms, aerospace, framework materials and the like. These excellent properties are mainly determined by the aromatic structure and amide bond in the macromolecular skeleton, and their existence makes the molecular chain in rigid rod shape and mutually interact through strong hydrogen bond. The acid or benzenesulfonic acid and other few strong protonic acids cannot be post-processed by a tape casting method, but due to the high melting point, high glass transition temperature (Tg) and insolubility of PPTA, phase change occurs in the production process of the para-aramid polymer, and the final product exists in the form of solid particles and is only dissolved in concentrated sulfur, so that the requirements on equipment and a production process are extremely high, and the wide application of the PPTA is greatly limited.
The rubber has a curled long-chain molecular structure and weak secondary force existing among molecules, so that the rubber material presents unique viscoelastic performance, and has good shock absorption, sound insulation and buffering performances. Rubber components are widely used for shock isolation and shock absorption because of their hysteresis, damping and reversible large deformation characteristics. The hysteresis and internal friction characteristics of rubber are generally expressed by loss factors, and the larger the loss factor is, the more remarkable the damping and heat generation of the rubber is, and the more remarkable the damping effect is. Butyl rubber (HR) and nitrile rubber (NBR) have the largest dissipation factor and are therefore commonly used as vibration damping materials.
However, the rubber has the problems of short service life and frequent replacement in shock absorption, the main factor is that the rubber is a bad conductor due to thermal oxidation, mechanical energy absorbed by the shock absorption cannot be dissipated in time after being converted into heat energy, so the temperature of the rubber is increased, and the temperature rise not only reduces the performance of a rubber product, but also accelerates the thermal oxidation aging process of the rubber product, thereby shortening the service life of the rubber product. The market needs the product that shock attenuation is effectual, and long service life.
Disclosure of Invention
The invention provides the damping rubber and the preparation method thereof, and the damping rubber has excellent stability and mechanical property and can obviously prolong the service life of the rubber.
In order to solve the technical problems, the invention adopts the following technical scheme:
a shock-absorbing rubber is characterized in that,
consists of modified aramid fiber and rubber.
Also comprises an accelerator, a plasticizer, an anti-aging agent, carbonyl iron powder, sulfur, resin, a reactive diluent and a photoinitiator.
Preferably, the damping rubber is composed of, by weight, 140-180 parts of rubber, 4-6 parts of modified aramid fiber, 4-6 parts of epoxy resin, 1-5 parts of a photoinitiator, 1-2 parts of an accelerator, 1-3 parts of a plasticizer, 2-4 parts of an anti-aging agent, 1-5 parts of carbonyl iron powder, 3-6 parts of sulfur and 3-10 parts of a reactive diluent.
Preferably, the damping rubber is composed of 140-180 parts of nitrile rubber, 4-6 parts of liquid modified para-aramid, 4-6 parts of alicyclic epoxy resin, 1-5 parts of photoinitiator, 1-2 parts of accelerator, 1-3 parts of plasticizer, 2-4 parts of anti-aging agent, 1-5 parts of carbonyl iron powder, 3-6 parts of sulfur and 3-10 parts of reactive diluent in parts by weight.
The alicyclic epoxy resin is a polymerization product of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylcarboxylate, bis- (3, 4-epoxycyclohexylmethyl) adipate, 3, 4-epoxycyclohexylmethyl methacrylate, 3, 4-epoxycyclohexylmethacrylate, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylformate and caprolactone, one or more of 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 4-vinyl-1-cyclohexene diepoxide, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester and 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexanecarboxylic acid) ester; the photoinitiator is one or a mixture of more of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl benzophenone, bis (2, 4, 6-trimethylbenzoyl) phenyl phosphorus oxide, alpha' -dimethyl benzil ketal, isopropyl thioxanthone, benzophenone and 2,4, 6-trimethylbenzoyl diphenyl phosphorus oxide, triaryl hexafluoro phosphonium phosphate, triaryl hexafluoro antimonic acid sulfonium salt and diaryl hexafluoro iodonium phosphate; the accelerator is one or more than two of an accelerator TMTD, an accelerator M and an accelerator ZDMC in any proportion; the anti-aging agent is one or more than two of anti-aging agent 4020, anti-aging agent RD and anti-aging agent NBC in any proportion; the plasticizer is one or more than two of dibutyl phthalate, epoxy octyl stearate and dioctyl adipate in any proportion; the active diluent is one or a mixture of any more of 3-ethyl-3-oxetanyl methanol, 3' - (oxybis methylene) bis (3-ethyl) oxetane, 1,2,8, 9-diepoxy-4-vinyl cyclohexene and vinyl ether; the particle size of the carbonyl iron powder is 2-5 mu m.
The preparation method of the damping rubber comprises the following steps:
preparing liquid modified para-aramid:
1) preparing a solution: adding a monomer A and a monomer B into a reaction kettle, pumping an organic solvent, heating to 30-80 ℃ under the protection of nitrogen, stirring until the monomer A and the monomer B are dissolved, wherein the total molar concentration of the monomer A and the monomer B is 0.30-0.60 mol/L, and the molar ratio of the monomer A to the monomer B is 1.00-2.22: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-15-10 ℃ while stirring;
3) adding a monomer C: adding a monomer C with the molar quantity equal to the sum of the monomer A and the monomer B into the cooling solution in the step 2) under the stirring condition at the temperature of between 15 ℃ below zero and 10 ℃;
4) preparing liquid modified para-aramid: reacting for 30-45 min at-15-10 ℃ under stirring, and defoaming for 20-30 min at-0.15-0.098 MPa and 25 +/-5 ℃ to obtain liquid modified para-aramid;
the monomer A is one of p-phenylenediamine and o-chloro-p-phenylenediamine or two of p-phenylenediamine and o-chloro-p-phenylenediamine in any proportion;
the monomer B is one or two of 3,4 '-diaminodiphenyl ether and 4,4' -diaminodiphenyl ether in any proportion;
the monomer C is terephthaloyl chloride;
the organic solvent is one or two of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) in any proportion;
preparing damping rubber:
5) preparing damping rubber: the preparation method comprises the steps of firstly putting rubber, modified aramid fiber, alicyclic epoxy resin and active diluent into an internal mixer, plastifying for 8-20 min at the temperature of 70-110 ℃, then putting a photoinitiator, an accelerator, a plasticizer, an anti-aging agent, carbonyl iron powder and sulfur into the internal mixer, mixing for 8-15 min at the temperature of 120-140 ℃, cooling to room temperature, and discharging to obtain the shock-absorbing rubber.
Preferably, the mixing in the step 5) is carried out under the action of a magnetic field, and the magnetic field is 100-1000 mT.
The invention has the following beneficial technical effects:
1. the liquid modified para-aramid produced according to the method of the patent keeps excellent physical and chemical properties of the para-aramid polymer, and simultaneously, the modified para-aramid polymer has good fluidity and is beneficial to being mixed with rubber.
2. The alicyclic epoxy resin is added into the rubber, so that the rubber has plasticizing and tackifying functions, and rubber molecular chains at an adhesion interface can be plasticized and diffused to the surface of the fiber in the rubber vulcanization process, so that the wettability of the rubber to the fiber is improved.
3. The addition of the photoinitiator in the invention can obviously shorten the treatment time.
4. The rubber produced by the method has the advantages of good heat shrinkage resistance, large damping coefficient and good anti-seismic effect.
5. The mixing is carried out under the action of a magnetic field, so that the mechanical strength of the damping rubber can be obviously improved.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The damping rubber is composed of 160 parts of nitrile rubber, 5 parts of liquid modified para-aramid, 5 parts of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl carboxylate, 3 parts of bis (2, 4, 6-trimethyl benzoyl) phenyl phosphorus oxide, 3 parts of accelerator TMTD1, 2 parts of dibutyl phthalate, 3 parts of anti-aging agent RD, 3 parts of carbonyl iron powder, 4 parts of sulfur and 6 parts of 3, 3' - (oxybis methylene) bis (3-ethyl) oxetane according to parts by weight.
The damping rubber is prepared by the following steps:
preparing liquid modified para-aramid:
1) preparing a solution: adding o-chloro-p-phenylenediamine and 3,4' -diaminodiphenyl ether into a reaction kettle, pumping N, N-dimethylformamide, heating to 60 ℃ under the protection of nitrogen, stirring until the N, N-dimethylformamide is dissolved, wherein the total molar concentration of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether is 0.40mol/L, and the molar ratio of the o-chloro-p-phenylenediamine to the 3,4' -diaminodiphenyl ether is 1.5: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-5 ℃ while stirring;
3) adding paraphthaloyl chloride: adding paraphthaloyl chloride with the molar quantity equal to the sum of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether into the cooling solution in the step 2) at the temperature of between 5 ℃ below zero and 5 ℃ under the stirring condition;
4) preparing liquid modified para-aramid: reacting for 35min under the stirring condition at the temperature of between 5 ℃ below zero and 5 ℃, and defoaming for 20min under the conditions that the pressure is 0.098MPa and the temperature is 25 +/-5 ℃ to obtain liquid modified para-aramid;
preparing damping rubber:
5) preparing damping rubber: firstly putting nitrile rubber, liquid modified para-aramid, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate and 3, 3' - (oxydimethylene) bis (3-ethyl) oxetane into an internal mixer, plasticating for 15min at the temperature of 90 ℃, then putting bis (2, 4, 6-trimethylbenzoyl) phenyl phosphorus oxide, an accelerator TMTD, dibutyl phthalate, an anti-aging agent RD, carbonyl iron powder and sulfur into the internal mixer, mixing for 12min at the temperature of 125 ℃ and the magnetic field of 200mT, cooling to room temperature, and discharging to obtain the shock-absorbing rubber.
Example 2
The damping rubber is composed of 160 parts of nitrile rubber, 5 parts of liquid modified para-aramid, 5 parts of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl carboxylic ester, 3 parts of triaryl hexafluoro phosphonium salt, 3 parts of accelerator TMTD1, 2 parts of dibutyl phthalate, 3 parts of anti-aging agent RD, 3 parts of carbonyl iron powder, 4 parts of sulfur and 6 parts of 3, 3' - (oxybis methylene) bis (3-ethyl) oxetane according to parts by weight.
The damping rubber is prepared by the following steps:
preparing liquid modified para-aramid:
1) preparing a solution: adding o-chloro-p-phenylenediamine and 3,4' -diaminodiphenyl ether into a reaction kettle, pumping N, N-dimethylformamide, heating to 60 ℃ under the protection of nitrogen, stirring until the N, N-dimethylformamide is dissolved, wherein the total molar concentration of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether is 0.40mol/L, and the molar ratio of the o-chloro-p-phenylenediamine to the 3,4' -diaminodiphenyl ether is 1.5: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-5 ℃ while stirring;
3) adding paraphthaloyl chloride: adding paraphthaloyl chloride with the molar quantity equal to the sum of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether into the cooling solution in the step 2) at the temperature of between 5 ℃ below zero and 5 ℃ under the stirring condition;
4) preparing liquid modified para-aramid: reacting for 35min under the stirring condition at the temperature of between 5 ℃ below zero and 5 ℃, and defoaming for 20min under the conditions that the pressure is 0.098MPa and the temperature is 25 +/-5 ℃ to obtain liquid modified para-aramid;
preparing damping rubber:
5) preparing damping rubber: firstly putting nitrile rubber, liquid modified para-aramid, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate and 3, 3' - (oxydimethylene) bis (3-ethyl) oxetane into an internal mixer, plasticating for 15min at the temperature of 90 ℃, then putting triaryl sulfur hexafluorophosphate onium salt, accelerant TMTD, dibutyl phthalate, anti-aging agent RD, carbonyl iron powder and sulfur into the internal mixer, mixing for 12min at the temperature of 125 ℃ and the magnetic field of 200mT, cooling to room temperature, and discharging to obtain the shock-absorbing rubber.
Example 3
The damping rubber is composed of 160 parts of nitrile rubber, 5 parts of liquid modified para-aramid, 5 parts of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl carboxylate, 2 parts of bis (2, 4, 6-trimethyl benzoyl) phenyl phosphorus oxide, 1 part of triaryl hexafluoro phosphonium phosphate sulfonium salt, 1 parts of accelerator TMTD, 2 parts of dibutyl phthalate, 3 parts of anti-aging agent RD, 3 parts of carbonyl iron powder, 4 parts of sulfur and 6 parts of 3, 3' - (oxybis methylene) bis (3-ethyl) oxetane according to parts by weight.
The damping rubber is prepared by the following steps:
preparing liquid modified para-aramid:
1) preparing a solution: adding o-chloro-p-phenylenediamine and 3,4' -diaminodiphenyl ether into a reaction kettle, pumping N, N-dimethylformamide, heating to 60 ℃ under the protection of nitrogen, stirring until the N, N-dimethylformamide is dissolved, wherein the total molar concentration of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether is 0.40mol/L, and the molar ratio of the o-chloro-p-phenylenediamine to the 3,4' -diaminodiphenyl ether is 1.5: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-5 ℃ while stirring;
3) adding paraphthaloyl chloride: adding paraphthaloyl chloride with the molar quantity equal to the sum of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether into the cooling solution in the step 2) at the temperature of between 5 ℃ below zero and 5 ℃ under the stirring condition;
4) preparing liquid modified para-aramid: reacting for 35min under the stirring condition at the temperature of between 5 ℃ below zero and 5 ℃, and defoaming for 20min under the conditions that the pressure is 0.098MPa and the temperature is 25 +/-5 ℃ to obtain liquid modified para-aramid;
preparing damping rubber:
5) preparing damping rubber: the preparation method comprises the steps of firstly putting nitrile rubber, liquid modified para-aramid, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate and 3, 3' - (oxydimethylene) bis (3-ethyl) oxetane into an internal mixer, plasticating for 15min at the temperature of 90 ℃, then putting bis (2, 4, 6-trimethylbenzoyl) phenyl phosphorus oxide, triaryl hexafluorophosphate sulfonium salt, an accelerator TMTD, dibutyl phthalate, an anti-aging agent RD, carbonyl iron powder and sulfur into the internal mixer, mixing for 12min at the temperature of 125 ℃ and the magnetic field of 200mT, cooling to room temperature, and discharging to obtain the shock-absorbing rubber.
Example 4
The damping rubber is composed of 160 parts of nitrile rubber, 5 parts of liquid modified para-aramid, 5 parts of 3, 4-epoxy cyclohexyl methyl-3, 4-epoxy cyclohexyl carboxylate, 1 part of bis (2, 4, 6-trimethyl benzoyl) phenyl phosphorus oxide, 2 parts of triaryl phosphonium hexafluorophosphate sulfonium salt, 1 parts of accelerator TMTD, 2 parts of dibutyl phthalate, 3 parts of anti-aging agent RD, 3 parts of carbonyl iron powder, 4 parts of sulfur and 6 parts of 3, 3' - (oxybismethylene) bis (3-ethyl) oxetane according to parts by weight.
The damping rubber is prepared by the following steps:
preparing liquid modified para-aramid:
1) preparing a solution: adding o-chloro-p-phenylenediamine and 3,4' -diaminodiphenyl ether into a reaction kettle, pumping N, N-dimethylformamide, heating to 60 ℃ under the protection of nitrogen, stirring until the N, N-dimethylformamide is dissolved, wherein the total molar concentration of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether is 0.40mol/L, and the molar ratio of the o-chloro-p-phenylenediamine to the 3,4' -diaminodiphenyl ether is 1.5: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-5 ℃ while stirring;
3) adding paraphthaloyl chloride: adding paraphthaloyl chloride with the molar quantity equal to the sum of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether into the cooling solution in the step 2) at the temperature of between 5 ℃ below zero and 5 ℃ under the stirring condition;
4) preparing liquid modified para-aramid: reacting for 35min under the stirring condition at the temperature of between 5 ℃ below zero and 5 ℃, and defoaming for 20min under the conditions that the pressure is 0.098MPa and the temperature is 25 +/-5 ℃ to obtain liquid modified para-aramid;
preparing damping rubber:
5) preparing damping rubber: the preparation method comprises the steps of firstly putting nitrile rubber, liquid modified para-aramid, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate and 3, 3' - (oxydimethylene) bis (3-ethyl) oxetane into an internal mixer, plasticating for 15min at the temperature of 90 ℃, then putting bis (2, 4, 6-trimethylbenzoyl) phenyl phosphorus oxide, triaryl hexafluorophosphate sulfonium salt, an accelerator TMTD, dibutyl phthalate, an anti-aging agent RD, carbonyl iron powder and sulfur into the internal mixer, mixing for 12min at the temperature of 125 ℃ and the magnetic field of 200mT, cooling to room temperature, and discharging to obtain the shock-absorbing rubber.
Example 5
The damping rubber is composed of 160 parts by weight of hydrogenated nitrile rubber, 5 parts by weight of liquid modified para-aramid, 5 parts by weight of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate, 3 parts by weight of triaryl hexafluorophosphate sulfonium salt, 3 parts by weight of accelerator TMTD1, 2 parts by weight of dibutyl phthalate, 3 parts by weight of anti-aging agent RD, 3 parts by weight of carbonyl iron powder, 4 parts by weight of sulfur and 6 parts by weight of 3, 3' - (oxybis methylene) bis (3-ethyl) oxetane.
The damping rubber is prepared by the following steps:
preparing liquid modified para-aramid:
1) preparing a solution: adding o-chloro-p-phenylenediamine and 3,4' -diaminodiphenyl ether into a reaction kettle, pumping N, N-dimethylformamide, heating to 60 ℃ under the protection of nitrogen, stirring until the N, N-dimethylformamide is dissolved, wherein the total molar concentration of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether is 0.40mol/L, and the molar ratio of the o-chloro-p-phenylenediamine to the 3,4' -diaminodiphenyl ether is 1.5: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-5 ℃ while stirring;
3) adding paraphthaloyl chloride: adding paraphthaloyl chloride with the molar quantity equal to the sum of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether into the cooling solution in the step 2) at the temperature of between 5 ℃ below zero and 5 ℃ under the stirring condition;
4) preparing liquid modified para-aramid: reacting for 35min under the stirring condition at the temperature of between 5 ℃ below zero and 5 ℃, and defoaming for 20min under the conditions that the pressure is 0.098MPa and the temperature is 25 +/-5 ℃ to obtain liquid modified para-aramid;
preparing damping rubber:
5) preparing damping rubber: firstly, putting hydrogenated nitrile rubber, liquid modified para-aramid, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate and 3, 3' - (oxybispropylene) bis (3-ethyl) oxetane into an internal mixer, plasticating for 15min at the temperature of 90 ℃, then putting triaryl sulfur hexafluorophosphate sulfonium salt, an accelerator TMTD, dibutyl phthalate, an anti-aging agent RD, carbonyl iron powder and sulfur into the internal mixer, mixing for 12min at the temperature of 125 ℃ and the magnetic field of 200mT, cooling to room temperature, and discharging to obtain the shock-absorbing rubber.
Example 6
The damping rubber is composed of 160 parts by weight of butyl rubber, 5 parts by weight of liquid modified para-aramid, 5 parts by weight of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate, 3 parts by weight of triaryl hexafluorophosphate sulfonium salt, 3 parts by weight of accelerator TMTD1, 2 parts by weight of dibutyl phthalate, 3 parts by weight of anti-aging agent RD, 3 parts by weight of carbonyl iron powder, 4 parts by weight of sulfur and 6 parts by weight of 3, 3' - (oxybis methylene) bis (3-ethyl) oxetane.
The damping rubber is prepared by the following steps:
preparing liquid modified para-aramid:
1) preparing a solution: adding o-chloro-p-phenylenediamine and 3,4' -diaminodiphenyl ether into a reaction kettle, pumping N, N-dimethylformamide, heating to 60 ℃ under the protection of nitrogen, stirring until the N, N-dimethylformamide is dissolved, wherein the total molar concentration of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether is 0.40mol/L, and the molar ratio of the o-chloro-p-phenylenediamine to the 3,4' -diaminodiphenyl ether is 1.5: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-5 ℃ while stirring;
3) adding paraphthaloyl chloride: adding paraphthaloyl chloride with the molar quantity equal to the sum of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether into the cooling solution in the step 2) at the temperature of between 5 ℃ below zero and 5 ℃ under the stirring condition;
4) preparing liquid modified para-aramid: reacting for 35min under the stirring condition at the temperature of between 5 ℃ below zero and 5 ℃, and defoaming for 20min under the conditions that the pressure is 0.098MPa and the temperature is 25 +/-5 ℃ to obtain liquid modified para-aramid;
preparing damping rubber:
5) preparing damping rubber: the method comprises the steps of firstly putting butyl rubber, liquid modified para-aramid, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate and 3, 3' - (oxydimethylene) bis (3-ethyl) oxetane into an internal mixer, plasticating for 15min at the temperature of 90 ℃, putting triaryl thiophosphonium hexafluorophosphate, an accelerator TMTD, dibutyl phthalate, an anti-aging agent RD, carbonyl iron powder and sulfur into the internal mixer, mixing for 12min at the temperature of 125 ℃ and the magnetic field of 200mT, cooling to room temperature, and discharging to obtain the shock-absorbing rubber.
Example 7
The damping rubber is composed of 160 parts of nitrile rubber, 5 parts of liquid modified para-aramid, 5 parts of bisphenol A epoxy resin, 3 parts of triaryl hexafluorophosphate sulfonium salt, 1 parts of accelerator TMTD, 2 parts of dibutyl phthalate, 3 parts of anti-aging agent RD, 3 parts of carbonyl iron powder, 4 parts of sulfur and 6 parts of 3, 3' - (oxybis methylene) bis (3-ethyl) oxetane according to parts by weight.
The damping rubber is prepared by the following steps:
preparing liquid modified para-aramid:
1) preparing a solution: adding o-chloro-p-phenylenediamine and 3,4' -diaminodiphenyl ether into a reaction kettle, pumping N, N-dimethylformamide, heating to 60 ℃ under the protection of nitrogen, stirring until the N, N-dimethylformamide is dissolved, wherein the total molar concentration of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether is 0.40mol/L, and the molar ratio of the o-chloro-p-phenylenediamine to the 3,4' -diaminodiphenyl ether is 1.5: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-5 ℃ while stirring;
3) adding paraphthaloyl chloride: adding paraphthaloyl chloride with the molar quantity equal to the sum of the o-chloro-p-phenylenediamine and the 3,4' -diaminodiphenyl ether into the cooling solution in the step 2) at the temperature of between 5 ℃ below zero and 5 ℃ under the stirring condition;
4) preparing liquid modified para-aramid: reacting for 35min under the stirring condition at the temperature of between 5 ℃ below zero and 5 ℃, and defoaming for 20min under the conditions that the pressure is 0.098MPa and the temperature is 25 +/-5 ℃ to obtain liquid modified para-aramid;
preparing damping rubber:
5) preparing damping rubber: firstly putting nitrile rubber, liquid modified para-aramid, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl carboxylate and 3, 3' - (oxydimethylene) bis (3-ethyl) oxetane into an internal mixer, plasticating for 15min at the temperature of 90 ℃, then putting triaryl sulfur hexafluorophosphate onium salt, accelerant TMTD, dibutyl phthalate, anti-aging agent RD, carbonyl iron powder and sulfur into the internal mixer, mixing for 12min at the temperature of 125 ℃ and the magnetic field of 200mT, cooling to room temperature, and discharging to obtain the shock-absorbing rubber.
Example 8
The damping rubber is composed of 40 parts by weight of natural rubber, 100 parts by weight of nitrile rubber, 2 parts by weight of modified para-aramid, 3 parts by weight of meta-aramid, 3 parts by weight of bisphenol A epoxy resin, 2 parts by weight of diglycidyl tetrahydrophthalate, 1 part by weight of triaryl hexafluoroantimonate sulfonium salt, 2 parts by weight of diaryl iodonium hexafluorophosphate, 1 parts by weight of accelerator M, 1 part by weight of dibutyl phthalate, 1 part by weight of octyl epoxystearate, 3 parts by weight of anti-aging agent NBC, 2 parts by weight of carbonyl iron powder, 3 parts by weight of sulfur, 2 parts by weight of 3, 3' - (oxybis methylene) bis (3-ethyl) oxetane and 2 parts by weight of 1,2,8, 9-diepoxy-4-vinylcyclohexene.
The preparation method of the damping rubber comprises the following steps:
preparing liquid modified para-aramid:
1) preparing a solution: adding a monomer A and a monomer B into a reaction kettle, pumping an organic solvent, heating to 30 ℃ under the protection of nitrogen, and stirring until the monomer A and the monomer B are dissolved, wherein the total molar concentration of the monomer A and the monomer B is 0.50mol/L, and the molar ratio of the monomer A to the monomer B is 1.79: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-5 ℃ while stirring;
3) adding a monomer C: adding a monomer C with the molar quantity equal to the sum of the monomer A and the monomer B into the cooling solution in the step 2) at the temperature of minus 8 ℃ under the stirring condition;
4) preparing liquid modified para-aramid: reacting for 35min at the temperature of minus 10 ℃ under stirring, and defoaming for 20min at the pressure of minus 0.10MPa and the temperature of 25 +/-5 ℃ to obtain liquid modified para-aramid;
the monomer A is a composition of p-phenylenediamine and o-chloro-p-phenylenediamine according to a mass ratio of 1: 1;
the monomer B is a composition of 3,4 '-diaminodiphenyl ether and 4,4' -diaminodiphenyl ether in a mass ratio of 1: 2;
the monomer C is terephthaloyl chloride;
the organic solvent is a composition of N, N-Dimethylformamide (DMF) and N-methylpyrrolidone (NMP) according to a mass ratio of 1: 2;
preparing damping rubber:
5) preparing damping rubber: the method comprises the steps of firstly putting natural rubber, nitrile rubber, modified para-aramid, meta-aramid, bisphenol A epoxy resin, tetrahydrophthalic acid diglycidyl ester, 2 parts of 3, 3' - (oxydimethylene) bis (3-ethyl) oxetane and 1,2,8, 9-diepoxy-4-vinylcyclohexene into an internal mixer, plastifying for 10min at the temperature of 100 ℃, then putting triaryl hexafluoroantimonate sulfonium salt, diaryl iodonium hexafluorophosphate, an accelerator M1, dibutyl phthalate, epoxy octyl stearate, an anti-aging agent NBC, carbonyl iron powder and sulfur into the internal mixer, mixing for 10min at the temperature of 140 ℃ and the magnetic field of 100-1000 mT, and cooling to room temperature to obtain the shock-absorbing rubber.
Example 9
The damping rubber is composed of 40 parts by weight of natural rubber, 100 parts by weight of nitrile rubber, 2 parts by weight of modified meta-aramid, 3 parts by weight of bisphenol A epoxy resin, 2 parts by weight of diglycidyl tetrahydrophthalate, 1 part by weight of triaryl hexafluoroantimonate sulfonium salt, 2 parts by weight of diaryl iodonium hexafluorophosphate, 1 parts by weight of accelerator M, 1 part by weight of dibutyl phthalate, 1 part by weight of octyl epoxystearate, 3 parts by weight of anti-aging agent NBC, 2 parts by weight of carbonyl iron powder, 3 parts by weight of sulfur, 2 parts by weight of 3, 3' - (oxybis methylene) bis (3-ethyl) oxetane and 2 parts by weight of 1,2,8, 9-diepoxy-4-vinylcyclohexene.
The preparation method of the damping rubber comprises the following steps:
preparing liquid modified meta-aramid:
1) preparing a solution: adding a monomer A and a monomer B into a reaction kettle, pumping an organic solvent, heating to 30 ℃ under the protection of nitrogen, and stirring until the monomer A and the monomer B are dissolved, wherein the total molar concentration of the monomer A and the monomer B is 0.50mol/L, and the molar ratio of the monomer A to the monomer B is 1.79: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-5 ℃ while stirring;
3) adding a monomer C: adding a monomer C with the molar quantity equal to the sum of the monomer A and the monomer B into the cooling solution in the step 2) at the temperature of minus 8 ℃ under the stirring condition;
4) preparing liquid modified meta-aramid: reacting for 35min at the temperature of minus 10 ℃ under stirring, and defoaming for 20min at the pressure of minus 0.10MPa and the temperature of 25 +/-5 ℃ to obtain liquid modified para-aramid;
the monomer A is a composition of m-phenylenediamine and o-chloro-m-phenylenediamine in a mass ratio of 1: 1;
the monomer B is a composition of 3,4 '-diaminodiphenyl ether and 4,4' -diaminodiphenyl ether in a mass ratio of 1: 2;
the monomer C is isophthaloyl dichloride;
the organic solvent is a composition of N, N-Dimethylformamide (DMF) and N-methylpyrrolidone (NMP) according to a mass ratio of 1: 2;
preparing damping rubber:
5) preparing damping rubber: the method comprises the steps of firstly putting natural rubber, nitrile rubber, modified meta-aramid, bisphenol A epoxy resin, diglycidyl tetrahydrophthalate, 2 parts of 3, 3' - (oxybispropylene) bis (3-ethyl) oxetane and 1,2,8, 9-diepoxy-4-vinylcyclohexene into an internal mixer, plastifying for 10min at the temperature of 100 ℃, then putting triaryl hexafluoroantimonate sulfonium salt, diaryl iodonium hexafluorophosphate, an accelerator M1, dibutyl phthalate, epoxy octyl stearate, an anti-aging agent NBC, carbonyl iron powder and sulfur into the internal mixer, mixing for 10min at the temperature of 140 ℃ and the magnetic field of 100-1000 mT, and cooling to room temperature to obtain the shock-absorbing rubber.
The beneficial effects of the present invention are further illustrated below in conjunction with experimental data:
1, materials and methods:
1.1 test site: laboratory of certain rubber production enterprises of cigarette benches.
1.2 test detection: the tensile strength, 100% stress at definite elongation, 200% stress at definite elongation, elongation at break and shore a hardness were measured at room temperature and are shown in table 1; the tensile strength retention and the tensile elongation retention were measured at 100 ℃ for 48 hours.
1.3 test materials: the rubber is provided by the cigarette tai antle rubber company, and the aramid fiber is uncoated para-aramid fiber provided by the cigarette tai and new materials company. Examples 1 to 7, comparative example 1 (the preparation method was the same as that of example 2 except that no epoxy resin was added), comparative example 2 (the preparation method was the same as that of example 2 except that no photoinitiator was added), comparative example 3 (the preparation method was the same as that of example 2 except that no carbonyl iron powder was added and no magnetic field was added), and a blank (the preparation method was the same as that of example 2 except that the para-aramid fiber was not modified) were respectively followed.
The detection method comprises the following steps: the test was performed according to ASTM D-412 test method and Shore A hardness test method.
2 results and analysis
Table 1 tensile strength, 100% tensile stress, 200% tensile stress, final elongation and shore a hardness test data.
TABLE 1
Table 2100 ℃,48h, examining tensile strength retention and ultimate elongation retention
TABLE 2
| Tensile Strength holding ratio (%) | Final elongation retention (%) | Shore A hardness (degree) | |
| Example 1 | 53.3 | 69.72 | 62 |
| Example 2 | 62.31 | 79.52 | 64 |
| Example 3 | 54.12 | 70.55 | 63 |
| Example 4 | 59.03 | 75.03 | 61 |
| Example 5 | 61.22 | 78.12 | 60 |
| Example 6 | 60.37 | 77.88 | 61 |
| Example 7 | 57.22 | 74.21 | 62 |
| Comparative example 1 | 51.31 | 65.37 | 46 |
| Comparative example 2 | 51.97 | 67.21 | 48 |
| Comparison 3 | 50.55 | 62.53 | 54 |
| Blank space | 39.66 | 57.66 | 37 |
As can be seen from the data in tables 1 and 2, the blank effect is the worst, and the damping effect is the best in example 2; from the data of the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 4, it can be seen that the tensile strength, the tensile stress, the final elongation, the tensile strength retention rate and the final elongation retention rate of the rubber are gradually enhanced with the increase of the amount of the cationic photoinitiator, which indicates that the cationic photoinitiator is better than the common photoinitiator; the comparison of the data of the embodiment 2, the embodiment 5 and the embodiment 6 can obtain that the selected nitrile rubber is superior to other rubbers in the aspect of damping effect; the comparison of the data of the embodiment 2 and the embodiment 7 can show that the damping effect of the cycloaliphatic epoxy resin is better than that of the common epoxy resin; the comparison of the data of the example 2 and the comparative example 1 shows that the tensile strength, the tensile stress, the final elongation, the retention rate of the tensile strength and the retention rate of the final elongation of the rubber are improved by adding the epoxy resin; comparing the data of example 2 and comparative example 2, it can be shown that the shock absorption effect of the added photoinitiator is better than that of the added photoinitiator; comparison of the data of example 3 and comparative example 3 shows that the addition of carbonyl iron powder and magnetic field can significantly improve the damping performance of the rubber.
In the aspect of aging resistance, compared with the detection results before and after thermal oxidation aging in tables 1 and 2, the tensile strength retention rate and the final elongation retention rate of the composite material are greatly improved in comparison with comparison 1, comparison 2, comparison 3 and blank in the invention, wherein the epoxy resin is alicyclic epoxy resin, the photoinitiators are all cationic photoinitiators, and the rubber is nitrile butadiene rubber, and the embodiment 2 is superior to other embodiments in the aspect of aging resistance.
Claims (6)
1. A shock-absorbing rubber is characterized in that,
the modified para-aramid fiber rubber comprises liquid modified para-aramid fiber and rubber, and also comprises alicyclic epoxy resin, an active diluent, a photoinitiator and carbonyl iron powder;
the preparation method of the damping rubber comprises the following steps:
preparing liquid modified para-aramid: 1) Preparing a solution: adding a monomer A and a monomer B into a reaction kettle, pumping an organic solvent, heating to 30-80 ℃ under the protection of nitrogen, stirring until the monomer A and the monomer B are dissolved, wherein the total molar concentration of the monomer A and the monomer B is 0.30-0.60 mol/L, and the molar ratio of the monomer A to the monomer B is 1.00-2.22: 1; 2) Cooling the solution: cooling the solution prepared in the step 1) to-15-10 ℃ while stirring; 3) Adding a monomer C: adding a monomer C with the molar quantity equal to the sum of the monomer A and the monomer B into the cooling solution in the step 2) under the stirring condition at the temperature of between 15 ℃ below zero and 10 ℃; 4) Preparing liquid modified para-aramid: reacting for 30-45 min at-15-10 ℃ under stirring, and defoaming for 20-30 min at-0.15-0.098 MPa and 25 +/-5 ℃ to obtain liquid modified para-aramid; the monomer A is one of p-phenylenediamine and o-chloro-p-phenylenediamine or two of p-phenylenediamine and o-chloro-p-phenylenediamine in any proportion; the monomer B is one or two of 3,4 '-diaminodiphenyl ether and 4,4' -diaminodiphenyl ether in any proportion;
the monomer C is terephthaloyl chloride; the organic solvent is one or two of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) in any proportion; preparing damping rubber: 5) Preparing damping rubber: firstly, rubber, modified aramid fiber, alicyclic epoxy resin and active diluent are put into an internal mixer, plasticating is carried out for 8-20 min at the temperature of 70-110 ℃, then a photoinitiator, an accelerator, a plasticizer, an anti-aging agent, carbonyl iron powder and sulfur are put into the internal mixer, mixing is carried out for 8-15 min at the temperature of 120-140 ℃, cooling is carried out to room temperature, and discharging is carried out, thus obtaining the damping rubber; the mixing is carried out under the action of a magnetic field, and the magnetic field is 100-1000 mT.
2. The cushion rubber according to claim 1, further comprising one of an accelerator, a plasticizer, an antioxidant and sulfur.
3. The damping rubber according to claim 2, wherein the damping rubber comprises, by weight, 140-180 parts of nitrile rubber, 4-6 parts of liquid modified para-aramid, 4-6 parts of alicyclic epoxy resin, 1-5 parts of photoinitiator, 1-2 parts of accelerator, 1-3 parts of plasticizer, 2-4 parts of anti-aging agent, 1-5 parts of carbonyl iron powder, 3-6 parts of sulfur and 3-10 parts of reactive diluent.
4. The cushion rubber according to claim 3, wherein the alicyclic epoxy resin is 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexylcarboxylate, bis- (3, 4-epoxycyclohexylmethyl) adipate, 3, 4-epoxycyclohexylmethyl methacrylate, 3, 4-epoxycyclohexylmethyl acrylate, a polymerization product of 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl formate and caprolactone, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 4-vinyl-1-cyclohexene diepoxide, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester and 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexanecarboxylic acid) ester; the photoinitiator is one or a mixture of more of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl benzophenone, bis (2, 4, 6-trimethylbenzoyl) phenyl phosphorus oxide, alpha' -dimethyl benzil ketal, isopropyl thioxanthone, benzophenone and 2,4, 6-trimethylbenzoyl diphenyl phosphorus oxide, triaryl hexafluoro phosphonium phosphate, triaryl hexafluoro antimonic acid sulfonium salt and diaryl hexafluoro iodonium phosphate; the accelerator is one or more than two of an accelerator TMTD, an accelerator M and an accelerator ZDMC in any proportion; the anti-aging agent is one or more than two of anti-aging agent 4020, anti-aging agent RD and anti-aging agent NBC in any proportion; the plasticizer is one or more than two of dibutyl phthalate, epoxy octyl stearate and dioctyl adipate in any proportion; the active diluent is one or a mixture of any more of 3-ethyl-3-oxetanyl methanol, 3' - (oxybis methylene) bis (3-ethyl) oxetane, 1,2,8, 9-diepoxy-4-vinyl cyclohexene and vinyl ether; the particle size of the carbonyl iron powder is 2-5 mu m.
5. The preparation method of the shock-absorbing rubber is characterized by comprising the following steps of:
preparing liquid modified para-aramid:
1) preparing a solution: adding a monomer A and a monomer B into a reaction kettle, pumping an organic solvent, heating to 30-80 ℃ under the protection of nitrogen, stirring until the monomer A and the monomer B are dissolved, wherein the total molar concentration of the monomer A and the monomer B is 0.30-0.60 mol/L, and the molar ratio of the monomer A to the monomer B is 1.00-2.22: 1;
2) cooling the solution: cooling the solution prepared in the step 1) to-15-10 ℃ while stirring;
3) adding a monomer C: adding a monomer C with the molar quantity equal to the sum of the monomer A and the monomer B into the cooling solution in the step 2) under the stirring condition at the temperature of between 15 ℃ below zero and 10 ℃;
4) preparing liquid modified para-aramid: reacting for 30-45 min at-15-10 ℃ under stirring, and defoaming for 20-30 min at-0.15-0.098 MPa and 25 +/-5 ℃ to obtain liquid modified para-aramid;
the monomer A is one of p-phenylenediamine and o-chloro-p-phenylenediamine or two of p-phenylenediamine and o-chloro-p-phenylenediamine in any proportion;
the monomer B is one or two of 3,4 '-diaminodiphenyl ether and 4,4' -diaminodiphenyl ether in any proportion;
the monomer C is terephthaloyl chloride;
the organic solvent is one or two of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) in any proportion;
preparing damping rubber:
5) preparing damping rubber: the preparation method comprises the steps of firstly putting rubber, modified aramid fiber, alicyclic epoxy resin and active diluent into an internal mixer, plastifying for 8-20 min at the temperature of 70-110 ℃, then putting a photoinitiator, an accelerator, a plasticizer, an anti-aging agent, carbonyl iron powder and sulfur into the internal mixer, mixing for 8-15 min at the temperature of 120-140 ℃, cooling to room temperature, and discharging to obtain the shock-absorbing rubber.
6. The process for producing a vibration damper rubber according to claim 5, wherein the kneading in the step 5) is carried out under the action of a magnetic field of 100 to 1000 mT.
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