CN105199153A - Damping rubber, preparation method of damping rubber and damping rubber member for vehicle - Google Patents
Damping rubber, preparation method of damping rubber and damping rubber member for vehicle Download PDFInfo
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- CN105199153A CN105199153A CN201410238013.2A CN201410238013A CN105199153A CN 105199153 A CN105199153 A CN 105199153A CN 201410238013 A CN201410238013 A CN 201410238013A CN 105199153 A CN105199153 A CN 105199153A
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Abstract
The invention relates to a hydroxyl-terminated polybutadiene damping rubber material. The hydroxyl-terminated polybutadiene damping rubber material comprises, by weight, 0.5-5 parts of a vulcanizing agent, 5-30 parts of hydroxyl-terminated polybutadiene, 20-100 parts of a strengthening agent, 5-20 parts of a plasticizer, 2-10 parts of a chemical antiager, 0.5-3.5 parts of a wax antiager, 2.5-13 parts of a sulfuration activator, and 0.5-8 parts of a promoter. Preferably, the hydroxyl-terminated polybutadiene damping rubber material also comprises 1-5 parts by weight of thiocyanuric acid. The invention also discloses a preparation method of the damping rubber material. The damping rubber material can be used in a damping rubber product for a vehicle, has good antifatigue performances, greatly prolongs a service life and reduces finished product use.
Description
Technical field
The present invention relates to a kind of yielding rubber and preparation method thereof, belong to rubber materials.
Background technology
Along with the development of modern industry, vibrations and noise have become the serious problems of every field: reduce performance accuracy, affect quality product, shorten product life, jeopardize security.In order to reduce even to eliminate vibrations, normal application various anti-vibration article, especially rubber damping product in reality.It can isolate vibrations and excitaton source effectively, can also relax the vibrations of vibration body, therefore be widely used in the vibration isolation of the power machines such as various Motor vehicles, aircraft, ships.
For the yielding rubber of general application, usual need add the strengthening agent of certain consumption, normally various carbon black and white carbon black, just can obtain corresponding intensity and damping and amortization, but in the use procedure of product, under Tension and Compression power effect repeatedly, the stress relaxation produced in material, often have little time in deformation period, result is that the inner stress produced has little time dispersion, cross-link bond between rubber molecule destroys, thus causes rubber item performance to have greatly changed to cause the decline of fatigue property.
Summary of the invention
Technical problem to be solved by this invention is rubber under periodically repeatedly repetitive distortion, intermolecular cross-link bond can be made to produce fracture, thus destruction product quality affects work-ing life after certain hour.
In order to solve the problem, the invention provides a kind of yielding rubber material, comprising following component: main rubber, hydroxy-end capped polyhutadiene, vulcanizing agent, auxiliary agent.Described auxiliary agent is strengthening agent, softening agent, chemical antiager, wax class anti-aging agent, vulcanization leveller, promotor.Hydroxy-end capped polyhutadiene is with the addition of in yielding rubber provided by the present invention, due to the double bond active group that hydroxy-end capped polyhutadiene molecular chain contains, repetitive distortion is subject to and after causing the molecular rupture be cross-linked at rubber, still can again react with the bioactive molecule of breaking part, keep the integrity of rubber molecule, thus make formula materials obtain good resistance to fatigue, effectively extend the work-ing life of rubber product.Especially when being added into trithiocyanuric acid in filling a prescription, because trithiocyanuric acid is to the modifying function of hydroxy-terminated polybutadienes, add the activity of double bond group on hydroxy-terminated polybutadienes molecular weight, the connection between this hydroxy-terminated polybutadienes molecular chain and main rubber is more prone to.
Described yielding rubber can be applicable in vehicle (automobile or motorcycle) yielding rubber product.The present invention compared with prior art tool has the following advantages: the consistency between each material of rubber combination of the present invention is good, interaction between material is strong, the rubber performance of preparation is excellent, determine tensile stress conservation rate high, the rubber parts antifatigue life-span of preparation is long, can be widely used in automobile-used (automobile or motorcycle) shock absorbing rubber product, improve work-ing life, reduce use cost.
Present invention also offers a kind of preparation method of yielding rubber material, preparation process comprises following steps:
(1) a certain proportion of natural rubber, cis-1,4-polybutadiene rubber mixture are dropped into Banbury mixer, plasticate and obtain Blend rubber;
(2) after the Blend rubber described in step (1) being parked a few hours, then add a certain amount of strengthening agent, hydroxy-end capped polyhutadiene, trithiocyanuric acid, softening agent, chemical antiager, wax class anti-aging agent, zinc oxide, stearic acid, mixing rear slice parks cooling;
(3) in mixing uniform mixture in step (2), add a certain amount of vulcanizing agent and promotor mixes on a mill until, slice after thin-pass, obtains yielding rubber.
Embodiment
Technical scheme of the present invention relates to a kind of yielding rubber composition, and described elastomeric material comprises following composition: main rubber, vulcanizing agent, auxiliary agent, also comprises hydroxy-end capped polyhutadiene in described yielding rubber.
Under preferable case, with the main rubber of 100 weight parts for benchmark, described vulcanizing agent is 0.5 ~ 5 weight part, and described hydroxy-end capped polyhutadiene is 5 ~ 30 weight parts.
Described vulcanizing agent is sulphur or sulfocompound, is preferably sulphur, one or more in 4,4'-dimorpholinyl disulfide.Can make main rubber generation vulcanization crosslinking, the mass parts of its relative 100 weight part main rubber components is 0.5 ~ 5 weight part, 1 ~ 4 weight part under preferable case.
Described hydroxy-end capped polyhutadiene is improved rubber antifatigue solarization, extends the effect in product work-ing life.With natural rubber, cis-1,4-polybutadiene rubber composition for main rubber product, weathering process be based on rubber molecular chain continue be cross-linked.By the process of corsslinking molecular bond rupture and self-crosslinking again that rubber item occurs under rubber product is subject to repetitive distortion, and this self-crosslinking phenomenon of rubber molecular chain can change the original characteristic of rubber product, make product become more and more harder, elasticity also worse and worse.Due to containing double bond active group on hydroxy-end capped polyhutadiene molecule, can again react with the bioactive molecule of breaking part, the self-crosslinking of the rubber molecular chain after effective minimizing is aging, extends product life.Described hydroxy-end capped polyhutadiene can pass through commercially available, as Sartomer Specialty Chemicals LBH-2000.The content of its relative 100 weight part main rubber components is 5 ~ 30 weight parts, is 8 ~ 25 weight parts under preferable case.
Under preferable case, also comprise trithiocyanuric acid in described yielding rubber, the relative 100 weight part main rubber content of described trithiocyanuric acid are 1-5 weight part.Trithiocyanuric acid energy modification hydroxy-terminated polybutadienes, increases the activity of its double bond group, stops the self-crosslinking of aging rear rubber molecular chain further, makes rubber product keep its elasticity and snappiness, extends the life-span of goods further.
Hydroxy-end capped polyhutadiene and trithiocyanuric acid can only add according to certain consumption, and when addition is very few, to bear effective molecular chain of distortion after weathering very few for product, elasticity and kindliness poor, affect product life; And consumption too much time, be unfavorable for thermal motion and the Stress transmit of segment, network chain easily produces stress concentration, can affect product work-ing life equally.
Under preferable case, described auxiliary agent is strengthening agent, softening agent, chemical antiager, wax class anti-aging agent, vulcanization leveller, promotor.
Described strengthening agent is carbon black, can regulate rubber hardness, the mechanical property of Reinforced Rubber and wear resisting property.The content of its relative 100 weight part main rubber components is 20 ~ 100 weight parts.
Described softening agent is naphthenic hydrocarbon oils or aromatic oil, can regulate rubber hardness, facilitate compounding rubber, increases production efficiency.The content of its relative 100 weight part main rubber components is 5 ~ 20 weight parts, is 8 ~ 18 weight parts under preferable case.
Described chemical antiager is Ursol D or organic sulfide class, can be N, N '-two (betanaphthyl) Ursol D, N-phenyl-N '-cyclohexyl Ursol D, N, N '-di tolyl p phenylenediamine, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, preferred N, N '-two (betanaphthyl) Ursol D, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, 2-mercaptobenzimidazole, zinc salt of 2 mercaptobenzimidazole or nickel dibutyl dithiocarbamate; Be preferably one or more in 2-mercaptobenzimidazole, N, N '-two (betanaphthyl) Ursol D or N-sec.-propyl-N '-diphenyl-para-phenylene diamine.Have the functions such as heat-resisting endowmentization, ozone ageing, the content of its relative 100 weight part main rubber components is 2 ~ 10 weight parts, is 2 ~ 6 weight parts under preferable case.
Described wax class anti-aging agent is paraffin, has the effect of resistance to ozone-induced cracking.The content of its relative 100 weight part main rubber components is 0.5 ~ 3.5 weight part.
Vulcanization leveller is made up of zinc oxide and stearic acid, can effectively improve vulcanization of rubber activity.In the high-temperature reaction process of rubber, zinc oxide and stearic acid reaction, then form intermediate product with promotor, and most heel vulcanizing agent effect completes the vulcanization crosslinking of rubber jointly.Relative 100 weight part main rubber component zinc oxide and stearic content are respectively 2 ~ 10 weight parts, 0.5 ~ 3 weight part, and namely part by weight is 2 ~ 10:0.5 ~ 3.Under preferable case, zinc oxide and stearic mass parts are respectively 2 ~ 8 weight parts, 1 ~ 2.5 weight part.Promotor is thiazoles, sulfenamide or dithiocar-bamate, is preferably N-cyclohexyl-2-[4-morpholinodithio sulphenamide, dibenzothiazyl disulfide, one or more in ziram.Can effectively improve vulcanization reaction speed, the content of its relative 100 weight part main rubber components is 0.5 ~ 8 weight part, 0.5 ~ 5 weight part under preferable case.
The invention still further relates to a kind of preparation method of yielding rubber composition, comprise following steps:
(1) the cis-1,4-polybutadiene rubber mixture of the natural rubber of 40 ~ 80 weight parts, 20 ~ 60 weight parts is dropped into Banbury mixer, plasticate and obtain Blend rubber in 2 ~ 10 minutes;
(2) after the Blend rubber described in step (1) being parked 8 ~ 72 hours, add polyhutadiene, the trithiocyanuric acid of 1 ~ 5 weight part, 5 ~ 20 parts by weight of plasticizer, 2 ~ 10 weight part chemical antiagers, 0.5 ~ 3.5 weight part wax class anti-aging agent, 2 ~ 10 part by weight of zinc oxide, 0.5 ~ 3 weight part stearic acid that 20 ~ 100 weight part strengthening agents, 5 ~ 30 weight parts are hydroxy-end capped, at 100-200 DEG C, mix slice after 3-20 minute and park cooling;
(3) in mixing uniform mixture in step (2), add a certain amount of 0.5 ~ 5 weight part vulcanizing agent and 0.5 ~ 8 weight part promotor mixes on a mill until, after thin-pass 3 ~ 10 times, slice is for subsequent use.
Blend rubber is parked the dispersing property that 8 ~ 72 hours can improve Blend rubber in step (2), make product obtain better homogeneity; Melting temperature in step (2) should control in a proper range, is unfavorable for the melting dispersion of component when temperature is too low, the too high volatilization accelerating the components such as the aging of main rubber and softening agent of temperature.
Below in conjunction with embodiment, the present invention is further described in detail, but is not limited to this.
All raw materials in embodiment described in the present invention refer in particular to as non-, are commercially available prod.
embodiment 1
Yielding rubber composition described in the present embodiment, composed of the following components: natural rubber RSS3(Thailand No. 3 smoked sheets) 65 weight parts, cis-1,4-polybutadiene rubber BR9000(SINOPEC Beijing Yanshan Company) 35 weight parts, strengthening agent N550(Tianjin goldschmidt chemical corporation is produced) 20 weight parts, strengthening agent N774(Tianjin goldschmidt chemical corporation is produced) 45 weight parts, hydroxy-end capped polyhutadiene LBH-2000(Sartomer Specialty Chemicals) 15 parts, the softening agent TUDALEN65(Germany Chinese is holy) 18 weight parts, chemical antiager N, N '-two (betanaphthyl) Ursol D (chemical plant, China Petrochemical Industry Nanjing) 2 weight parts, chemical antiager 2-mercaptobenzimidazole (Huangyan East Zhejiang province Xiang Zhu Chemical Co., Ltd.) 1.0 weight parts, wax class anti-aging agent No. 58 SEMI-REFINED PARAFFIN WAX (Sinopec Group) 2 weight parts, zinc oxide (Liuzhou Xin Pin company limited) 8 weight parts, stearic acid (the polite Chemical Co., Ltd. in Hong Kong) 1.0 weight parts, N-cyclohexyl-2 benzothiazole sulphenamide (Puyang WeiLin chemical engineering Co., Ltd) 1.0 weight part, dibenzothiazyl disulfide (Puyang WeiLin chemical engineering Co., Ltd) 0.8 weight part, sulphur (Ke Mao rubber-plastics material company limited) 1.5 weight parts.
The preparation of rubber combination:
(1) according to the above ratio natural rubber, cis-1,4-polybutadiene rubber mixture are dropped into Banbury mixer, plasticate and obtain Blend rubber in 5 minutes;
(2), after above-mentioned Blend rubber being parked 16 hours, add strengthening agent, hydroxy-end capped polyhutadiene, softening agent, chemical antiager, wax class anti-aging agent, zinc oxide, stearic acid, after mixing 240s, slice parks cooling;
(3) rubber unvulcanizate of above-mentioned cooling and vulcanizing agent, promotor are mixed on a mill until, after thin-pass 5 times, slice is for subsequent use, obtains rubber combination A1.
The preparation of rubber testing exemplar:
Under 155 DEG C of conditions, rubber combination A1 obtained above is put into 200T vulcanizing press (
chengdu Hangfa Hydraulic Construction Co., Ltd.) in carry out compression molding, obtain the rubber parts B1 that thickness is 5 millimeters, rubber parts B1 is as pin hole, bubble etc. meet the finished product of service requirements without obvious flaw.
embodiment 2
Yielding rubber composition described in the present embodiment, composed of the following components: natural rubber RSS3(Thailand No. 3 smoked sheets) 80 weight parts, cis-1,4-polybutadiene rubber BR9000(SINOPEC Beijing Yanshan Company) 20 weight parts, strengthening agent N774(Tianjin goldschmidt chemical corporation is produced) 60 weight parts, hydroxy-end capped polyhutadiene LBH-2000(Sartomer Specialty Chemicals) 8 parts, trithiocyanuric acid (Shanxi-Prov Inst of Chemical Industry) 3 parts, the softening agent naphthenic oil 450(Germany Chinese is holy) 12 weight parts, chemical antiager N-sec.-propyl-N '-diphenyl-para-phenylene diamine (chemical plant, China Petrochemical Industry Nanjing) 1.5 weight parts, chemical antiager 2-mercaptobenzimidazole (Huangyan East Zhejiang province Xiang Zhu Chemical Co., Ltd.) 2.0 weight parts, wax class anti-aging agent Lay mattress wax _ 654(Rhein Chemie Corporation) 1.5 weight parts, zinc oxide (Liuzhou Xin Pin company limited) 5 weight parts, stearic acid (the polite Chemical Co., Ltd. in Hong Kong) 1.5 weight parts, ziram (Puyang WeiLin chemical engineering Co., Ltd) 0.2 weight part, dibenzothiazyl disulfide (Puyang WeiLin chemical engineering Co., Ltd) 1.2 weight part, sulphur (Ke Mao rubber-plastics material company limited) 2.0 weight parts.
The preparation of rubber combination:
(1) according to the above ratio natural rubber, cis-1,4-polybutadiene rubber mixture are dropped into Banbury mixer, plasticate and obtain Blend rubber in 3 minutes;
(2), after above-mentioned Blend rubber being parked 24 hours, add strengthening agent, hydroxy-end capped polyhutadiene, trithiocyanuric acid, softening agent, chemical antiager, wax class anti-aging agent, zinc oxide, stearic acid, after mixing 320s, slice parks cooling;
(3) rubber unvulcanizate of above-mentioned cooling and vulcanizing agent, promotor are mixed on a mill until, after thin-pass 6 times, slice is for subsequent use, obtains rubber combination A2.
The preparation of rubber testing exemplar:
Under 155 DEG C of conditions, rubber combination A2 obtained above is put into 200T vulcanizing press (
chengdu Hangfa Hydraulic Construction Co., Ltd.) in carry out compression molding, obtain the rubber parts B2 that thickness is 5 millimeters, rubber parts B2 is as pin hole, bubble etc. meet the finished product of service requirements without obvious flaw.
embodiment 3
Yielding rubber composition described in the present embodiment, composed of the following components: natural rubber RSS3(Thailand No. 3 smoked sheets) 75 weight parts, cis-1,4-polybutadiene rubber BR9000(SINOPEC Beijing Yanshan Company) 25 weight parts, strengthening agent N550(Tianjin goldschmidt chemical corporation is produced) 15 weight parts, strengthening agent N774(Tianjin goldschmidt chemical corporation is produced) 50 weight parts, hydroxy-end capped polyhutadiene LBH-2000(Sartomer Specialty Chemicals) 10 parts, the softening agent naphthenic oil 450(Germany Chinese is holy) 10 weight parts, chemical antiager N-sec.-propyl-N '-diphenyl-para-phenylene diamine (chemical plant, China Petrochemical Industry Nanjing) 1.0 weight parts, chemical antiager 2-mercaptobenzimidazole (Huangyan East Zhejiang province Xiang Zhu Chemical Co., Ltd.) 1.5 weight parts, wax class anti-aging agent Lay mattress wax _ 654(Rhein Chemie Corporation) 1 weight part, zinc oxide (Liuzhou Xin Pin company limited) 4 weight parts, stearic acid (the polite Chemical Co., Ltd. in Hong Kong) 2 weight parts, ziram (Puyang WeiLin chemical engineering Co., Ltd) 0.1 weight part, dibenzothiazyl disulfide (Puyang WeiLin chemical engineering Co., Ltd) 1.5 weight part, sulphur (Ke Mao rubber-plastics material company limited) 1.8 weight parts.
The preparation of rubber combination:
(1) according to the above ratio natural rubber, cis-1,4-polybutadiene rubber mixture are dropped into Banbury mixer, plasticate and obtain Blend rubber in 3 minutes;
(2), after above-mentioned Blend rubber being parked 24 hours, add strengthening agent, hydroxy-end capped polyhutadiene, softening agent, chemical antiager, wax class anti-aging agent, zinc oxide, stearic acid, after mixing 320s, slice parks cooling;
(3) rubber unvulcanizate of above-mentioned cooling and vulcanizing agent, promotor are mixed on a mill until, after thin-pass 6 times, slice is for subsequent use, obtains rubber combination A3.
The preparation of rubber testing exemplar:
Under 155 DEG C of conditions, rubber combination A3 obtained above is put into 200T vulcanizing press (
chengdu Hangfa Hydraulic Construction Co., Ltd.) in carry out compression molding, obtain the rubber parts B3 that thickness is 5 millimeters, rubber parts B3 is as pin hole, bubble etc. meet the finished product of service requirements without obvious flaw.
embodiment 4
Yielding rubber composition described in the present embodiment, composed of the following components: natural rubber RSS3(Thailand No. 3 smoked sheets) 55 weight parts, cis-1,4-polybutadiene rubber BR9000(SINOPEC Beijing Yanshan Company) 45 weight parts, strengthening agent N550(Tianjin goldschmidt chemical corporation is produced) 49 weight parts, hydroxy-end capped polyhutadiene LBH-2000(Sartomer Specialty Chemicals) 22 parts, the softening agent naphthenic oil 450(Germany Chinese is holy) 5 weight parts, the softening agent TUDALEN65(Germany Chinese is holy) 5 weight parts, chemical antiager N-sec.-propyl-N '-diphenyl-para-phenylene diamine (chemical plant, China Petrochemical Industry Nanjing) 1.0 weight parts, chemical antiager N, N '-two (betanaphthyl) Ursol D (chemical plant, China Petrochemical Industry Nanjing) 0.8 weight part, chemical antiager 2-mercaptobenzimidazole (Huangyan East Zhejiang province Xiang Zhu Chemical Co., Ltd.) 1.3 weight parts, wax class anti-aging agent No. 58 SEMI-REFINED PARAFFIN WAX (Sinopec Group) 1.0 weight parts, wax class anti-aging agent Lay mattress wax _ 654(Rhein Chemie Corporation) 1.0 weight parts, zinc oxide (Liuzhou Xin Pin company limited) 7 weight parts, stearic acid (the polite Chemical Co., Ltd. in Hong Kong) 2.0 weight parts, N-cyclohexyl-2 benzothiazole sulphenamide (Puyang WeiLin chemical engineering Co., Ltd) 0.8 weight part, ziram (Puyang WeiLin chemical engineering Co., Ltd) 0.2 weight part, dibenzothiazyl disulfide (Puyang WeiLin chemical engineering Co., Ltd) 0.8 weight part, sulphur (Ke Mao rubber-plastics material company limited) 2.5 weight parts.
The preparation of rubber combination:
(1) according to the above ratio natural rubber, cis-1,4-polybutadiene rubber mixture are dropped into Banbury mixer, plasticate and obtain Blend rubber in 4 minutes;
(2), after above-mentioned Blend rubber being parked 24 hours, add strengthening agent, hydroxy-end capped polyhutadiene, softening agent, chemical antiager, wax class anti-aging agent, zinc oxide, stearic acid, after mixing 220s, slice parks cooling;
(3) rubber unvulcanizate of above-mentioned cooling and vulcanizing agent, promotor are mixed on a mill until, after thin-pass 4 times, slice is for subsequent use, obtains rubber combination A4.
The preparation of rubber testing exemplar:
Under 155 DEG C of conditions, rubber combination A4 obtained above is put into 200T vulcanizing press (
chengdu Hangfa Hydraulic Construction Co., Ltd.) in carry out compression molding, obtain the rubber parts B4 that thickness is 5 millimeters, rubber parts B4 is as pin hole, bubble etc. meet the finished product of service requirements without obvious flaw.
embodiment 5
Yielding rubber composition described in the present embodiment, composed of the following components: natural rubber RSS3(Thailand No. 3 smoked sheets) 58 weight parts, cis-1,4-polybutadiene rubber BR9000(SINOPEC Beijing Yanshan Company) 42 weight parts, strengthening agent N550(Tianjin goldschmidt chemical corporation is produced) 45 weight parts, hydroxy-end capped polyhutadiene LBH-2000(Sartomer Specialty Chemicals) 20 parts, trithiocyanuric acid (Shanxi-Prov Inst of Chemical Industry) 4 parts, the softening agent TUDALEN65(Germany Chinese is holy) 9 weight parts, chemical antiager N, N '-two (betanaphthyl) Ursol D (chemical plant, China Petrochemical Industry Nanjing) 1.2 weight parts, chemical antiager 2-mercaptobenzimidazole (Huangyan East Zhejiang province Xiang Zhu Chemical Co., Ltd.) 1.0 weight parts, wax class anti-aging agent No. 58 SEMI-REFINED PARAFFIN WAX (Sinopec Group) 2.0 weight parts, zinc oxide (Liuzhou Xin Pin company limited) 7 weight parts, stearic acid (the polite Chemical Co., Ltd. in Hong Kong) 2.0 weight parts, ziram (Puyang WeiLin chemical engineering Co., Ltd) 0.2 weight part, dibenzothiazyl disulfide (Puyang WeiLin chemical engineering Co., Ltd) 1.4 weight part, sulphur (Ke Mao rubber-plastics material company limited) 2.2 weight parts.
The preparation of rubber combination:
(1) according to the above ratio natural rubber, cis-1,4-polybutadiene rubber mixture are dropped into Banbury mixer, plasticate and obtain Blend rubber in 4 minutes;
(2), after above-mentioned Blend rubber being parked 18 hours, add strengthening agent, hydroxy-end capped polyhutadiene, trithiocyanuric acid, softening agent, chemical antiager, wax class anti-aging agent, zinc oxide, stearic acid, after mixing 360s, slice parks cooling;
(3) rubber unvulcanizate of above-mentioned cooling and vulcanizing agent, promotor are mixed on a mill until, after thin-pass 7 times, slice is for subsequent use, obtains rubber combination A5.
The preparation of rubber testing exemplar:
Under 155 DEG C of conditions, rubber combination A5 obtained above is put into 200T vulcanizing press (
chengdu Hangfa Hydraulic Construction Co., Ltd.) in carry out compression molding, obtain the rubber parts B5 that thickness is 5 millimeters, rubber parts B5 is as pin hole, bubble etc. meet the finished product of service requirements without obvious flaw.
embodiment 6
Yielding rubber composition described in the present embodiment, composed of the following components: natural rubber RSS3(Thailand No. 3 smoked sheets) 69 weight parts, cis-1,4-polybutadiene rubber BR9000(SINOPEC Beijing Yanshan Company) 31 weight parts, strengthening agent N550(Tianjin goldschmidt chemical corporation is produced) 22 weight parts, strengthening agent N774(Tianjin goldschmidt chemical corporation is produced) 39 weight parts, hydroxy-end capped polyhutadiene LBH-2000(Sartomer Specialty Chemicals) 28 parts, the softening agent naphthenic oil 450(Germany Chinese is holy) 9 weight parts, chemical antiager N-sec.-propyl-N '-diphenyl-para-phenylene diamine (chemical plant, China Petrochemical Industry Nanjing) 1.4 weight parts, chemical antiager 2-mercaptobenzimidazole (Huangyan East Zhejiang province Xiang Zhu Chemical Co., Ltd.) 1.6 weight parts, wax class anti-aging agent Lay mattress wax _ 654(Rhein Chemie Corporation) 2.5 weight parts, zinc oxide (Liuzhou Xin Pin company limited) 6 weight parts, stearic acid (the polite Chemical Co., Ltd. in Hong Kong) 1.8 weight parts, ziram (Puyang WeiLin chemical engineering Co., Ltd) 0.2 weight part, dibenzothiazyl disulfide (Puyang WeiLin chemical engineering Co., Ltd) 1.8 weight part, sulphur (Ke Mao rubber-plastics material company limited) 2.3 weight parts.
The preparation of rubber combination:
(1) according to the above ratio natural rubber, cis-1,4-polybutadiene rubber mixture are dropped into Banbury mixer, plasticate and obtain Blend rubber in 6 minutes;
(2), after above-mentioned Blend rubber being parked 8 hours, add strengthening agent, hydroxy-end capped polyhutadiene, softening agent, chemical antiager, wax class anti-aging agent, zinc oxide, stearic acid, after mixing 260s, slice parks cooling;
(3) rubber unvulcanizate of above-mentioned cooling and vulcanizing agent, promotor are mixed on a mill until, after thin-pass 6 times, slice is for subsequent use, obtains rubber combination A6.
The preparation of rubber testing exemplar:
Under 155 DEG C of conditions, rubber combination A6 obtained above is put into 200T vulcanizing press (
chengdu Hangfa Hydraulic Construction Co., Ltd.) in carry out compression molding, obtain the rubber parts B6 that thickness is 5 millimeters, rubber parts B6 is as pin hole, bubble etc. meet the finished product of service requirements without obvious flaw.
embodiment 7
Except not plasticizer-containing, wax class anti-aging agent, all the other components are identical with embodiment five with making method, obtain rubber combination A7.
Under 155 DEG C of conditions, rubber combination A7 obtained above is put into 200T vulcanizing press (
chengdu Hangfa Hydraulic Construction Co., Ltd.) in carry out compression molding, obtain the rubber parts B7 that thickness is 5 millimeters, rubber parts B7 is as pin hole, bubble etc. meet the finished product of service requirements without obvious flaw.
embodiment 8
Except not containing except trithiocyanuric acid, softening agent, wax class anti-aging agent, all the other components are identical with embodiment five with making method, obtain rubber combination A8.
Under 155 DEG C of conditions, rubber combination A8 obtained above is put into 200T vulcanizing press (
chengdu Hangfa Hydraulic Construction Co., Ltd.) in carry out compression molding, obtain the rubber parts B8 that thickness is 5 millimeters, rubber parts B8 is as pin hole, bubble etc. meet the finished product of service requirements without obvious flaw.
comparative example 1
Yielding rubber composition described in this comparative example, composed of the following components: natural rubber RSS3(Thailand No. 3 smoked sheets) 65 weight parts, cis-1,4-polybutadiene rubber BR9000(SINOPEC Beijing Yanshan Company) 35 weight parts, strengthening agent N550(Tianjin goldschmidt chemical corporation is produced) 20 weight parts, strengthening agent N774(Tianjin goldschmidt chemical corporation is produced) 45 weight parts, the softening agent TUDALEN65(Germany Chinese is holy) 18 weight parts, chemical antiager N, N '-two (betanaphthyl) Ursol D (chemical plant, China Petrochemical Industry Nanjing) 2 weight parts, chemical antiager 2-mercaptobenzimidazole (Huangyan East Zhejiang province Xiang Zhu Chemical Co., Ltd.) 1.0 weight parts, wax class anti-aging agent No. 58 SEMI-REFINED PARAFFIN WAX (Sinopec Group) 2 weight parts, zinc oxide (Liuzhou Xin Pin company limited) 8 weight parts, stearic acid (the polite Chemical Co., Ltd. in Hong Kong) 1.0 weight parts, N-cyclohexyl-2 benzothiazole sulphenamide (Puyang WeiLin chemical engineering Co., Ltd) 1.0 weight part, dibenzothiazyl disulfide (Puyang WeiLin chemical engineering Co., Ltd) 0.8 weight part, sulphur (Ke Mao rubber-plastics material company limited) 1.5 weight parts.
The preparation of rubber combination:
(1) according to the above ratio natural rubber, cis-1,4-polybutadiene rubber mixture are dropped into Banbury mixer, plasticate and obtain Blend rubber in 5 minutes;
(2), after above-mentioned Blend rubber being parked 16 hours, add strengthening agent, softening agent, chemical antiager, wax class anti-aging agent, zinc oxide, stearic acid, after mixing 240s, slice parks cooling;
(3) rubber unvulcanizate of above-mentioned cooling and vulcanizing agent, promotor are mixed on a mill until, after thin-pass 5 times, slice is for subsequent use, obtains rubber combination DA1.
The preparation of rubber testing exemplar:
Under 155 DEG C of conditions, rubber combination DA1 obtained above is put into 200T vulcanizing press (
chengdu Hangfa Hydraulic Construction Co., Ltd.) in carry out compression molding, obtain the rubber parts DB1 that thickness is 5 millimeters, rubber parts DB1 is as pin hole, bubble etc. meet the finished product of service requirements without obvious flaw.
comparative example 2
Yielding rubber composition described in this comparative example, composed of the following components: natural rubber RSS3(Thailand No. 3 smoked sheets) 55 weight parts, cis-1,4-polybutadiene rubber BR9000(SINOPEC Beijing Yanshan Company) 45 weight parts, strengthening agent N550(Tianjin goldschmidt chemical corporation is produced) 49 weight parts, the softening agent naphthenic oil 450(Germany Chinese is holy) 5 weight parts, the softening agent TUDALEN65(Germany Chinese is holy) 5 weight parts, chemical antiager N-sec.-propyl-N '-diphenyl-para-phenylene diamine (chemical plant, China Petrochemical Industry Nanjing) 1.0 weight parts, chemical antiager N, N '-two (betanaphthyl) Ursol D (chemical plant, China Petrochemical Industry Nanjing) 0.8 weight part, chemical antiager 2-mercaptobenzimidazole (Huangyan East Zhejiang province Xiang Zhu Chemical Co., Ltd.) 1.3 weight parts, wax class anti-aging agent No. 58 SEMI-REFINED PARAFFIN WAX (Sinopec Group) 1.0 weight parts, wax class anti-aging agent Lay mattress wax _ 654(Rhein Chemie Corporation) 1.0 weight parts, zinc oxide (Liuzhou Xin Pin company limited) 7 weight parts, stearic acid (the polite Chemical Co., Ltd. in Hong Kong) 2.0 weight parts, N-cyclohexyl-2 benzothiazole sulphenamide (Puyang WeiLin chemical engineering Co., Ltd) 0.8 weight part, ziram (Puyang WeiLin chemical engineering Co., Ltd) 0.2 weight part, dibenzothiazyl disulfide (Puyang WeiLin chemical engineering Co., Ltd) 0.8 weight part, sulphur (Ke Mao rubber-plastics material company limited) 2.5 weight parts.
The preparation of rubber combination:
(1) according to the above ratio natural rubber, cis-1,4-polybutadiene rubber mixture are dropped into Banbury mixer, plasticate and obtain Blend rubber in 4 minutes;
(2), after above-mentioned Blend rubber being parked 24 hours, add strengthening agent, softening agent, chemical antiager, wax class anti-aging agent, zinc oxide, stearic acid, after mixing 220s, slice parks cooling;
(3) rubber unvulcanizate of above-mentioned cooling and vulcanizing agent, promotor are mixed on a mill until, after thin-pass 4 times, slice is for subsequent use, obtains rubber combination DA2.
The preparation of rubber testing exemplar:
Under 155 DEG C of conditions, rubber combination DA2 obtained above is put into 200T vulcanizing press (
chengdu Hangfa Hydraulic Construction Co., Ltd.) in carry out compression molding, obtain the rubber parts DB2 that thickness is 5 millimeters, rubber parts DB2 is as pin hole, bubble etc. meet the finished product of service requirements without obvious flaw.
performance test:
1, fatigue performance test: adopt GB/T15584-1995 " mensuration of vulcanized rubber temperature rise and fatigue performance in angular test " described method, detects the rubber B1 ~ B8 of embodiment 1 ~ 8 and comparative example 1 ~ 2 preparation and the fatigue performance of DB1 ~ DB2.
2, mechanical behavior under high temperature test
100% stress at definite elongation of testing example 1-8 and comparative example 1-2 under 90 DEG C and 120 DEG C of environment, drawing process is with reference to GB/T528-1998 " mensuration of vulcanized rubber or thermoplastic elastomer tensile stress-strain performance ".
3, test result is as shown in table 1
Yielding rubber test result described in table 1 embodiment 1 ~ 8 and comparative example 1 ~ 2
| Project | 90 DEG C of stress at definite elongation conservation rate/% | 120 DEG C of stress at definite elongation conservation rate/% | Fatigue lifetime/ten thousand times |
| Embodiment 1 | 65 | 62 | 45.3 |
| Embodiment 2 | 68 | 64 | 47.8 |
| Embodiment 3 | 64 | 62 | 45.5 |
| Embodiment 4 | 63 | 61 | 44.4 |
| Embodiment 5 | 67 | 65 | 48.6 |
| Embodiment 6 | 66 | 64 | 45.1 |
| Embodiment 7 | 66 | 63 | 48.3 |
| Embodiment 8 | 65 | 62 | 45.8 |
| Comparative example 1 | 53 | 45 | 26.6 |
| Comparative example 2 | 52 | 43 | 27.2 |
From above-mentioned test result, with the addition of trithiocyanuric acid in embodiment 2,5, its life-span is higher than embodiment 1,3,4,6, and the improvement fatigue performance of interpolation to hydroxy terminated polybutadiene of visible trithiocyanuric acid has promoter action; And do not add its fatigue performance of rubber of hydroxy terminated polybutadiene in comparative example 1,2 and stress at definite elongation conservation rate all poor; In auxiliary agent, softening agent, wax class anti-aging agent etc. mainly have impact to processing procedure, and on the finished product life-span, the impact of aspect is little.Consistency between each material of rubber combination of the present invention is good, interaction between material is strong, the rubber performance of preparation is excellent, determine tensile stress conservation rate high, the rubber parts antifatigue life-span of preparation is long, can be widely used in vehicle (automobile or motorcycle) shock absorbing rubber product, improve and use work-ing life, reduce use cost.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments, and thus the apparent change of extending out or variation be still among the protection domain of the invention claim.
Claims (18)
1. a yielding rubber, is characterized in that, comprises following component: main rubber, vulcanizing agent, auxiliary agent, also comprises hydroxy-end capped polyhutadiene in described yielding rubber.
2. yielding rubber according to claim 1, it is characterized in that, with the main rubber of 100 weight parts for benchmark, described vulcanizing agent is 0.5 ~ 5 weight part, and described hydroxy-end capped polyhutadiene is 5 ~ 30 weight parts.
3. according to the arbitrary described yielding rubber of claim 1-2, it is characterized in that, also include trithiocyanuric acid in described yielding rubber, the main rubber content of relative 100 weight parts of described trithiocyanuric acid is 1-5 weight part.
4. yielding rubber according to claim 1, it is characterized in that, described main rubber is polydiene, and described polydiene is the composition of natural rubber and cis-1,4-polybutadiene rubber.
5. yielding rubber according to claim 4, it is characterized in that, natural rubber is 40 ~ 80 weight parts in the composition of described natural rubber and cis-1,4-polybutadiene rubber by weight, and cis-1,4-polybutadiene rubber is 20 ~ 60 weight parts.
6. yielding rubber according to claim 1, it is characterized in that, also include auxiliary agent in yielding rubber, is one or more in strengthening agent, softening agent, chemical antiager, wax class anti-aging agent, vulcanization leveller, promotor in described auxiliary agent.
7. yielding rubber according to claim 6, it is characterized in that, with the main rubber of 100 weight parts for benchmark, strengthening agent 20 ~ 100 weight part, softening agent 5 ~ 20 weight part, chemical antiager 2 ~ 10 weight part, wax class anti-aging agent 0.5 ~ 3.5 weight part, vulcanization leveller 2.5 ~ 13 weight part, promotor 0.5 ~ 8 weight part.
8. yielding rubber according to claim 6,7, is characterized in that, described vulcanization leveller is Zinic stearas or zinc oxide, stearic acid mixture; In described zinc oxide, stearic acid mixture, zinc oxide, stearic part by weight are 2 ~ 10:0.5 ~ 3.
9. according to the arbitrary described yielding rubber of claim 6, it is characterized in that, described strengthening agent is carbon black; Described softening agent is naphthenic hydrocarbon oils or aromatic oil; Described chemical antiager is Ursol D or organic sulfide class; Described vulcanizing agent is sulphur or sulfocompound; Described promotor is thiazoles, sulfenamide or dithiocar-bamate.
10. yielding rubber according to claim 9, it is characterized in that, described chemical antiager is N, N '-two (betanaphthyl) Ursol D, N-phenyl-N '-cyclohexyl Ursol D, N, N '-di tolyl p phenylenediamine, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, 2-mercaptobenzimidazole, zinc salt of 2 mercaptobenzimidazole, one or more in nickel dibutyl dithiocarbamate.
11. yielding rubbers according to claim 9, is characterized in that, described chemical antiager is N, N '-two (betanaphthyl) Ursol D, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, 2-mercaptobenzimidazole; Described vulcanizing agent is sulphur, one or more in 4,4'-dimorpholinyl disulfide; Described promotor is N-cyclohexyl-2-[4-morpholinodithio sulphenamide, dibenzothiazyl disulfide, one or more in ziram.
12., according to the preparation method of the arbitrary described yielding rubber of claim 1-11, comprise the steps:
(1) matrix resin is dropped into Banbury mixer, plasticate and obtain Blend rubber;
(2) after the Blend rubber described in step (1) being parked, then add hydroxy-end capped polyhutadiene, auxiliary agent, after mixing rear slice cooling, obtain compounding mixture;
(3) in the compounding mixture in step (2), add vulcanizing agent to mix on a mill until, slice after thin-pass, obtains described yielding rubber.
13. preparation methods according to claim 12, is characterized in that, in step (2), also add and have trithiocyanuric acid while adding auxiliary agent, and the main rubber content of relative 100 weight parts of described trithiocyanuric acid is 1-5 weight part.
14. preparation methods according to claim 12, is characterized in that, the auxiliary agent added in step (2) is one or more in strengthening agent, softening agent, chemical antiager, wax class anti-aging agent, vulcanization leveller; With the main rubber of 100 weight parts for benchmark, strengthening agent 20 ~ 100 weight part, softening agent 5 ~ 20 weight part, chemical antiager 2 ~ 10 weight part, wax class anti-aging agent 0.5 ~ 3.5 weight part, vulcanization leveller 2.5 ~ 13 weight part.
15. preparation methods according to claim 12, is characterized in that, in step (3), also add and have promotor while adding vulcanizing agent, and with the main rubber of 100 weight parts for benchmark, described promotor is 0.5 ~ 8 weight part.
16. preparation methods according to claim 12, is characterized in that, with the main rubber of 100 weight parts for benchmark, described vulcanizing agent is 0.5 ~ 5 weight part, and described hydroxy-end capped polyhutadiene is 5 ~ 30 weight parts.
17. preparation methods according to claim 12, is characterized in that, mixing in step (2) is carried out at 100 ~ 200 DEG C.
18. 1 kinds of automobile-used yielding rubber parts, are made up of the arbitrary described yielding rubber of claim 1-11.
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