CN104761912A - Damping silicon rubber with relatively small temperature effect and preparation method thereof - Google Patents
Damping silicon rubber with relatively small temperature effect and preparation method thereof Download PDFInfo
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Abstract
The invention relates to damping silicon rubber with a relatively small temperature effect and a preparation method thereof. The crude rubber of the damping silicon rubber is characterized in that a main chain of the crude rubber of the silicon rubber consists of methyl phenyl silicone chain elements, diethyl silicone chain elements, dimethyl silicone chain elements and methyl ethylene silicone chain elements with different content; the molecular weight of the crude rubber is more than 400 thousands; the crude rubber is prepared by copolymerizing methyl phenyl cyclosiloxane, diethyl cyclosiloxane, dimethyl cyclosiloxane and methyl ethylene cyclosiloxane in the presence of initiators of polypropylene oxide and the like. The crude rubber with the structure has good damping property in a relatively wide temperature range after being vulcanized, the dynamic loss factor and the modulus hardly change along with temperature changes, and the damping silicon rubber belongs to the field of organic silicon high polymer.
Description
Technical field
The invention belongs to silicon rubber preparation field, particularly a kind of have damping silicon rubber of less temperature effective and preparation method thereof.
Background technology
The elastomeric material that silicon rubber is is main chain with-Si-O-chain link, has excellent high-and low-temperature resistance performance, stable mechanical property under wide wide temperature range frequency.Silicon rubber can be used as damping material and is widely used in the fields such as aerospace, compensate for the shortcoming that conventional damping shock absorption material temperature range is narrow.But common silicon rubber damping factor less (being generally 0.05-0.1), or damping factor and dynamic modulus vary with temperature greatly, are difficult to meet the application higher to damping stability requirement.
Chinese patent CN102181056A discloses a kind of preparation method preparing damping silicon rubber, this damping silicon rubber is made up of diphenyl siloxane chain link, methylphenyl siloxane chain link, dimethyl siloxane chain link and methyl vinyl silicone chain link, when phenyl chain link molar content is greater than 20%, when aminomethyl phenyl structural unit/phenylbenzene structural unit mol ratio is 2/1, the silicon rubber obtained is-50-150 DEG C of temperature range internal loss factor tan δ >=0.3.Hollow glass micropearl is added and mica filler can make the damping factor of material bring up to 1.5 in mixing formula, but can raise along with temperature or reduce and suddenly decline ,-100 DEG C time, damping factor drops to less than 0.1, and this present invention is complicated, the used time is longer.
A kind of preparation method containing methyl phenyl vinyl damping silicon rubber is disclosed in Chinese patent CN1746224A, it is characterized in that in rubber containing methylphenyl siloxane chain link, dimethyl siloxane chain link and methyl vinyl silicone chain link, be used for dyeing through the white carbon black reinforcement of silazane process and ferric oxide by adding and be improve its thermotolerance, damping silicon rubber disclosed in this patent is-50 DEG C-100 DEG C temperature range internal damping factor t an δ >=0.2, and the temperature of p-less than 50 DEG C is not studied.A kind of methyl phenyl silicone rubber of low phenyl content is disclosed in Chinese patent CN101962480A, this rubber is formed by mechanical blendings such as low-phenyl silicone rubber, vinyl silicone oil, white carbon blacks, this material mechanical performance is poor, lower at use temperature scope-50 DEG C of-150 DEG C of internal damping coefficients, tan δ
maxbe no more than 0.4, especially below-20 DEG C, tan δ <0.1, shows that this damping material damping is at low temperatures bad.
US Patent No. 5332795 has openly prepared a kind of organosilicon Silica hydrogel containing phenyl group and trifluoropropyl group, material has good damping characteristic and resistance to low temperature, it is that micromolecular silicone oil is by crosslinked that the gel of this patent adopts, the lower crosslink density formed, intensity is low, and distortion is large, the material that can only use as weighting material, can not use as elastomerics, the damping capacity of material is larger by the impact of frequency.US Patent No. 6777486 discloses one and is dispersed in silicone oil by polymer hollow particles, powdered inorganic material, and preparation can be applicable to the organosilicon material of CD and car navigation device damping.
Summary of the invention
For solving the problem, the invention discloses a kind of organosilicon polymer in very wide temperature range with stable dissipation factor and dynamic modulus, the constructional feature of this polymkeric substance is: main chain is made up of di-ethyl siloxane chain link, methylphenyl siloxane chain link and (or) diphenyl siloxane chain link and a small amount of vinyl methyl siloxane chain link, molecular weight, more than 400,000, has good mechanical property.The steric effect of phenyl increases the interior rotational resistance of molecular chain, can improve the damping capacity of material, and the introducing of phenyl can also improve the ability of material radiation resistance, anti-oxidant and high-and low-temperature resistance.Introduce the resistance to low temperature that ethyl can improve rubber, and reduce the second-order transition temperature of rubber, make rubber under the low-down environment of temperature, still have excellent damping capacity.Because methyl phenyl ring siloxane is as tetramethyl tetraphenyl cyclotetrasiloxane, trimethyl triphenyl cyclotrisiloxane, pentamethyl-pentapheneyl D5s etc. are large with the ring strain of phenylbenzene cyclosiloxane as octaphenylcyclotetrasiloxane, anionic ring-opening polymerization activity is high, and hexaetcycletrisiloxane is greatly sterically hindered, anionic ring-opening polymerization activity is low, therefore, be difficult to the multipolymer preparing both, the present invention adopts methylphenyl siloxane mixed methylcyclosiloxane and (or) phenylbenzene cyclosiloxane, hexaetcycletrisiloxane, octamethylcyclotetrasiloxane and methylvinylcyclosiloxane, under anionic initiator existent condition, the feature of this anionic initiator is the mode adopting chain alkyl quaternary amine alkali, the high molecular silicon rubber containing methylphenyl siloxane chain link and (or) diphenyl siloxane chain link and di-ethyl siloxane chain link of preparation, this silicon rubber has excellent resistance to height, low-temperature performance, and damping capacity, and damping capacity is very little to the dependency of temperature, substantially remain unchanged in the very wide temperature range internal damping factor.
For achieving the above object, the present invention adopts following technical scheme:
A kind of damping silicon rubber with less temperature effective, described damping silicon rubber is by containing 0-50% methylphenyl siloxane chain link and/or diphenyl siloxane chain link, obtain through mixing, sulfuration with the copolymerization rubber of 10-99.5% di-ethyl siloxane chain link, and this copolymerization rubber has following structure:
Wherein, R is trimethylsiloxy group or dimethyl ethenyl siloxy; W/ (w+x+y+a+z) * 100%=0-70%; X/ (w+x+y+a+z) * 100%=10-99.5%; Y/ (w+x+y+a+z) * 100%=0-50%; A/ (w+x+y+a+z) * 100%=0-50%; (y+a)/(w+x+y+a+z) * 100%=0-50%; Z/ (w+x+y+a+z) * 100%=0.1-5%;
0≤W≤189190,392≤X≤200000,0≤Y≤73530,0≤A≤5050,4≤Z≤11628, molecular weight is 4.0 × 10
5-2.0 × 10
7.
There is a preparation method for the damping silicon rubber of less temperature effective, comprise the following steps:
(1) sily oxide and basic metal or alkaline earth metal hydroxides are added reactor according to the ratio of mol ratio 1:0.5, according to sily oxide, anhydrous inert solvent, the ratio of the mass ratio of poly(propylene oxide): 3-9:5-15:0.3-1 adds anhydrous inert solvent and molecular weight is the poly(propylene oxide) of 800-1000, closed reactor, be warming up to 100 DEG C of reaction 1-2hr, add corresponding with above-mentioned basic metal or alkaline earth metal hydroxides kind again, the elemental metals of identical mole number, continue reaction 1-2hr, add again with sily oxide mol ratio be the methyl phenyl ring siloxane of 3:1 and hexaetcycletrisiloxane mixture (wherein, the mol ratio of methyl phenyl ring siloxane and hexaetcycletrisiloxane is 1:1), 3-4hr is reacted at 70-120 DEG C, decompression steams small molecules, obtain initiator,
(2) by methyl phenyl ring siloxane (D
n ph, n=3-5) and/or phenylbenzene cyclosiloxane (D
n 2Ph, n=3-5), hexaetcycletrisiloxane, octamethylcyclotetrasiloxane, methylvinylcyclosiloxane join in reactor successively, vacuum-drying at 40-90 DEG C, passes into nitrogen; Be warming up to 80-180 DEG C, add initiator prepared by step (1), stirring reaction 30-60min in nitrogen atmosphere, continue balance 2-3h; Add acidic substance to neutralize, then remove lower-molecular substance, obtain copolymerization rubber;
(3) by rubber 30-40 weight part obtained in step (2) at mill mixing, and add 30-50 weight part white carbon black and 2-3 parts of peroxide vulcanizing agent, and evenly mixing, then carry out sulfuration, temperature: 120-180 DEG C, the time is 20-40min; Post vulcanization, temperature: 160-200 DEG C, the time is 30-40min, must obtain the high damping silicone rubber with less temperature effective.
Preferably, in step (1), described sily oxide refer to as hexamethyldisiloxane, divinyl disiloxane or tetraphenyl dimethyldisiloxane similar structures containing two Siliciumatom simple function organo-siloxanes, preferred tetramethyl divinyl siloxanes.
Preferably, alkali metal hydroxide described in step (1) or alkaline earth metal hydroxides refer to lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, hydrated barta or calcium hydroxide, and described basic metal, alkaline-earth metal refer to potassium metal, sodium Metal 99.5 or calcium metal.
Preferably, in step (2), described initiator is basic metal or alkaline-earth metal silicon alkoxide, and add-on is the 0.001%-1% of reactant quality.
Preferably, in step (2), the general structure of described methyl phenyl ring siloxane or phenylbenzene cyclosiloxane, hexaetcycletrisiloxane, octamethylcyclotetrasiloxane, methylvinylcyclosiloxane is:
If methyl phenyl ring siloxane, then R
1=methyl or phenyl, R
2=phenyl, n=3,4,5; If phenylbenzene cyclosiloxane, then R
1=R
2=phenyl, n=3,4,5; If hexaetcycletrisiloxane, then R
1=R
2=ethyl (C
2h
5-), n=3; If octamethylcyclotetrasiloxane, then R
1=R
2=methyl, n=4; If methylvinylcyclosiloxane, then R
1=methyl, R
2=vinyl (-CH=CH
2), n=3,4.
Preferably, in step (2), neutralizing acidic substance used is formic acid, acetic acid, oxalic acid, hydrochloric acid, phosphoric acid, phosphoric anhydride, SODIUM PHOSPHATE, MONOBASIC or CO
2, preferable formic acid, oxalic acid or CO
2.
Preferably, in step (2), add methyl phenyl ring siloxane and/or phenylbenzene cyclosiloxane 0.1-50 part, hexaetcycletrisiloxane 20-99.45 part, octamethylcyclotetrasiloxane 50-70 part, methylvinylcyclosiloxane 0.5-2 part, amounts to 100 parts.
Preferably, in step (2), described in remove lower-molecular substance method be: in vacuum tightness under-0.1MPa ~-0.095MPa, be warming up to T=150-200 DEG C, remove lower-molecular substance.
Preferably, in step (3), the temperature of preferred one step cure is 150-180 DEG C, and the temperature of post vulcanization is 180-200 DEG C.Preferred white carbon black is gas-phase silica, and preferred add-on is 40-50 part.Preferred peroxide vulcanizing agent is 2,4-dichlorobenzoperoxides (two-2,4) or two (tert-butyl peroxide) hexane (two-2,5) of 2,5-dimethyl-2,5-of 2-4 part.
Beneficial effect of the present invention:
(1) method adopting initiator provided by the invention to prepare, can guarantee that initiator activity is high, polymkeric substance one end is with predetermined functional group, and as silica-based in dimethyl ethenyl, methyldiphenyl base is silica-based, trimethyl silicon based, and this has very large effect to the performance improving polymkeric substance.
(2) phenyl siloxane chain link has larger volume, and make the internal friction resistance of sub-chain motion comparatively large, thus in-fighting is larger, and damping is better.And the introducing of phenyl can the regularity of larger reduction ethyl silicon rubber, reduces Tc and degree of crystallinity, thus improves the low temperature resistant energy of silicon rubber; The introducing of appropriate phenyl can improve the thermotolerance of ethyl silicon rubber.Thus, aminomethyl phenyl and (or) diphenyl siloxane chain link are incorporated in silicon rubber by the present invention, and the obtained ethyl silicon rubber containing phenyl, has better high-and low-temperature resistance performance.In addition, ethyl silicon rubber second-order transition temperature is very low, and the ethyl of introducing makes the second-order transition temperature of rubber move to low temperature, and this just substantially increases the damping capacity of rubber under low temperature, makes it be applicable to harsher envrionment conditions.Meanwhile, this copolymerization silicon rubber containing methylphenyl siloxane chain link and ethylsiloxane chain link achieves the effect of wide temperature zone high damping, and in wide temperature range, dissipation factor temperature influence is less, and damping capacity is stablized.
(3) polymkeric substance that the present invention prepares has very high molecular weight, can reach more than 400,000, rubber unvulcanizate excellent performance.
(4) add a small amount of methylvinylcyclosiloxane in the polymerization and the end of the chain is vinyl, make silicon rubber vulcanization activity of the present invention high, the compression set of products obtained therefrom is low, and performance is good.
(5) preparation method's technique of the present invention is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1: the infrared spectrogram of the aminomethyl phenyl diethyl copolymerization rubber that case study on implementation 4,8,9 is prepared
Fig. 2: the ultraviolet spectrogram of the aminomethyl phenyl diethyl copolymerization rubber that case study on implementation 4,8,9 is prepared
Fig. 3: case study on implementation 8 prepares cross-linked rubber DMA curve
Fig. 4: the cross-linked rubber dynamic modulus curve that case study on implementation 8 prepares
Embodiment
The present invention is further illustrated in conjunction with the embodiments, should be noted that following explanation is only to explain the present invention, not limiting its content.
Embodiment 1: 18.6g tetramethyl divinyl disiloxane and 2g sodium hydroxide powder are added voltage-resistant reactor, add 15ml dry toluene and 2g molecular weight is the poly(propylene oxide) of 1000, closed reactor, be warming up to 100 thermotonus 1hr, at being cooled to-5 DEG C, press-in 1.15g sodium silk, progressively be warming up to 80 DEG C, continue reaction 1hr, add the mixture of 40.8g methyl phenyl ring siloxane and 45.9g hexaetcycletrisiloxane again, 2hr is reacted at 100 DEG C, continue to be warming up to 120 DEG C steam toluene and react 1hr, be down to room temperature, obtain sodium hydroxide silicon alkoxide initiator.
Embodiment 2: 9.3g tetramethyl divinyl disiloxane and 1.425g calcium hydroxide powder are added voltage-resistant reactor, add 15ml dry toluene and 2g molecular weight is the poly(propylene oxide) of 1000, closed reactor, be warming up to 150 thermotonus 1hr, at being cooled to-5 DEG C, press-in 1g calcium silk, progressively be warming up to 80 DEG C, continue reaction 1hr, add the mixture of 20.4g methyl phenyl ring siloxane and 23g hexaetcycletrisiloxane again, 2hr is reacted at 100 DEG C, continue to be warming up to 120 DEG C steam toluene and react 1hr, be down to room temperature, obtain calcium hydroxide silicon alkoxide initiator.
Embodiment 3: as a comparison, ordinary method is adopted to prepare sodium hydroxide silicon alkoxide, 4g sodium hydroxide powder is added reactor, the mixture adding 10.2g methyl phenyl ring siloxane and 11.95g hexaetcycletrisiloxane is warming up to 100 thermotonus 1hr, add the mixture of 30.6g methyl phenyl ring siloxane and 35.85g hexaetcycletrisiloxane again, at 100 DEG C, react 2hr, continue to be warming up to 120 DEG C of reaction 1hr, be down to room temperature, obtain sodium hydroxide silicon alkoxide initiator.
Case study on implementation 4: by 41.86g hexaetcycletrisiloxane, 0.19g t etram-ethyltetravinylcyclotetrasiloxane (D
4 vi), 2.95g methyl phenyl ring siloxane joins in reactor, the lower 40 DEG C of dry 30min of vacuum condition; Use N
2replace three times; Temperature is increased to 160 DEG C, and add the silicon alkoxide (in sodium hydroxide) of the sodium hydroxide of case study on implementation 1 preparation accounting for reactant total mass 0.01%, fully stir, reaction system starts viscosity and increases to rapidly bag axle, stops stirring, and continues balance 2h; Material is proceeded to kneader and add the neutralization of 0.1g oxalic acid, heat up most 190 DEG C, remove small molecules under vacuo, cooling discharge, obtained methylphenyl siloxane chain link is 5%, and di-ethyl siloxane chain link is the copolymerization raw-silastic continuously copolymerization rubber of 94.5%, molecular weight 62.3 ten thousand.
Case study on implementation 5: rubber obtained in step (2) is carried out sulfuration.Take rubber 35g, be added in mill, make rubber bag be attached on cylinder, get 50 parts of gas-phase silica TS530, repeatedly mixing to evenly on cylinder, add 2 part of 2,4-dichlorobenzoperoxide (two-2,4), evenly mixing, thin-pass about 10 times, blanking slice.The one step cure temperature of copolymerization silicon rubber is set in 150 DEG C, and curing time is 20min, 180 DEG C of post vulcanization 30min, obtained cross-linked rubber.Cross-linked rubber tensile strength is 8.2MPa, and tear strength is 28KN/m.
Embodiment 6: adopt initiator prepared by case study on implementation 2, the methylphenyl siloxane chain link content prepared according to proportioning and the method for case study on implementation 3,4,5 is 5%, di-ethyl siloxane chain link to be the molecular weight of the copolymerization raw-silastic continuously of 94.5% be 51.2 ten thousand and the tensile strength of cross-linked rubber be 7.6MPa, tear strength is 26KN/m.
Embodiment 7: as a comparison, adopt initiator prepared by case study on implementation 3, the methylphenyl siloxane chain link content prepared according to proportioning and the method for case study on implementation 3-5 is 5%, di-ethyl siloxane chain link to be the molecular weight of the copolymerization raw-silastic continuously of 94.5% be 18.7 ten thousand and the tensile strength of cross-linked rubber be 5.2MPa, tear strength is 18KN/m.
Case study on implementation 8: by 39g hexaetcycletrisiloxane, 0.19g t etram-ethyltetravinylcyclotetrasiloxane (D
4 vi), 5.81g methyl phenyl ring siloxane adds in reactor successively, the lower 40 DEG C of dry 30min of vacuum condition; Use N
2replace three times; Temperature is increased to 160 DEG C, and add the silicon alkoxide (in sodium hydroxide) of the sodium hydroxide accounting for the preparation of reactant total mass 0.19g case study on implementation 1, fully stir, reaction system starts viscosity and increases to rapidly bag axle, stops stirring, and continues balance 2h; Material is proceeded to kneader and add the neutralization of 0.1g oxalic acid, heat up most 190 DEG C, remove small molecules under vacuo, cooling discharge, obtained methylphenyl siloxane chain link is 10%, and di-ethyl siloxane chain link is the copolymerization raw-silastic continuously of 89.5%, molecular weight 550,000.
Rubber obtained in above-mentioned case study on implementation is carried out sulfuration.Take rubber 35g, be added in mill, make rubber bag be attached on cylinder, get 50 parts of gas-phase silica TS530, repeatedly mixing to evenly on cylinder, add 2 part of 2,4-dichlorobenzoperoxide (two-2,4), evenly mixing, thin-pass about 10 times, blanking slice.The one step cure temperature of copolymerization silicon rubber is set in 150 DEG C, and curing time is 20min, 180 DEG C of post vulcanization 30min, obtained cross-linked rubber.Cross-linked rubber tensile strength is 8.4MPa, and tear strength is 30KN/m.Fig. 3 and Fig. 4 is dynamic properties curve and the dynamic modulus curve of the cross-linked rubber that this case study on implementation prepares, as we can see from the figure, its second-order transition temperature is-110 DEG C, tan δ can reach 0.5, and under-60 DEG C and higher temperature, the dissipation factor of rubber is all stabilized in 0.2-0.24, all little in the change of wide temperature range internal loss factor, shows little temperature effective; Modulus all remains unchanged more than-90 DEG C, shows the feature of good permanent modulus.
Case study on implementation 9: by 33.38g hexaetcycletrisiloxane, 0.35g t etram-ethyltetravinylcyclotetrasiloxane (D
4 vi), 11.27g methyl phenyl ring siloxane joins in reactor, the lower 40 DEG C of dry 30min of vacuum condition; Use N
2replace three times; Temperature is increased to 160 DEG C, and add the silicon alkoxide (in sodium hydroxide) of the sodium hydroxide of case study on implementation 1 preparation accounting for reactant total mass 0.01%, fully stir, reaction system starts viscosity and increases to rapidly bag axle, stops stirring, and continues balance 2h; Material is proceeded to kneader and add the neutralization of 0.1g oxalic acid, heat up most 190 DEG C, remove small molecules under vacuo, cooling discharge, obtained methylphenyl siloxane chain link is 20%, and di-ethyl siloxane chain link is the copolymerization raw-silastic continuously of 79%, molecular weight 55.7 ten thousand.
Rubber obtained in above-mentioned case study on implementation is carried out sulfuration.Take rubber 35g, be added in mill, make rubber bag be attached on cylinder, get 50 parts of gas-phase silica TS530, repeatedly mixing to evenly on cylinder, add 2 part of 2,4-dichlorobenzoperoxide (two-2,4), evenly mixing, thin-pass about 10 times, blanking slice.The one step cure temperature of copolymerization silicon rubber is set in 150 DEG C, and curing time is 20min, 180 DEG C of post vulcanization 30min, obtained cross-linked rubber.Cross-linked rubber tensile strength is 8.8MPa, and tear strength is 31KN/m.
Case study on implementation 10: by 33.38g hexaetcycletrisiloxane, 0.35g t etram-ethyltetravinylcyclotetrasiloxane (D
4 vi), 5.64g methyl phenyl ring siloxane and 8.21g phenylbenzene cyclosiloxane join in reactor, the lower 40 DEG C of dry 30min of vacuum condition; Use N
2replace three times; Temperature is increased to 160 DEG C, and add the silicon alkoxide (in sodium hydroxide) of the sodium hydroxide of case study on implementation 1 preparation accounting for reactant total mass 0.01%, fully stir, reaction system starts viscosity and increases to rapidly bag axle, stops stirring, and continues balance 2h; Material is proceeded to kneader and add the neutralization of 0.1g oxalic acid, heat up most 190 DEG C, remove small molecules under vacuo, cooling discharge, obtained methylphenyl siloxane chain link is 10%, and phenylbenzene chain link is 10%, di-ethyl siloxane chain link is the copolymerization raw-silastic continuously of 79%, molecular weight 580,000.
Rubber obtained in above-mentioned case study on implementation is carried out sulfuration.Take rubber 35g, be added in mill, make rubber bag be attached on cylinder, get 50 parts of gas-phase silica TS530, repeatedly mixing to even on cylinder, add 2 part of 2,5-two (tert-butyl peroxide) hexane (two-2 of dimethyl-2,5-, 5), evenly mixing, thin-pass about 10 times, blanking slice.The one step cure temperature of copolymerization silicon rubber is set in 150 DEG C, and curing time is 20min, 180 DEG C of post vulcanization 30min, obtained cross-linked rubber.Cross-linked rubber tensile strength is 9.0MPa, and tear strength is 22KN/m.
Case study on implementation 11: by 13g hexaetcycletrisiloxane, 18.9g tetramethyl-ring tetrasiloxane, 0.19g t etram-ethyltetravinylcyclotetrasiloxane (D
4 vi), 5.81g methyl phenyl ring siloxane adds in reactor successively, the lower 40 DEG C of dry 30min of vacuum condition; Use N
2replace three times; Temperature is increased to 160 DEG C, and add the silicon alkoxide (in sodium hydroxide) of the sodium hydroxide accounting for the preparation of reactant total mass 0.19g case study on implementation 1, fully stir, reaction system starts viscosity and increases to rapidly bag axle, stops stirring, and continues balance 2h; Material is proceeded to kneader and add the neutralization of 0.1g oxalic acid, heat up most 190 DEG C, remove small molecules under vacuo, cooling discharge, obtained methylphenyl siloxane chain link is 10%, di-ethyl siloxane chain link is 29.8%, and dimethyl siloxane chain link content is the copolymerization raw-silastic continuously of 59.6%, molecular weight 550,000.
Rubber obtained in above-mentioned case study on implementation is carried out sulfuration.Take rubber 35g, be added in mill, make rubber bag be attached on cylinder, get 50 parts of gas-phase silica TS530, repeatedly mixing to evenly on cylinder, add 2 part of 2,4-dichlorobenzoperoxide (two-2,4), evenly mixing, thin-pass about 10 times, blanking slice.The one step cure temperature of copolymerization silicon rubber is set in 150 DEG C, and curing time is 20min, 180 DEG C of post vulcanization 30min, obtained cross-linked rubber.Cross-linked rubber tensile strength is 8.6MPa, and tear strength is 37KN/m.
Case study on implementation 12: according to Monomer Formations and the condition of case study on implementation 11, add initiator prepared by case study on implementation 3, can only obtain the oyster white oily matter of thickness, curability is very poor.
Case study on implementation 13: according to the method for standard, the rubber that case study on implementation 4,8,9 prepares is carried out infrared and UV spectrum sign, Fig. 1 is the infrared spectrum of embodiment 4 (No. 2), 8 (No. 3), 9 (No. 4).The existence of the groups such as phenyl, ethyl, vinyl can be judged from figure.Fig. 2 is case study on implementation 4 (No. 2), the known phenyl that is absorbed as showing medium tenacity in 250-290nm of the uv-spectrogram of 8 (No. 3), 9 (No. 4) rubber absorbs, along with phenyl content is increased to 20% from 5%, the absorption of phenyl is increased successively.
Claims (10)
1. one kind has the damping silicon rubber of less temperature effective, it is characterized in that, described damping silicon rubber is by containing 0-50% methylphenyl siloxane chain link and/or diphenyl siloxane chain link, obtain through mixing, sulfuration with the copolymerization rubber of 10-99.5% di-ethyl siloxane chain link, and described copolymerization rubber has following structure:
Wherein, R is trimethylsiloxy group or dimethyl ethenyl siloxy; 0≤W≤189190,392≤X≤200000,0≤Y≤73530,0≤A≤5050,4≤Z≤11628, molecular weight is 4.0 × 10
5-2.0 × 10
7.
2. there is the damping silicon rubber of less temperature effective as claimed in claim 1, it is characterized in that, w/ (w+x+y+a+z) * 100=0-70%; X/ (w+x+y+a+z) * 100%=10-99.5%; Y/ (w+x+y+a+z) * 100%=0-50%; A/ (w+x+y+a+z) * 100%=0-50%; (y+a)/(w+x+y+a+z) * 100%=0-50%; Z/ (w+x+y+a+z) * 100%=0.1-5%.
3. there is a preparation method for the damping silicon rubber of less temperature effective, it is characterized in that, comprise the following steps:
(1) sily oxide and basic metal or alkaline earth metal hydroxides are added reactor according to the ratio of mol ratio 1:0.5, according to sily oxide, anhydrous inert solvent, the ratio of the mass ratio of poly(propylene oxide): 3-9:5-15:0.3-1 adds anhydrous inert solvent and molecular weight is the poly(propylene oxide) of 800-1000, closed reactor, be warming up to 100 DEG C of reaction 1-2hr, add corresponding with above-mentioned basic metal or alkaline earth metal hydroxides kind again, the elemental metals of identical mole number, continue reaction 1-2hr, add with sily oxide mol ratio is the methyl phenyl ring siloxane of 3:1 and the mixture of hexaetcycletrisiloxane again, 3-4hr is reacted at 70-120 DEG C, decompression steams small molecules, obtain initiator, in the mixture of described methyl phenyl ring siloxane and hexaetcycletrisiloxane, the mol ratio of methyl phenyl ring siloxane and hexaetcycletrisiloxane is 1:1,
(2) by methyl phenyl ring siloxane (D
n ph, n=3-5) and/or phenylbenzene cyclosiloxane (D
n 2Ph, n=3-5), hexaetcycletrisiloxane, octamethylcyclotetrasiloxane, methylvinylcyclosiloxane join in reactor successively, vacuum-drying at 40-90 DEG C, passes into nitrogen; Be warming up to 80-180 DEG C, add initiator prepared by step (1), stirring reaction 30-60min in nitrogen atmosphere, continue balance 2-3h; Add acidic substance to neutralize, then remove lower-molecular substance, obtain copolymerization rubber;
(3) by rubber 30-40 weight part obtained in step (2) at mill mixing, and add 30-50 weight part white carbon black and 2-3 parts of peroxide vulcanizing agent, and evenly mixing, then carry out sulfuration, temperature: 120-180 DEG C, the time is 20-40min; Post vulcanization, temperature: 160-200 DEG C, the time is 30min, must obtain the high damping silicone rubber with less temperature effective.
4. method as claimed in claim 2, it is characterized in that, in step (1), described sily oxide refer to as hexamethyldisiloxane, divinyl disiloxane or tetraphenyl dimethyldisiloxane similar structures containing two Siliciumatom simple function organo-siloxanes, preferred tetramethyl divinyl siloxanes.
5. method as claimed in claim 2, it is characterized in that, alkali metal hydroxide described in step (1) or alkaline earth metal hydroxides refer to lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, hydrated barta or calcium hydroxide, and described basic metal, alkaline-earth metal refer to potassium metal, sodium Metal 99.5 or calcium metal.
6. method as claimed in claim 2, it is characterized in that, in step (2), described initiator is basic metal or alkaline-earth metal silicon alkoxide, and add-on is the 0.001%-1% of reactant quality.
7. method as claimed in claim 2, it is characterized in that, in step (2), the general structure of described methyl phenyl ring siloxane or phenylbenzene cyclosiloxane, hexaetcycletrisiloxane, octamethylcyclotetrasiloxane, methylvinylcyclosiloxane is:
If methyl phenyl ring siloxane, then R
1=methyl or phenyl, R
2=phenyl, n=3,4,5; If phenylbenzene cyclosiloxane, then R
1=R
2=phenyl, n=3,4,5; If hexaetcycletrisiloxane, then R
1=R
2=ethyl (C
2h
5-), n=3; If octamethylcyclotetrasiloxane, then R
1=R
2=methyl, n=4; If methylvinylcyclosiloxane, then R
1=methyl, R
2=vinyl (-CH=CH
2), n=3,4.
8. method as claimed in claim 2, it is characterized in that, in step (2), neutralizing acidic substance used is formic acid, acetic acid, oxalic acid, hydrochloric acid, phosphoric acid, phosphoric anhydride, SODIUM PHOSPHATE, MONOBASIC or CO
2, preferable formic acid, oxalic acid or CO
2; Add methyl phenyl ring siloxane and (or) phenylbenzene cyclosiloxane 0.1-50 part, hexaetcycletrisiloxane 20-99.45 part, octamethylcyclotetrasiloxane 50-70 part, methylvinylcyclosiloxane 0.5-2 part, amount to 100 parts.
9. method as claimed in claim 2, is characterized in that, in step (2), described in remove lower-molecular substance method be: in vacuum tightness under-0.1MPa ~-0.095MPa, be warming up to T=150-200 DEG C, remove lower-molecular substance.
10. method as claimed in claim 2, it is characterized in that, in step (3), the temperature of preferred one step cure is 150-180 DEG C, and the temperature of post vulcanization is 180-200 DEG C; Preferred white carbon black is gas-phase silica, and preferred add-on is 40-50 part; Preferred peroxide vulcanizing agent is 2,4-dichlorobenzoperoxides (two-2,4) or two (tert-butyl peroxide) hexane (two-2,5) of 2,5-dimethyl-2,5-of 2-4 part.
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Cited By (11)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268433A (en) * | 1991-10-21 | 1993-12-07 | Shin-Etsu Chemical Co., Ltd. | Silicone composition and a highly damping hardened silicone material |
| CN101962480A (en) * | 2010-10-27 | 2011-02-02 | 航天材料及工艺研究所 | Low phenyl siloxane rubber-based wide temperature-range and high-damping material |
| CN103351628A (en) * | 2013-08-05 | 2013-10-16 | 中国工程物理研究院化工材料研究所 | High-modulus low-temperature damping silicon resin composition and preparation method thereof |
| CN103865272A (en) * | 2014-03-20 | 2014-06-18 | 株洲时代新材料科技股份有限公司 | Organic silicon impedance glue and preparation method thereof |
| CN104231637A (en) * | 2014-09-05 | 2014-12-24 | 国家电网公司 | Damping silicon rubber sound insulation material filled with glass microbeads |
-
2015
- 2015-04-07 CN CN201510161344.5A patent/CN104761912B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268433A (en) * | 1991-10-21 | 1993-12-07 | Shin-Etsu Chemical Co., Ltd. | Silicone composition and a highly damping hardened silicone material |
| CN101962480A (en) * | 2010-10-27 | 2011-02-02 | 航天材料及工艺研究所 | Low phenyl siloxane rubber-based wide temperature-range and high-damping material |
| CN103351628A (en) * | 2013-08-05 | 2013-10-16 | 中国工程物理研究院化工材料研究所 | High-modulus low-temperature damping silicon resin composition and preparation method thereof |
| CN103865272A (en) * | 2014-03-20 | 2014-06-18 | 株洲时代新材料科技股份有限公司 | Organic silicon impedance glue and preparation method thereof |
| CN104231637A (en) * | 2014-09-05 | 2014-12-24 | 国家电网公司 | Damping silicon rubber sound insulation material filled with glass microbeads |
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| CN105504826A (en) * | 2015-12-03 | 2016-04-20 | 中国航空工业集团公司北京航空材料研究院 | Silicone rubber material for flexible joint and preparation method of silicone rubber material |
| CN106188547A (en) * | 2016-07-08 | 2016-12-07 | 山东大学 | A kind of organosilicon damping additive and preparation method thereof |
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