CN101580605B - Composition of yielding rubber, preparation method thereof, yielding rubber and rubber part - Google Patents
Composition of yielding rubber, preparation method thereof, yielding rubber and rubber part Download PDFInfo
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- CN101580605B CN101580605B CN2008100818626A CN200810081862A CN101580605B CN 101580605 B CN101580605 B CN 101580605B CN 2008100818626 A CN2008100818626 A CN 2008100818626A CN 200810081862 A CN200810081862 A CN 200810081862A CN 101580605 B CN101580605 B CN 101580605B
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a composition of yielding rubber, a preparation method thereof, the yielding rubber and a rubber part, wherein the composition of the yielding rubber comprises native rubber, an unsaturated carboxylic acid, an activating agent, a strengthening agent, an accelerating agent and a vulcanizing agent. The composition for the yielding rubber greatly enhances the bonding strengthof rubber and metal, and the yielding rubber made from the composition has both favorable fatigue resistance and high mechanical strength.
Description
Technical field
The invention relates to a kind of composition and method of making the same of yielding rubber and yielding rubber and yielding rubber spare that obtains by said composition of being used for.
Background technology
In recent years, along with automobile enters average family, people the comfortableness of vehicle is also had higher requirement, so the effect of cushioning material are more and more important enjoying conveniently simultaneously.Rubber item is used as automobile-used cushioning material widely as a kind of resilient material, the combined shock absorption product of rubber and metal is widely used in the automobile suspension system, and riding comfort, stability and the tack that guarantees automobile had great important.Automobile travels under different road conditions, and damper element is bearing the power of tearing and twisting resistance in various degree for a long time, often because the bonding failure of metal and rubber, and causes the damage of shock absorber part.
CN1876703A discloses a kind of rubber combination of making sheet rubber in the damping and energy-consumption device that is specifically designed to, and said composition contains the 15-25 parts by weight of natural rubber, the paracril of 65-85 weight part, 0.9-1.5 the sulphur of weight part, 0.2-0.5 the vulkacit D of weight part, 1.2-1.6 the vulcanizing agent DM of weight part, 3.8-4.2 the zinc oxide of weight part, 1.4-1.6 the stearic acid of weight part, the high abrasion carbon black of 30-50 weight part, the dibutylester of 5-8 weight part, the resol of 3-6 weight part, 1.1-1.3 the anti-aging agent 1010N.A of weight part and the antioxidant D of 1.1-1.3 weight part.The bond strength that has rubber and metal of this rubber combination is low, makes this rubber combination can't satisfy the requirement of vehicle damping aspect.
Summary of the invention
First purpose of the present invention is in order to overcome the low problem of bond strength that existing yielding rubber exists rubber and metal, a kind of yielding rubber composition is provided, the yielding rubber that makes by said composition and the bond strength height of metal, and have good fatigue performance and physical strength, as tensile strength and tension set, make prolong the work-ing life of the yielding rubber spare that makes by said composition.
Second purpose of the present invention provides the described preparation of compositions method that is used for yielding rubber.
The 3rd purpose of the present invention provides a kind of yielding rubber.
The 4th purpose of the present invention provides a kind of yielding rubber spare.
The invention provides a kind of composition that is used for yielding rubber, wherein, said composition contains natural rubber, unsaturated carboxylic acid, promoting agent, strengthening agent, promotor and vulcanizing agent.
The present invention also provides the described preparation of compositions method that is used for yielding rubber, and wherein, this method comprises mixes natural rubber, unsaturated carboxylic acid, promoting agent, strengthening agent, promotor and vulcanizing agent.
The present invention also provides a kind of yielding rubber, and wherein, this yielding rubber is to make by the composition that is used for yielding rubber of the present invention is vulcanized.
The present invention also provides a kind of yielding rubber spare, and this yielding rubber spare comprises yielding rubber spare matrix, bonding coat and material layer, and attached on the yielding rubber matrix, wherein, described material layer is a yielding rubber of the present invention to described material layer by bonding coat.
The composition that is used for yielding rubber provided by the invention has greatly improved the cohesive strength of rubber and metal, and the yielding rubber that is made by said composition has good fatigue performance and physical strength.
Embodiment
The composition that is used for yielding rubber provided by the invention contains natural rubber, unsaturated carboxylic acid, promoting agent, strengthening agent, promotor and vulcanizing agent.
According to the present invention, the selectable range of described unsaturated carboxylic acid is wider, and under the preferable case, described unsaturated carboxylic acid can be selected from one or more in methacrylic acid, vinylformic acid and the undecylenic acid.
Natural rubber is to use the natural gum of gathering from rubber tree, through filtering, solidifying and make.The main component of natural rubber is a polyisoprene, and the present invention is not particularly limited described natural rubber, can be for well known to a person skilled in the art various natural rubbers.Natural rubber can be divided into standard glue, rubber smoked sheet, concentrated glue, white crepe, skim rubber and air-dried rubber sheet etc., and the most frequently used is standard glue and rubber smoked sheet.Standard glue belongs to latex, and glue juice solidifies after processing makes particulate state, domestic standard (SCR) one-level, secondary, three grades, level Four are equivalent to the world market No. 5, No. 10, No. 20, No. 50 standard glue.Natural gum after the collection through filtering, adds formic acid and solidifies laminarly, will make rubber smoked sheet after its smoke dry(ing), i.e. RSS (Ribbed Smoked Sheet), and its standard class is divided into RSS No. one to No. five.According to national GB8081-87 standard, standard glue is divided into 4 grades, comprises SCR5 (primary standard glue), SCR10 (secondary standard glue), SCR20 (grade III Standard glue) and SCR50 (level Four standard glue).According to national GB8089-87 standard, rubber smoked sheet is divided into 5 grades, comprises RSSI, RSS2, RSS3, RSS4 and RSS5.The natural rubber that uses in the specific embodiment of the invention preferably includes No. 1 smoked sheet of No. 3 smoked sheets of Thailand and Indonesia.Generally, the weight-average molecular weight of described natural rubber is between 60,000 to 4,000,000, and the dispersion index of described molecular weight is 3-7.Described molecular weight distributing index is meant the ratio of weight-average molecular weight and number-average molecular weight.That is, be used for characterizing the width or the polymolecularity of molecular weight distribution.The molecular weight distribution of natural rubber is a bimodal distribution, promptly, comprise low molecular weight part and high molecular part, the high molecular part of natural rubber can provide excellent mechanical property, low molecular weight part can provide good processibility, therefore, the bimodal distribution of natural rubber has guaranteed the processibility of natural rubber and the good combination of mechanical property.
According to the present invention, in the described composition, the content of promoting agent, strengthening agent and promotor can in very large range change, under the preferable case, with respect to 100 parts by weight of natural rubber, the content of described unsaturated carboxylic acid is the 1-15 weight part, the content of described promoting agent is the 1-10 weight part, the content of described strengthening agent is the 20-80 weight part, and the content of described promotor is the 1-5 weight part, and the content of described vulcanizing agent is the 0.1-5 weight part; More preferably, with respect to 100 parts by weight of natural rubber, the content of described unsaturated carboxylic acid is the 5-15 weight part, the content of described promoting agent is the 5-10 weight part, the content of described strengthening agent is the 40-60 weight part, the content of described promotor is the 2-4 weight part, and the content of described vulcanizing agent is the 0.5-3 weight part.
Among the present invention, described promoting agent can be the promoting agent that is used for rubber combination of various routines, it can play the effect of activation promotor, for example, Zinic stearas, described Zinic stearas can be commercially available, and also can prepare according to the method for well known to a person skilled in the art, for example, can obtain Zinic stearas by adopting the reaction of zinc oxide and stearic acid.
Described strengthening agent can be the strengthening agent that is used for rubber combination of various routines, for example can be in carbon black, potter's clay, lime carbonate and the sal epsom one or more, described carbon black can be the various carbon blacks that are used for rubber combination, for example can be among carbon black N539, carbon black N774, carbon black N550 and the carbon black N330 one or more; Described potter's clay can be nanometer potter's clay, and for example, the average particle diameter of described nanometer potter's clay can be the 200-700 nanometer, is preferably the 300-500 nanometer.
According to the present invention, described promotor can be the promotor that is used for rubber combination of various routines, for example can be in thiazole promotor, sulphenamide promotor and the thiuram accelerator one or more.
Described thiazole promotor can be dibenzothiazyl disulfide, 2-benzothiazolyl mercaptan, zinc 2-mercaptobenzothiazole salt, 2 (4-morpholinodithio) benzothiazole and N, one or more in N-diethyl-dithio oxygen base benzothiazole.
Described sulphenamide promotor can be N cyclohexyl 2 benzothiazole sulfenamide, N tert butyl benzothiazole 2 sulfenamide, N-oxygen diethylene base-2-[4-morpholinodithio sulphenamide, N, one or more in N-dicyclohexyl-2-[4-morpholinodithio sulphenamide and N-oxygen diethylidene thiocarbamyl-N '-oxygen diethylidene sulphenamide.
Described thiuram accelerator can be in tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, disulfide diisobutyl thiuram, tetra-benzyl thiram disulfide, bis-pentamethylenethiuram tetrasulfide and the tetrabutylthiuram disulfide one or more.
Among the present invention; described vulcanizing agent can be the vulcanizing agent that is used for rubber combination of various routines; comprise morphine quinoline vulcanizing agent and/or sulphur; described morphine quinoline vulcanizing agent is dithiodimorpholine and/or four sulfurations, two morphine quinolines; the morphine quinoline vulcanizing agent that meets above-mentioned condition can be by arriving of being purchased; for example, the DTDM of Huangyan East Sea chemical industry company limited production.
According to the present invention, can also contain tenderizer and/or anti-aging agent in the described composition.
Described tenderizer can be the tenderizer that is used for rubber combination of various routines, for example can be paraffin oil and/or naphthenic oil; Described paraffin oil is the mixture from the resulting colorless and odorless of crude oil fractionation, its main component is straight chain or branched paraffin, described paraffin oil can be commercially available, for example paraffin oil KP300, the paraffin oil KP500, the paraffin oil KP600 that produce of No. 300 paraffin oils producing of Shanghai lubricating oil plant and Hebei Ke Yuan lubricant company limited.
Described naphthenic oil is to be the mixture of main component with naphthenic hydrocarbon, described naphthenic oil can be commercially available, for example the naphthenic oil of the naphthenic oil of the naphthenic oil of Dalian oil seven factories production, the production of Xiamen pterosaur petrochemical industry company limited and the production of Hebei Ke Yuan lubricant company limited.
With respect to 100 parts by weight of natural rubber, the content of described tenderizer is greater than 0 to 20 weight part, is preferably the 3-10 weight part.
Described anti-aging agent can be the anti-aging agent that is used for rubber combination of various routines, for example, can be in Ursol D anti-aging agent, quinoline anti-aging agent and the Wax-for preventing rubber one or more.
Described Ursol D anti-aging agent can be N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine, N, N '-two (1,4-dimethyl amyl group) one or more in Ursol D, N-cyclohexyl-N '-diphenyl-para-phenylene diamine and N-sec.-propyl-N '-diphenyl-para-phenylene diamine, be preferably N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine; Described quinoline anti-aging agent is selected from 2,2,4-trimethylammonium-1,2-dihyaroquinoline, 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline and 6-phenyl-2,2,4-trimethylammonium-1, one or more in the 2-dihyaroquinoline.
The rubber physical antioxidant that described Wax-for preventing rubber is made up of paraffin and little smart wax, described Wax-for preventing rubber can be commercially available, for example, the 58# SEMI-REFINED PARAFFIN WAX that Science and Technology Ltd. produces is contained in the RPW-2 and the Jinchang, Guangzhou of the production of the rich chemical industry company limited of Guangzhou wound.
With respect to 100 weight part natural rubbers, the content of described anti-aging agent is greater than 0 to 8 weight part, is preferably the 2-4 weight part.
According to method of the present invention, described blended condition comprises that mixing temperature is 40-80 ℃, and mixing time is 2-30 minute, and under the preferable case, described mixing temperature is 50-70 ℃, and mixing time is 5-20 minute.
The present invention also provides the described preparation of compositions method that is used for yielding rubber, and wherein, this method comprises mixes natural rubber, unsaturated carboxylic acid, promoting agent, strengthening agent, promotor and vulcanizing agent.Described mixing with natural rubber, unsaturated carboxylic acid, promoting agent, strengthening agent, promotor and vulcanizing agent can be carried out also simultaneously can proceed step by step, under the preferable case, earlier with natural rubber, promoting agent, strengthening agent, tenderizer and unsaturated carboxylic acid mixing 5-15 minute, place after 15-40 minute, again with promotor and vulcanizing agent mixing 1-5 minute.
When adopting preferable methods to prepare said composition, be not included in the described mixing time described storage period.
If also contain tenderizer and/or anti-aging agent in the described composition, method provided by the invention also is included in and obtains yielding rubber with before the composition, in the mixture that contains natural rubber, promoting agent, strengthening agent, unsaturated carboxylic acid, promotor and vulcanizing agent that obtains, add tenderizer and/or anti-aging agent, and the step that mixes.Described tenderizer and/or anti-aging agent can add simultaneously also and can add step by step, and the order of adding does not have remarkable influence to the performance of composition.
The kind of above-mentioned various raw materials and consumption have been done detailed description hereinbefore, do not repeat them here.
The present invention also provides a kind of yielding rubber, and wherein, this yielding rubber is to make by the composition that is used for yielding rubber of the present invention is vulcanized.Described sulfurized method is conventionally known to one of skill in the art, and for example, described sulfurized method comprises heating composition of the present invention, and the condition of heating comprises that the temperature of heating is 150-180 ℃, and the time of heating is 10-30 minute.Specifically can adopt the method for compression molding.
The present invention also provides a kind of yielding rubber spare, and this yielding rubber spare comprises yielding rubber spare matrix, bonding coat and material layer, and attached on the yielding rubber matrix, wherein, described material layer is a yielding rubber of the present invention to described material layer by bonding coat.Concrete preparation method can form bonding coat for elder generation's adhesive coating on the yielding rubber matrix, places after 5-10 minute, yielding rubber spare matrix is put into mould locate, and puts into the composition that is used for yielding rubber of the present invention, and sulfidization molding.
Those skilled in the art can select suitable yielding rubber spare matrix as required, and described yielding rubber spare matrix is generally metallic matrix, for example can be the charcoal steel; The kind of described tackiness agent is conventionally known to one of skill in the art, for example, can be selected from 205 tackiness agent (company limited is learned in Dehua, Lip river, Shanghai) and/or 220 tackiness agent (company limited is learned in Dehua, Lip river, Shanghai).
Under the preferable case, before forming bonding coat on the metallic matrix, comprise also metallic matrix carried out the surface-treated step that described surface-treated method is conventionally known to one of skill in the art, for example, can adopt methods such as sandblast, bonderizing.
Below by embodiment the present invention is described in more detail.
Embodiment 1
Present embodiment is used to illustrate the preparation of compositions that is used for yielding rubber provided by the invention
With 100 parts by weight of natural rubber (No. 3 smoked sheets of Thailand); the carbon black N774 of 20 weight parts (Shanghai Cabot); the carbon black N550 of 20 weight parts (Shanghai Cabot); 8 weight part naphthenic oils (Maoming City wide bright specialty oil products factory); the stearic acid of 1 weight part (the polite chemical industry in Hong Kong company limited; SA1801); the zinc oxide of 5 weight parts (Liuzhou zinc product company limited); 10 weight part methacrylic acids (chemical pure) (Tianjin City Chemical Agent Research Institute); 1.5 parts by weight of rubber protection wax 58# SEMI-REFINED PARAFFIN WAX (paraffin series saturated alkane) (Science and Technology Ltd. is contained in the Jinchang, Guangzhou); 1 weight part antioxidant BLE-W (acetone and pentanoic pyrocondensation thing) (rubber helps chemical industry company limited in Huangyan East Zhejiang province); (N-(1 for 2 weight part anti-aging agent 4020; the 3-dimethylbutyl)-the N-diphenyl-para-phenylene diamine) (rubber helps chemical industry company limited in Huangyan East Zhejiang province); 0.5 weight part altax (dibenzothiazyl disulfide) (East Sea, Zhejiang Huangyan factory); 1.2 weight part accelerant CZ (N cyclohexyl 2 benzothiazole sulfenamide) (auxiliary reagent factory, northeast, Shenyang); 0.5 weight part vulcanizing agent DTDM (4; the 4-dithiodimorpholine) (Shanghai Jing Hai chemical industry company limited) and 1.5 weight part vulcanizing agent S-80 (sulphur predispersion) (Science and Technology Ltd. is contained in the Jinchang, Guangzhou) join in 0.5 liter of Banbury mixer; under 55 ℃ of conditions, mixed 15 minutes, obtain being used for the composition A1 of yielding rubber.
Comparative Examples 1
The explanation of this Comparative Examples is used for the preparation of the reference composition of yielding rubber
Be used for the composition of yielding rubber according to the preparation of the method for embodiment 1, different is, does not contain methacrylic acid in the described composition, obtains being used for the reference composition AC1 of yielding rubber.
Embodiment 2
Present embodiment is used to illustrate the preparation of compositions that is used for yielding rubber provided by the invention
With 100 parts by weight of natural rubber (No. 1 smoked sheet of Indonesia); the carbon black N774 of 40 weight parts (Shanghai Cabot); the carbon black N550 of 20 weight parts (Shanghai Cabot); 15 weight part lime carbonate; 5 weight part naphthenic oils (Maoming City wide bright specialty oil products factory); 5 weight part paraffin oil KP300 (Hebei Ke Yuan lubricant company limited product); 5 weight part Zinic stearass (hundred million trade Co., Ltds are opened up in Guangzhou); 15 weight part methacrylic acids (chemical pure) (Tianjin City Chemical Agent Research Institute); 1.5 parts by weight of rubber protection wax 58# SEMI-REFINED PARAFFIN WAX (Science and Technology Ltd. is contained in the Jinchang, Guangzhou); 1 weight part antioxidant BLE-W (rubber helps chemical industry company limited in Huangyan East Zhejiang province); 2 weight part anti-aging agent 4020 (rubber helps chemical industry company limited in Huangyan East Zhejiang province); 2 weight part altaxs (East Sea, Zhejiang Huangyan factory); 2 weight part accelerant CZs (auxiliary reagent factory, northeast, Shenyang); 1.5 weight part vulcanizing agent DTDM (Shanghai Jing Hai chemical industry company limited) and 1.5 weight part vulcanizing agent S-80 (Science and Technology Ltd. is contained in the Jinchang, Guangzhou) join in 0.5 liter of Banbury mixer; under 65 ℃ of conditions, mixed 6 minutes, obtain being used for the composition A2 of yielding rubber.
Embodiment 3
Present embodiment is used to illustrate the preparation of compositions that is used for yielding rubber provided by the invention
With 100 parts by weight of natural rubber (No. 3 smoked sheets of Thailand); the carbon black N774 of 20 weight parts (Shanghai Cabot); 5 weight part Zinic stearass (hundred million trade Co., Ltds are opened up in Guangzhou); 6 weight part methacrylic acids (chemical pure) (Tianjin City Chemical Agent Research Institute); 1.5 parts by weight of rubber protection wax 58# SEMI-REFINED PARAFFIN WAX (Science and Technology Ltd. is contained in the Jinchang, Guangzhou); 1 weight part antioxidant BLE-W (rubber helps chemical industry company limited in Huangyan East Zhejiang province); 2 weight part anti-aging agent 4020 (rubber helps chemical industry company limited in Huangyan East Zhejiang province); 1.5 weight part altax (East Sea, Zhejiang Huangyan factory); 1.5 weight part accelerant CZ (auxiliary reagent factory, northeast, Shenyang); 1 weight part vulcanizing agent DTDM (Shanghai Jing Hai chemical industry company limited) joins in 0.5 liter of Banbury mixer; under 55 ℃ of conditions, mixed 10 minutes, obtain being used for the composition A3 of yielding rubber.
Embodiment 4
Present embodiment is used to illustrate the preparation of compositions that is used for yielding rubber provided by the invention
With 100 parts by weight of natural rubber (No. 3 smoked sheets of Thailand); the carbon black N774 of 20 weight parts (Shanghai Cabot); the carbon black N550 of 20 weight parts (Shanghai Cabot); 8 weight part Zinic stearass (hundred million trade Co., Ltds are opened up in Guangzhou); 10 weight part methacrylic acids (chemical pure) (Tianjin City Chemical Agent Research Institute); 0.5 weight part altax (East Sea, Zhejiang Huangyan factory); 1.2 weight part accelerant CZ (auxiliary reagent factory, northeast, Shenyang); 0.5 weight part vulcanizing agent DTDM (Shanghai Jing Hai chemical industry company limited) and 1.5 weight part vulcanizing agent S-80 (Science and Technology Ltd. is contained in the Jinchang, Guangzhou) join in 0.5 liter of Banbury mixer; under 55 ℃ of conditions, mixed 10 minutes, obtain being used for the composition A4 of yielding rubber.
Embodiment 5
Present embodiment is used to illustrate the preparation of compositions that is used for yielding rubber provided by the invention
Be used for the composition of yielding rubber according to the preparation of the method for embodiment 1, different is, replaces methacrylic acid with vinylformic acid, obtains being used for the reference composition A5 of yielding rubber.
Embodiment 6
Present embodiment is used to illustrate the preparation of compositions that is used for yielding rubber provided by the invention
Be used for the composition of yielding rubber according to the preparation of the method for embodiment 1, different is, replaces methacrylic acid with undecylenic acid, obtains being used for the reference composition A6 of yielding rubber.
Embodiment 7
Present embodiment is used to illustrate the preparation of yielding rubber provided by the invention
Under 160 ℃ of conditions, the composition A1 that is used for yielding rubber that embodiment 1 is obtained puts into 50T vulcanizing press (Chengdu Hangfa Hydraulic Construction Co., Ltd.) and carries out compression molding, and curing time is 12 minutes, obtains thickness and be 2 millimeters yielding rubber B1.
Comparative Examples 2
This Comparative Examples is used to illustrate the preparation of reference yielding rubber
According to embodiment 7 described methods the reference composition AC1 that is used for yielding rubber that Comparative Examples 1 obtains is carried out compression molding, obtain thickness and be 2 millimeters yielding rubber BC1.
Embodiment 8-12
Present embodiment is used to illustrate the preparation of yielding rubber provided by the invention
According to embodiment 7 described methods, the composition A2-A6 that is used for yielding rubber that embodiment 2-6 is obtained carries out compression molding, and different is, curing temperature is 150 ℃, and curing time is 25 minutes, obtains thickness and be 2 millimeters yielding rubber B2-B6.
Embodiment 13-18
Present embodiment is used to illustrate the performance test of yielding rubber
The yielding rubber that embodiment 7-12 is obtained carries out bond strength detection, low-temperature performance detection and the thermal aging property detection of fatigue performance detection, hardness detection, tensile property detection, rubber and metal in accordance with the following methods:
Fatigue performance detects
According to GB 9870-88 standard, static load is 500 newton, and dynamic load is 1000 newton, and loading direction is an X-direction, and frequency is 4 hertz, detects the fatigue performance of yielding rubber, and the result is as shown in table 1.
Hardness test
According to GB/T 531-92 standard, build up 6 millimeters standard film with the standard film of 3 yielding rubbers, test international hardness (IRHD), the result is as shown in table 1.
Tensile property detects
According to the 1 type dumbbell shaped cut-off knife of stipulating among the GB/T528-92 yielding rubber B1-B6 being cut into the dumbbell shaped standard film, is 25 ℃ at probe temperature, and pulling speed is under the condition of 500 mm/min, test tensile strength and tensile yield, and the result is as shown in table 1.
The bond strength of rubber and metal detects
With some bottom surfaces diameter is 26 millimeters, thickness is that 10 millimeters disc metallic matrix (climbing No. 45 steel that steel group produces) carries out the surface sand-blasting processing, then 205 glue (company limited is learned in Dehua, Lip river, Shanghai) are coated in this metallic surface, place after 5 minutes, obtain the bonding coat that thickness is the 0.3-0.5 millimeter, the metallic matrix that is attached with bonding coat is placed in the mould (mould is the mold pressing mould), the composition A1-A6 that is used for yielding rubber that then embodiment 1-6 is obtained is coated in the bonding coat of this metallic matrix respectively, under 170 ℃, heat-treated 5 minutes, take out, cooling obtains yielding rubber spare C1-C6 (rubber layer thickness is about 2 millimeters) respectively.
Detect the bond strength of yielding rubber and the metal of above-mentioned yielding rubber spare C1-C6 respectively according to GB 11211-89 standard, the result is as shown in table 1.
Resistance to low temperature detects
According to GB/T 1682-94 standard, yielding rubber B1-B6 is cut into long 25.0 millimeters, wide 6.0 millimeters sample respectively, do refrigerant with industrial alcohol and dry ice, test temperature limit of brittleness, the result is as shown in table 1.
Thermal aging property detects
According to GB 3512-83 standard, detect the thermal aging property of yielding rubber B1-B6, temperature is 70 ℃, and the time is 48 hours, and the result is as shown in table 1.
Comparative Examples 3
This Comparative Examples is used to illustrate the performance test of reference yielding rubber
Method according to embodiment 13-18, the reference yielding rubber BC1 that Comparative Examples 2 is obtained carries out fatigue performance detection, hardness detection, tensile property detection, low-temperature performance detects and thermal aging property detects, the bond strength that the yielding rubber spare CC1 that the reference yielding rubber composition AC1 that Comparative Examples 1 is obtained prepares carries out yielding rubber and metal detects, and the result is as shown in table 1.
Table 1
As can be seen from Table 1, among the yielding rubber spare C1-C6 that embodiment of the invention 13-18 obtains, the bonding strength of yielding rubber and metal is up to more than the 3.6MPa, and among the reference yielding rubber spare CC1 that Comparative Examples 3 obtains, the bonding strength of yielding rubber and metal only is 1.82MPa, illustrate that the composition that is used for yielding rubber provided by the invention can significantly improve the yielding rubber spare yielding rubber that obtains and the bonding strength between the metal, simultaneously, the fatigue performance of the yielding rubber B1-B6 that embodiment of the invention 7-12 obtains reaches more than 400,000 times, and the fatigue performance of the reference yielding rubber BC1 that Comparative Examples 2 obtains only is 21.5 ten thousand times, illustrates that the composition that is used for yielding rubber provided by the invention can improve the fatigue performance of the yielding rubber that obtains significantly; In addition, the tensile strength of the yielding rubber B1-B6 that embodiment of the invention 7-12 obtains and elongation at break reach respectively more than 20MPa and 500%, and the tensile strength of the reference yielding rubber BC1 that Comparative Examples 2 obtains and elongation at break only are 18.1MPa and 457%, illustrate that the composition that is used for yielding rubber provided by the invention can improve the mechanical property of the yielding rubber that obtains significantly, as fracture tensile strength and elongation at break; In addition, low-temperature performance and the warm air oxidation susceptibility of the yielding rubber B1-B6 that obtains of embodiment of the invention 7-12 are also better; In sum, the composition that is used for yielding rubber provided by the invention can improve the over-all properties of the yielding rubber that obtains significantly, can satisfy requirement of vehicle damping.
Claims (13)
1. composition that is used for yielding rubber, it is characterized in that, said composition contains natural rubber, unsaturated carboxylic acid, promoting agent, strengthening agent, promotor and vulcanizing agent, wherein, with respect to 100 parts by weight of natural rubber, the content of described unsaturated carboxylic acid is the 1-15 weight part, the content of described promoting agent is the 1-10 weight part, the content of described strengthening agent is the 20-80 weight part, and the content of described promotor is the 1-5 weight part, and the content of described vulcanizing agent is the 0.1-5 weight part.
2. composition according to claim 1, wherein, with respect to 100 parts by weight of natural rubber, the content of described unsaturated carboxylic acid is the 5-15 weight part, the content of described promoting agent is the 5-10 weight part, the content of described strengthening agent is the 40-60 weight part, and the content of described promotor is the 2-4 weight part, and the content of described vulcanizing agent is the 0.5-3 weight part.
3. composition according to claim 1 and 2, wherein, described unsaturated carboxylic acid is selected from one or more in methacrylic acid, vinylformic acid and the undecylenic acid.
4. composition according to claim 1 and 2, wherein, described promoting agent is a Zinic stearas; Described strengthening agent is selected from one or more in carbon black, potter's clay, lime carbonate and the sal epsom.
5. composition according to claim 1 and 2, wherein, described promotor is one or more in thiazole promotor, sulphenamide promotor and the thiuram accelerator; Described thiazole promotor is selected from dibenzothiazyl disulfide, 2-benzothiazolyl mercaptan, zinc 2-mercaptobenzothiazole salt, 2 (4-morpholinodithio) benzothiazole and N, one or more in N-diethyl-dithio oxygen base benzothiazole; Described sulphenamide promotor is selected from N cyclohexyl 2 benzothiazole sulfenamide, N tert butyl benzothiazole 2 sulfenamide, N-oxygen diethylene base-2-[4-morpholinodithio sulphenamide, N, one or more in N-dicyclohexyl-2-[4-morpholinodithio sulphenamide and N-oxygen diethylidene thiocarbamyl-N '-oxygen diethylidene sulphenamide; Described thiuram accelerator is selected from one or more in tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, disulfide diisobutyl thiuram, tetra-benzyl thiram disulfide, bis-pentamethylenethiuram tetrasulfide and the tetrabutylthiuram disulfide.
6. composition according to claim 1 and 2, wherein, described vulcanizing agent is morphine quinoline vulcanizing agent and/or sulphur, described morphine quinoline vulcanizing agent is dithiodimorpholine and/or four sulfurations, two morphine quinolines.
7. composition according to claim 1 and 2, wherein, described composition also contains tenderizer and/or anti-aging agent, and described tenderizer is paraffin oil and/or naphthenic oil, and described anti-aging agent is selected from one or more in Ursol D anti-aging agent, quinoline anti-aging agent and the Wax-for preventing rubber; Described Ursol D anti-aging agent is selected from N-(1, the 3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine, N, in N '-two (1,4-dimethyl amyl group) Ursol D, N-cyclohexyl-N '-diphenyl-para-phenylene diamine and N-sec.-propyl-N '-diphenyl-para-phenylene diamine one or more; Described quinoline anti-aging agent is selected from 2,2,4-trimethylammonium-1,2-dihyaroquinoline, 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline and 6-phenyl-2,2,4-trimethylammonium-1, one or more in the 2-dihyaroquinoline; With respect to 100 parts by weight of natural rubber, the content of described tenderizer is greater than 0 to 20 weight part, and the content of described anti-aging agent is greater than 0 to 8 weight part.
8. the described preparation of compositions method of claim 1, it is characterized in that, this method comprises mixes natural rubber, unsaturated carboxylic acid, promoting agent, strengthening agent, promotor and vulcanizing agent, wherein, with respect to 100 parts by weight of natural rubber, the content of described unsaturated carboxylic acid is the 1-15 weight part, the content of described promoting agent is the 1-10 weight part, the content of described strengthening agent is the 20-80 weight part, and the content of described promotor is the 1-5 weight part, and the content of described vulcanizing agent is the 0.1-5 weight part.
9. method according to claim 8, wherein, described blended condition comprises that mixing temperature is 40-80 ℃, mixing time is 2-30 minute.
10. method according to claim 8, wherein, described blended method comprises earlier natural rubber, promoting agent, strengthening agent, tenderizer and unsaturated carboxylic acid mixing 5-15 minute, places after 15-40 minute, again with promotor and vulcanizing agent mixing 1-5 minute.
11. a yielding rubber is characterized in that, this yielding rubber makes by any described composition among the claim 1-7 is vulcanized.
12. yielding rubber according to claim 11, wherein, described sulfurized method comprises any described composition among the heating claim 1-6, and the condition of heating comprises that the temperature of heating is 150-180 ℃, and the time of heating is 10-30 minute.
13. a yielding rubber spare, this yielding rubber spare comprises yielding rubber spare matrix, bonding coat and material layer, and described material layer attached on the yielding rubber matrix, is characterized in that by bonding coat described material layer is claim 11 or 12 described yielding rubbers.
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CN102359544B (en) * | 2011-08-01 | 2013-06-26 | 舟山市奥盛汽车传动带制造有限公司 | Driving belt and manufacturing method thereof |
JP5928273B2 (en) * | 2012-09-20 | 2016-06-01 | 株式会社ブリヂストン | Method for producing rubber composition |
CN102924765A (en) * | 2012-11-23 | 2013-02-13 | 上海众力投资发展有限公司 | Suspension rubber composite for automobile and processing process for same |
CN103897232B (en) * | 2014-03-28 | 2016-03-02 | 宁国九鼎橡塑制品有限公司 | A kind of rubber step department and production method thereof |
FR3044314B1 (en) * | 2015-12-01 | 2017-11-10 | Michelin & Cie | RUBBER COMPOSITION BASED ON NATURAL RUBBER HAVING MOLECULAR MASS DISTRIBUTION, SECAMED VIEW, BIMODAL, PROCESS FOR PREPARATION AND PNEUMATIC COMPONENT |
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CN106750591A (en) * | 2016-12-12 | 2017-05-31 | 芜湖集拓橡胶技术有限公司 | Thermostable natural rubber anti-vibration article is formulated |
CN107286413A (en) * | 2017-06-27 | 2017-10-24 | 宁波拓普集团股份有限公司 | A kind of preparation method of high damping cushion rubber |
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