CN113583307A - High-viscoelasticity rubber shock absorbing piece and preparation method thereof - Google Patents
High-viscoelasticity rubber shock absorbing piece and preparation method thereof Download PDFInfo
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- CN113583307A CN113583307A CN202110953929.6A CN202110953929A CN113583307A CN 113583307 A CN113583307 A CN 113583307A CN 202110953929 A CN202110953929 A CN 202110953929A CN 113583307 A CN113583307 A CN 113583307A
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- vulcanizing
- cerium oxide
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 77
- 239000005060 rubber Substances 0.000 title claims abstract description 77
- 230000035939 shock Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 28
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 28
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- 239000004945 silicone rubber Substances 0.000 claims abstract description 23
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 20
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- 229920005556 chlorobutyl Polymers 0.000 claims abstract description 11
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 229920003049 isoprene rubber Polymers 0.000 claims abstract description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008117 stearic acid Substances 0.000 claims abstract description 11
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- 238000002156 mixing Methods 0.000 claims description 21
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- 239000002994 raw material Substances 0.000 claims description 15
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- 239000000203 mixture Substances 0.000 claims description 14
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- 238000000465 moulding Methods 0.000 claims description 10
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
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- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 5
- 239000011280 coal tar Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
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- 229940068124 pine tar Drugs 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical group CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 5
- 229960002447 thiram Drugs 0.000 claims description 5
- 238000009966 trimming Methods 0.000 claims description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 5
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- 239000004636 vulcanized rubber Substances 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 2
- STSDHUBQQWBRBH-UHFFFAOYSA-N n-cyclohexyl-1,3-benzothiazole-2-sulfonamide Chemical compound N=1C2=CC=CC=C2SC=1S(=O)(=O)NC1CCCCC1 STSDHUBQQWBRBH-UHFFFAOYSA-N 0.000 claims description 2
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- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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
- C08L7/00—Compositions of natural rubber
-
- 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
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to a high-viscoelasticity rubber shock absorbing part and a preparation method thereof, wherein the rubber comprises the following components in parts by weight: 30-50 parts of natural rubber, 20-40 parts of chlorinated butyl rubber, 10-15 parts of isoprene rubber, 10-20 parts of acrylate rubber, 5-10 parts of methyl vinyl silicone rubber, 1-2 parts of methyl silicone resin, 12-14 parts of softener, 5-8 parts of anti-aging agent, 10-20 parts of fumed silica, 5-15 parts of diphenylsilanediol, 0.2-0.6 part of nano cerium oxide, 0.3-1.2 parts of sodium carbonate, 0.8-1.6 parts of sulfur, 2-5 parts of vulcanizing agent, 1-1.8 parts of stearic acid, 8-12 parts of operating oil, 1.1-1.7 parts of accelerator, 6-14 parts of plasticizer and 0.5-1.2 parts of tin dioxide. The rubber has strong ageing resistance and corrosion resistance, the high temperature resistance and the low temperature resistance are obviously improved, good elasticity can be kept in high temperature and low temperature environments, and the service life of the rubber shock absorbing part is prolonged.
Description
Technical Field
The invention relates to the technical field of automobile parts, in particular to a high-viscoelasticity rubber shock absorption piece and a preparation method thereof.
Background
The rubber shock absorbing component has the characteristics of high elasticity and high viscosity. The elasticity of rubber is generated by the change of the coiled molecular conformation, and the rubber intermolecular interaction can obstruct the movement of molecular chains, thereby showing the characteristic of viscous damping, so that the stress and the strain are always in an unbalanced state.
In the prior art, the function of the rubber shock absorbing part is very important in the driving process of the existing automobile, however, the existing rubber shock absorbing part is easily corroded by temperature, oil, ozone, sunlight and chemical solvents, so that the performance is changed and aged, and after the existing rubber shock absorbing part is subjected to the action of long-time large load, the phenomenon of looseness is easily generated. The high temperature resistance and the low temperature resistance of the rubber shock absorber are relatively poor, the common rubber shock absorber usually uses natural rubber, the upper limit of the temperature is 70 ℃, and when the temperature is higher than the upper limit, the rubber loses elasticity due to aging; the lower temperature limit is 0 ℃ and below this limit the rubber loses its elasticity due to vitrification.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high-viscoelasticity rubber shock absorbing part and a preparation method thereof.
The above object of the present invention is achieved by the following technical solutions:
a high-viscoelasticity rubber shock absorbing part comprises the following components in parts by weight:
30-50 parts of natural rubber, 20-40 parts of chlorinated butyl rubber, 10-15 parts of isoprene rubber, 10-20 parts of acrylate rubber, 5-10 parts of methyl vinyl silicone rubber, 1-2 parts of methyl silicone resin, 12-14 parts of softener, 5-8 parts of anti-aging agent, 10-20 parts of fumed silica, 5-15 parts of diphenylsilanediol, 0.2-0.6 part of nano cerium oxide, 0.3-1.2 parts of sodium carbonate, 0.8-1.6 parts of sulfur, 2-5 parts of vulcanizing agent, 1-1.8 parts of stearic acid, 8-12 parts of operating oil, 1.1-1.7 parts of accelerator, 6-14 parts of plasticizer and 0.5-1.2 parts of tin dioxide.
The present invention in a preferred example may be further configured to: the anti-aging agent is one or a mixture of two of N-phenyl-alpha-aniline, N-N' -diphenyl-p-phenylenediamine and N-phenyl-alpha-aniline W.
The present invention in a preferred example may be further configured to: the accelerant is one or a mixture of two of N-cyclohexyl-2-benzothiazole sulfonamide, N- (oxydiethylene) -2-benzothiazole sulfonamide and 2, 2' -dithiodibenzothiazole.
The present invention in a preferred example may be further configured to: the softener is one or more than one of paraffin oil, petroleum resin, coal tar, coumarone resin, vegetable oil and pine tar.
The present invention in a preferred example may be further configured to: the vulcanizing agent is tetramethyl thiuram disulfide.
The present invention in a preferred example may be further configured to: the plasticizer is diethyl phthalate.
A preparation method of a high-viscoelasticity rubber shock absorbing piece comprises the following steps:
s1: preparing nano cerium oxide, dissolving cerium chloride in deionized water at 70-85 ℃ to form a yellow transparent cerium chloride aqueous solution, wherein the mass fraction of the cerium chloride is 0.25-0.3, and then mixing the cerium chloride and sodium carbonate according to a molar ratio of 1: (1.5-1.7) slowly pouring a sodium carbonate solution into a cerium chloride solution while stirring, and standing and aging for 40min to obtain a milky loose precipitate cerium hydroxide;
pouring the product into a suction filter funnel for suction filtration, washing the product for 9 times by using deionized water, finally washing the product for 2 times by using absolute ethyl alcohol, putting the washed paste into a drying oven with the temperature of 130-140 ℃ for drying for 2.5h, then calcining the dried paste for 4.5h at the temperature of 320 ℃ to obtain light yellow nano cerium oxide powder, and sealing and packaging the light yellow nano cerium oxide powder for later use;
s2: preparing synthetic rubber, namely preparing raw materials for each component of rubber of the shock absorbing part according to a proportion, wherein the raw materials comprise natural rubber, chlorinated butyl rubber, isoprene rubber, acrylate rubber, methyl vinyl silicone rubber, methyl silicone resin, a softening agent, an anti-aging agent, fumed silica, diphenyl silanediol, sodium carbonate, sulfur, stearic acid, operating oil, an accelerator, a plasticizer and tin dioxide;
sequentially putting the raw materials into an internal mixer, adding nano cerium oxide, synthesizing rubber by the internal mixer, uniformly mixing for one section, then carrying out heat treatment under the condition of 180 ℃ for 50min, finally adding a vulcanizing agent, uniformly mixing, thinly passing and then carrying out sheet discharging;
s4: molding and vulcanizing, namely performing open mixing molding on the prepared synthetic rubber at 70-80 ℃ through an open mill, putting the molded rubber into a mold in vulcanizing equipment, and vulcanizing the rubber for 10-15 min;
s5: and (4) secondary vulcanization, namely putting the vulcanized product obtained in the step S4 in an environment at 185 ℃ for secondary vulcanization for 40 min.
S6: and (4) finishing the finished product, namely trimming the secondarily vulcanized rubber to prepare a shock absorbing part, inspecting, packaging, and warehousing for storage.
The present invention in a preferred example may be further configured to: in step S4, the vulcanization process is: pressure of 195-215 Kgf/cm2The temperature is 170-180 ℃, and the vulcanizing time is 510-680 seconds.
In summary, the invention includes at least one of the following beneficial technical effects:
the shock absorbing part prepared by the high-viscoelasticity rubber formula has strong ageing resistance and corrosion resistance, the high temperature resistance and the low temperature resistance are obviously improved, good elasticity can be kept in high temperature and low temperature environments, and the service life of the rubber shock absorbing part is prolonged. Any measure that increases the mobility of the molecular chain and weakens the intermolecular interaction will lower the glass transition temperature, and any measure that decreases the crystallization ability and crystallization speed of the polymer will increase the elasticity of the polymer and improve the cold resistance. Wherein, diethyl phthalate is added to weaken intermolecular force, thereby improving the cold resistance of the rubber.
Wherein the main chain of the methyl vinyl silicone rubber molecule consists of silicon atoms and oxygen atoms alternately, and the bond energy of the silicon-oxygen bond is 370 kJ.mol-1Carbon-carbon bond energy 240 kJ. mol higher than that of general rubber-1Much larger and therefore thermally stable. Cerium oxide with particles reduced to a certain degree is added into the methyl vinyl silicone rubber as a heat-resistant additive, so that oxidative crosslinking of the side chain of the methyl vinyl silicone rubber can be prevented, and the thermal oxidation stability of the side group is improved.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The first embodiment is as follows:
the invention discloses a high-viscoelasticity rubber shock absorbing part which comprises the following components in parts by weight: 30 parts of natural rubber, 20 parts of chlorinated butyl rubber, 10 parts of isoprene rubber, 10 parts of acrylate rubber, 5 parts of methyl vinyl silicone rubber, 1 part of methyl silicone resin, 12 parts of softener, 5 parts of anti-aging agent, 10 parts of fumed silica, 5 parts of diphenyl silanediol, 0.2 part of nano cerium oxide, 0.3 part of sodium carbonate, 0.8 part of sulfur, 2 parts of vulcanizing agent, 1 part of stearic acid, 8 parts of operating oil, 1.1 part of accelerator, 6 parts of plasticizer and 0.5 part of tin dioxide.
The anti-aging agent is one or a mixture of two of N-phenyl-alpha-aniline, N-N '-diphenyl-p-phenylenediamine and N-phenyl-alpha-aniline W, the accelerator is one or a mixture of two of N-cyclohexyl-2-benzothiazole sulfenamide, N- (oxydiethylene) -2-benzothiazole sulfenamide and 2, 2' -dithiodibenzothiazyl, the softener is one or a mixture of more of paraffin oil, petroleum resin, coal tar, coumarone resin, vegetable oil and pine tar, the vulcanizing agent is tetramethyl thiuram disulfide, and the plasticizer is diethyl phthalate.
Referring to fig. 1, a method for preparing a highly viscoelastic rubber shock absorber includes the following steps:
s1: preparing nano cerium oxide, dissolving cerium chloride in deionized water at 70 ℃ to form a yellow transparent cerium chloride aqueous solution, wherein the mass fraction of the cerium chloride is 0.25, and then mixing the cerium chloride and sodium carbonate according to a molar ratio of 1: slowly pouring a sodium carbonate solution into a cerium chloride solution according to the proportion of 1.5, stirring while pouring, standing and aging for 40min to obtain a milky loose precipitate cerium hydroxide;
pouring the product into a suction filter funnel for suction filtration, washing the product for 9 times by using deionized water, finally washing the product for 2 times by using absolute ethyl alcohol, putting the washed paste into a drying oven at 130 ℃ for drying for 2.5h, then calcining the dried paste for 4.5h at 320 ℃ to obtain light yellow nano cerium oxide powder, and sealing and packaging the light yellow nano cerium oxide powder for later use;
s2: preparing synthetic rubber, namely preparing raw materials for each component of rubber of the shock absorbing part according to a proportion, wherein the raw materials comprise natural rubber, chlorinated butyl rubber, isoprene rubber, acrylate rubber, methyl vinyl silicone rubber, methyl silicone resin, a softening agent, an anti-aging agent, fumed silica, diphenyl silanediol, sodium carbonate, sulfur, stearic acid, operating oil, an accelerator, a plasticizer and tin dioxide;
sequentially putting the raw materials into an internal mixer, adding nano cerium oxide, synthesizing rubber by the internal mixer, uniformly mixing for one section, then carrying out heat treatment under the condition of 180 ℃ for 50min, finally adding a vulcanizing agent, uniformly mixing, thinly passing and then carrying out sheet discharging;
s4: molding and vulcanizing, namely performing open mixing molding on the prepared synthetic rubber at 70 ℃ through an open mill, putting the molded rubber into a mold in vulcanizing equipment, and vulcanizing the rubber for 10 min;
s5: and (4) secondary vulcanization, namely putting the vulcanized product obtained in the step S4 in an environment at 185 ℃ for secondary vulcanization for 40 min.
S6: and (4) finishing the finished product, namely trimming the secondarily vulcanized rubber to prepare a shock absorbing part, inspecting, packaging, and warehousing for storage.
In step S4, the vulcanization process is: pressure 195Kgf/cm2The temperature was 170 ℃ and the vulcanization time was 510 seconds.
Example two:
a high-viscoelasticity rubber shock absorbing part comprises the following components in parts by weight: 50 parts of natural rubber, 40 parts of chlorinated butyl rubber, 15 parts of isoprene rubber, 20 parts of acrylate rubber, 10 parts of methyl vinyl silicone rubber, 2 parts of methyl silicone resin, 14 parts of softener, 8 parts of anti-aging agent, 20 parts of fumed silica, 15 parts of diphenyl silanediol, 0.6 part of nano cerium oxide, 1.2 parts of sodium carbonate, 1.6 parts of sulfur, 5 parts of vulcanizing agent, 1.8 parts of stearic acid, 12 parts of operating oil, 1.7 parts of accelerator, 14 parts of plasticizer and 1.2 parts of tin dioxide.
The anti-aging agent is one or a mixture of two of N-phenyl-alpha-aniline, N-N '-diphenyl-p-phenylenediamine and N-phenyl-alpha-aniline W, the accelerator is one or a mixture of two of N-cyclohexyl-2-benzothiazole sulfenamide, N- (oxydiethylene) -2-benzothiazole sulfenamide and 2, 2' -dithiodibenzothiazyl, the softener is one or a mixture of more of paraffin oil, petroleum resin, coal tar, coumarone resin, vegetable oil and pine tar, the vulcanizing agent is tetramethyl thiuram disulfide, and the plasticizer is diethyl phthalate.
A preparation method of a high-viscoelasticity rubber shock absorbing piece comprises the following steps:
s1: preparing nano cerium oxide, dissolving cerium chloride in deionized water at 85 ℃ to form a yellow transparent cerium chloride aqueous solution, wherein the mass fraction of cerium chloride is 0.3, and then mixing the cerium chloride and sodium carbonate according to a molar ratio of 1: 1.7, slowly pouring a sodium carbonate solution into a cerium chloride solution while stirring, and standing and aging for 40min to obtain a milky loose precipitate cerium hydroxide;
pouring the product into a suction filter funnel for suction filtration, washing the product for 9 times by using deionized water, finally washing the product for 2 times by using absolute ethyl alcohol, putting the washed paste into a drying oven at 140 ℃ for drying for 2.5h, then calcining the dried paste for 4.5h at 320 ℃ to obtain light yellow nano cerium oxide powder, and sealing and packaging the light yellow nano cerium oxide powder for later use;
s2: preparing synthetic rubber, namely preparing raw materials for each component of rubber of the shock absorbing part according to a proportion, wherein the raw materials comprise natural rubber, chlorinated butyl rubber, isoprene rubber, acrylate rubber, methyl vinyl silicone rubber, methyl silicone resin, a softening agent, an anti-aging agent, fumed silica, diphenyl silanediol, sodium carbonate, sulfur, stearic acid, operating oil, an accelerator, a plasticizer and tin dioxide;
sequentially putting the raw materials into an internal mixer, adding nano cerium oxide, synthesizing rubber by the internal mixer, uniformly mixing for one section, then carrying out heat treatment under the condition of 180 ℃ for 50min, finally adding a vulcanizing agent, uniformly mixing, thinly passing and then carrying out sheet discharging;
s4: molding and vulcanizing, namely performing open mixing molding on the prepared synthetic rubber at 80 ℃ through an open mill, putting the molded rubber into a mold in vulcanizing equipment, and vulcanizing the rubber for 15 min;
s5: and (4) secondary vulcanization, namely putting the vulcanized product obtained in the step S4 in an environment at 185 ℃ for secondary vulcanization for 40 min.
S6: and (4) finishing the finished product, namely trimming the secondarily vulcanized rubber to prepare a shock absorbing part, inspecting, packaging, and warehousing for storage.
In step S4, the vulcanization process is: pressure 215Kgf/cm2The temperature was 180 ℃ and the vulcanization time was 680 seconds.
Example three:
a high-viscoelasticity rubber shock absorbing part comprises the following components in parts by weight: 40 parts of natural rubber, 30 parts of chlorinated butyl rubber, 12.5 parts of isoprene rubber, 15 parts of acrylate rubber, 7 parts of methyl vinyl silicone rubber, 1.5 parts of methyl silicone resin, 13 parts of softener, 7 parts of anti-aging agent, 15 parts of fumed silica, 10 parts of diphenyl silanediol, 0.4 part of nano cerium oxide, 0.75 part of sodium carbonate, 1.2 parts of sulfur, 3 parts of vulcanizing agent, 1.4 parts of stearic acid, 10 parts of operating oil, 1.4 parts of accelerator, 10 parts of plasticizer and 0.8 part of tin dioxide.
The anti-aging agent is one or a mixture of two of N-phenyl-alpha-aniline, N-N '-diphenyl-p-phenylenediamine and N-phenyl-alpha-aniline W, the accelerator is one or a mixture of two of N-cyclohexyl-2-benzothiazole sulfenamide, N- (oxydiethylene) -2-benzothiazole sulfenamide and 2, 2' -dithiodibenzothiazyl, the softener is one or a mixture of more of paraffin oil, petroleum resin, coal tar, coumarone resin, vegetable oil and pine tar, the vulcanizing agent is tetramethyl thiuram disulfide, and the plasticizer is diethyl phthalate.
A preparation method of a high-viscoelasticity rubber shock absorbing piece comprises the following steps:
s1: preparing nano cerium oxide, namely dissolving cerium chloride in deionized water at 77 ℃ to form a yellow transparent cerium chloride aqueous solution, wherein the mass fraction of the cerium chloride is 0.275, and then mixing the cerium chloride and sodium carbonate according to a molar ratio of 1: slowly pouring a sodium carbonate solution into a cerium chloride solution according to the proportion of 1.6, stirring while pouring, standing and aging for 40min to obtain a milky loose precipitate cerium hydroxide;
pouring the product into a suction filter funnel for suction filtration, washing the product for 9 times by using deionized water, finally washing the product for 2 times by using absolute ethyl alcohol, putting the washed paste into a 135 ℃ oven for drying for 2.5h, then calcining the dried paste for 4.5h at 320 ℃ to obtain light yellow nano cerium oxide powder, and sealing and packaging the light yellow nano cerium oxide powder for later use;
s2: preparing synthetic rubber, namely preparing raw materials for each component of rubber of the shock absorbing part according to a proportion, wherein the raw materials comprise natural rubber, chlorinated butyl rubber, isoprene rubber, acrylate rubber, methyl vinyl silicone rubber, methyl silicone resin, a softening agent, an anti-aging agent, fumed silica, diphenyl silanediol, sodium carbonate, sulfur, stearic acid, operating oil, an accelerator, a plasticizer and tin dioxide;
sequentially putting the raw materials into an internal mixer, adding nano cerium oxide, synthesizing rubber by the internal mixer, uniformly mixing for one section, then carrying out heat treatment under the condition of 180 ℃ for 50min, finally adding a vulcanizing agent, uniformly mixing, thinly passing and then carrying out sheet discharging;
s4: molding and vulcanizing, namely performing open mixing molding on the prepared synthetic rubber at 75 ℃ through an open mill, putting the molded rubber into a mold in vulcanizing equipment, and vulcanizing the rubber for 13 min;
s5: and (4) secondary vulcanization, namely putting the vulcanized product obtained in the step S4 in an environment at 185 ℃ for secondary vulcanization for 40 min.
S6: and (4) finishing the finished product, namely trimming the secondarily vulcanized rubber to prepare a shock absorbing part, inspecting, packaging, and warehousing for storage.
In step S4, the vulcanization process is: pressure 205Kgf/cm2The temperature was 175 ℃ and the vulcanization time was 600 seconds.
TABLE 1
| Kind of rubber | Heat resistance limit temperature of | Heat-resistant safety temperature DEG C | Cold resistance limit temperature DEG C |
| Natural rubber | 70 | 50 | 0 |
| Example one | 260 | 230 | -60 |
| Example two | 255 | 215 | -55 |
| EXAMPLE III | 290 | 260 | -75 |
Referring to the table 1, the heat resistance and the cold resistance of the natural rubber, the synthetic rubber of the first embodiment, the synthetic rubber of the second embodiment, and the synthetic rubber of the third embodiment are respectively tested to obtain the test results, and the test results show that the heat resistance and the cold resistance of the synthetic rubber prepared under the three conditions of the embodiment are greatly improved compared with the common natural rubber, so that the use requirements of the rubber shock absorbing part under different environments are met, and the service life of the rubber is prolonged.
The implementation principle of the embodiment is as follows: the shock absorbing part prepared by the high-viscoelasticity rubber formula has strong ageing resistance and corrosion resistance, the high temperature resistance and the low temperature resistance are obviously improved, good elasticity can be kept in high temperature and low temperature environments, and the service life of the rubber shock absorbing part is prolonged. Any measure that increases the mobility of the molecular chain and weakens the intermolecular interaction will lower the glass transition temperature, and any measure that decreases the crystallization ability and crystallization speed of the polymer will increase the elasticity of the polymer and improve the cold resistance. Wherein, diethyl phthalate is added to weaken intermolecular force, thereby improving the cold resistance of the rubber.
Wherein the main chain of the methyl vinyl silicone rubber molecule consists of silicon atoms and oxygen atoms alternately, and the bond energy of the silicon-oxygen bond is 370 kJ.mol-1Carbon-carbon bond energy 240 kJ. mol higher than that of general rubber-1Much larger and therefore thermally stable. The nano cerium oxide with particles being small to a certain degree is added into the methyl vinyl silicone rubber as a heat-resistant additive, so that the oxidative crosslinking of the side chain of the methyl vinyl silicone rubber can be prevented, and the thermal oxidation stability of the side group is improved.
The methyl silicone resin has a structure similar to that of methyl vinyl silicone rubber, and is also a polymer with an Si-0 bond as a main chain, and the methyl silicone resin has a methyl group and a phenyl group as a side group, so that the methyl silicone resin has better compatibility with the methyl vinyl silicone rubber. And adding a small amount of methyl silicone resin, and uniformly dispersing the methyl silicone resin in the rubber compound of the methyl vinyl silicone rubber under the mixing action. During vulcanization, the rubber and the surface of the resin are bonded by rare chemical bonds and intermolecular hydrogen bonds, and thus, have a certain reinforcing effect. However, since the inorganic filler has less adhesion to rigid polymers (thermosetting plastics) than to elastic rubbers and the vulcanizate always follows these weak points, the amount of silicone resin added is not too large, which would otherwise reduce the mechanical properties of the silicone rubber, preferably 1 to 2 parts.
The methyl vinyl silicone rubber degradation process mainly comprises oxidation and thermal degradation, wherein methyl oxidation and crosslinking reaction are carried out at 170 ℃, the reaction activation energy is 126kJ/mol, the breakage degradation of Si-0 bonds is mainly carried out at 175-180 ℃, and the reaction activation energy is 184 kJ/mol. The methyl silicone resin weakens the possibility that the main chain is easy to generate the trip type degradation reaction to a certain extent, and the addition of the methyl silicone resin destroys the spiral structure of the methyl vinyl silicone rubber, so that the probability of the trip type main chain degradation reaction which is easy to generate under the conditions of high temperature, water, silicon hydroxyl or residual catalyst is reduced, and the heat resistance is improved.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (8)
1. A high viscoelasticity rubber shock absorber is characterized in that: the composition comprises the following components in parts by weight:
30-50 parts of natural rubber, 20-40 parts of chlorinated butyl rubber, 10-15 parts of isoprene rubber, 10-20 parts of acrylate rubber, 5-10 parts of methyl vinyl silicone rubber, 1-2 parts of methyl silicone resin, 12-14 parts of softener, 5-8 parts of anti-aging agent, 10-20 parts of fumed silica, 5-15 parts of diphenylsilanediol, 0.2-0.6 part of nano cerium oxide, 0.3-1.2 parts of sodium carbonate, 0.8-1.6 parts of sulfur, 2-5 parts of vulcanizing agent, 1-1.8 parts of stearic acid, 8-12 parts of operating oil, 1.1-1.7 parts of accelerator, 6-14 parts of plasticizer and 0.5-1.2 parts of tin dioxide.
2. A highly viscoelastic rubber suspension as set forth in claim 1, wherein: the anti-aging agent is one or a mixture of two of N-phenyl-alpha-aniline, N-N' -diphenyl-p-phenylenediamine and N-phenyl-alpha-aniline W.
3. A highly viscoelastic rubber suspension as set forth in claim 1, wherein: the accelerant is one or a mixture of two of N-cyclohexyl-2-benzothiazole sulfonamide, N- (oxydiethylene) -2-benzothiazole sulfonamide and 2, 2' -dithiodibenzothiazole.
4. A highly viscoelastic rubber suspension as set forth in claim 1, wherein: the softener is one or more than one of paraffin oil, petroleum resin, coal tar, coumarone resin, vegetable oil and pine tar.
5. A highly viscoelastic rubber suspension as set forth in claim 1, wherein: the vulcanizing agent is tetramethyl thiuram disulfide.
6. A highly viscoelastic rubber suspension as set forth in claim 1, wherein: the plasticizer is diethyl phthalate.
7. A preparation method of a high-viscoelasticity rubber shock absorbing part is characterized by comprising the following steps: the method comprises the following steps:
s1: preparing nano cerium oxide, dissolving cerium chloride in deionized water at 70-85 ℃ to form a yellow transparent cerium chloride aqueous solution, wherein the mass fraction of the cerium chloride is 0.25-0.3, and then mixing the cerium chloride and sodium carbonate according to a molar ratio of 1: (1.5-1.7) slowly pouring a sodium carbonate solution into a cerium chloride solution while stirring, and standing and aging for 40min to obtain a milky loose precipitate cerium hydroxide;
pouring the product into a suction filter funnel for suction filtration, washing the product for 9 times by using deionized water, finally washing the product for 2 times by using absolute ethyl alcohol, putting the washed paste into a drying oven with the temperature of 130-140 ℃ for drying for 2.5h, then calcining the dried paste for 4.5h at the temperature of 320 ℃ to obtain light yellow nano cerium oxide powder, and sealing and packaging the light yellow nano cerium oxide powder for later use;
s2: preparing synthetic rubber, namely preparing raw materials for each component of rubber of the shock absorbing part according to a proportion, wherein the raw materials comprise natural rubber, chlorinated butyl rubber, isoprene rubber, acrylate rubber, methyl vinyl silicone rubber, methyl silicone resin, a softening agent, an anti-aging agent, fumed silica, diphenyl silanediol, sodium carbonate, sulfur, stearic acid, operating oil, an accelerator, a plasticizer and tin dioxide;
sequentially putting the raw materials into an internal mixer, adding nano cerium oxide, synthesizing rubber by the internal mixer, uniformly mixing for one section, then carrying out heat treatment under the condition of 180 ℃ for 50min, finally adding a vulcanizing agent, uniformly mixing, thinly passing and then carrying out sheet discharging;
s4: molding and vulcanizing, namely performing open mixing molding on the prepared synthetic rubber at 70-80 ℃ through an open mill, putting the molded rubber into a mold in vulcanizing equipment, and vulcanizing the rubber for 10-15 min;
s5: and (4) secondary vulcanization, namely putting the vulcanized product obtained in the step S4 in an environment at 185 ℃ for secondary vulcanization for 40 min.
S6: and (4) finishing the finished product, namely trimming the secondarily vulcanized rubber to prepare a shock absorbing part, inspecting, packaging, and warehousing for storage.
8. A highly viscoelastic rubber suspension as set forth in claim 7, wherein: in step S4, the vulcanization process is: pressure of 195-215 Kgf/cm2The temperature is 170-180 ℃, and the vulcanizing time is 510-680 seconds.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114479632A (en) * | 2021-12-30 | 2022-05-13 | 江苏朗科建材科技有限公司 | Solvent-free polyurethane spraying process for steel pipe surface |
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