CN101016392A - Crosslinking-type rubber-base damping material and preparing method thereof - Google Patents
Crosslinking-type rubber-base damping material and preparing method thereof Download PDFInfo
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- CN101016392A CN101016392A CN 200710063460 CN200710063460A CN101016392A CN 101016392 A CN101016392 A CN 101016392A CN 200710063460 CN200710063460 CN 200710063460 CN 200710063460 A CN200710063460 A CN 200710063460A CN 101016392 A CN101016392 A CN 101016392A
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Abstract
The invention discloses a cross bonding type rubber group damping material and preparing method, which comprises the following steps: choosing rubber material; adding into phenols organic small molecule as damping function additive and proper organic inclusive agent; supplying good mechanical property for rubber group damping material; improving damping property of material. The loss factor (eta) of material is higher, which can express good tensile strength and extension at break.
Description
Technical field:
The present invention relates to a kind of crosslinking-type rubber-base damping material and preparation method thereof.
Background technology:
Novel Applicaltion of damping material can make the stealthy performance of sound of naval vessel equipment produce qualitative leap, occupies very important position in the marine material research in future.Rubber-base damping material is a kind of base mateiral of realizing modern high technology.
The damping mechanism of conventional rubber-base damping material is based on the visco-elasticity of macromolecular material, and hysteresis phenomenon that polymer takes place under the repeated stress effect and mechanics loss are its basic reasons that produces damping action.The mechanics loss of material is bigger, wideer, the warm thresholding in glass transition temperature territory and outside atmosphere more meet, and damping better.
The vitrifying zone of transformation of single macromolecular material is narrower, uses the requirement that often can't satisfy wide temperature territory, broadband damping as damping material.For widening the vitrifying zone of transformation of damping material, the most frequently used method has blend, copolymerization, inorganic filling etc.
Thereby the principle of blend is to make polymer alloy have the peak width at half height of the structure expansion damping peak of micron-scale phase separation by blend, makes the trench of two (or a plurality of) glass transition region rise to the plateau region.Blend can be widened the warm territory of damping to a certain extent, and kinds such as rubber and blend rubber, rubber and plastic blend and rubber and fiber blend are arranged.
Copolymerization comprises graft copolymerization and block copolymerization, and graft copolymerization can make the in-fighting peak of multipolymer increase, and block copolymerization can make the glass transition temperature territory of multipolymer broaden, and can improve the damping capacity of material to a certain extent.
Inorganic filling refers to add mineral fillers such as mica, carbon black, talcum powder, vermiculite in polymkeric substance, produce friction when being in contact with one another owing to filler grain between particle, and also there are friction in particle and macromolecule interfacial simultaneously, thereby improve the damping capacity of material.
Above several method is the conventional means that improves the polymkeric substance damping capacity, can improve the in-fighting peak of material to a certain extent and widen its glass transition region, improves the damping capacity of material.But the amplitude that improves is limited.
Wu Chi fly to wait " state of aggregation of hindered phenol is to the influence of the dynamic properties of chlorinatedpolyethylene " (Chinese Journal ofPolymer Science, 2004,01:7-16) reported a kind of high-performance damping material.Hindered amine, Hinered phenols organic micromolecule compound are added formation binary organic hybrid body in chlorinatedpolyethylene (CPE), the polyacrylate polymers, effectively improved the damping capacity of material.But this method is only applicable to chlorinatedpolyethylene (CPE), polyacrylate polymers, and range of application is limited.
Three Pus just with her rattan wise man also (safe tex Co., Ltd., Tokyo, Japan) polymer matrix composite of a kind of high damping properties and preparation method thereof is disclosed at " shock material composition " in (CN1488664A).This material is a matrix with organic polymer (as acrylic elastomer), adds damping improving agent and inorganic and/or organic filler, has high dissipation factor and wide available temperature range.Vibration damping agent in this material is specific hindered phenol, and its chemical constitution is the branched hydrocarbyl that does not have 4 or more carbon atoms at two ortho positions of hydroxyl.This material mainly is applicable to vibration damping, and for the sound wave damping, especially the sound wave damping of low-frequency range is undesirable.
Wu Chi flies to wait (Tokai Rubber Industrial Co., Ltd, Japanese Komaki) to disclose a kind of polymer-based damping composite material as vibration damper and sound-proof material at " high damping properties matrix material " in (US6265475).This material is a matrix with the acrylic elastomer with polar side chain, add organic damping improving agents such as hindered phenol, hindered amine, bi-ester of phosphite, phosphate compound or nitrogenous basic cpd, be applicable to damping vibration and sound insulation, for the sound wave damping, especially the sound wave damping of low-frequency range is undesirable.
Summary of the invention
The object of the present invention is to provide a kind of crosslinking-type rubber-base damping material and preparation method thereof, adding the phenols organic molecule in selected elastomeric material is damping function additive and suitable organic compatilizer, makes the rubber-base damping material that obtains improve the damping capacity of material significantly when having mechanical property preferably.Particularly, the dissipation factor of material (η, just losstangenttan) is higher, makes material show high-caliber damping capacity in wideer range of frequency.Simultaneously, do not carrying out under the situation of filler reinforcement, bill of material reveals excellent tensile strength and elongation at break.
A kind of crosslinking-type rubber-base damping material provided by the invention is a kind of rubber-base composite material that comprises the damping function additive, and it is characterized in that: this damping function additive is the phenols organic molecule, and is selected from a kind of in following two kinds of phenols organic molecules:
(1) 3,9-pair 1,1-dimethyl-2[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] and ethyl-2,4,6,8-four oxa-volution (5,5)-undecanes }, structural formula is:
(2) four [β-(3,5-two-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, structural formula is:
In the above-mentioned crosslinking-type rubber-base damping material, the mass ratio of phenols organic molecule and base rubber is 10-100: 100, and scope is 40-60 preferably: 100.
Said base rubber is: isoprene-isobutylene rubber, paracril or styrene-butadiene rubber(SBR).
Above-mentioned base rubber can also add contain polar group resin as organic compatilizer, said organic compatilizer is polyvinyl chloride (PVC) RESINS, polyurethanes resin or resol.The mass ratio of organic compatilizer and rubber is 10-30: 90-70 in this base rubber.
The present invention also provides a kind of preparation method of crosslinking-type rubber-base damping material, phenols organic molecule and base rubber is more mixing than room temperature by the above-mentioned quality that provides, again through after high-temperature mixing, cooling, interpolation sulfuration cooperation system and the sulfuration, obtain the high-performance crosslinking-type rubber-base damping material, it is characterized in that: the temperature of high-temperature mixing is to be higher than fusing point 5-30 ℃ of phenolic group organic molecule; Curing temperature is to be higher than fusing point 10-30 ℃ of phenolic group organic molecule.
Process such as said mixing, sulfuration all is means of Rubber processing preparation technology routine among the above-mentioned preparation method, and it also is that this field is commonly used that the sulfuration that needs to add cooperates system, and using priciple is known.Sulfuration cooperation system generally comprises vulcanization leveller (as: zinc oxide, stearic acid) and vulcanization accelerator (as: dibenzothiazyl disulfide (altax), vulkacit D (vulkacit D), tetramethyl-thiuram disulfide (TM monex TD) and vulcanizing agent (as: sulphur S, brominated phenolic resin).The consumption of vulcanization system is high more, and the cross-linking density of rubber is also high more, otherwise then low more.For any elastomeric material, need moderate cross-linking density.
Rubber-base damping material of the present invention can be made Any shape, size at different applicable objects, is generally the sheet moulded products.Can select to use the sheet material of respective thickness according to the performance of specific application target and needs.
All properties test of the present invention is all carried out according to corresponding national standards.Can find out obviously that from the dynamic properties and the mechanical performance data of embodiments of the invention and Comparative Examples the rubber-base damping material of the inventive method preparation has high dissipation factor (η) and wide available temperature range, is a kind of novel damping material; The homodisperse of phenols small molecules in rubber matrix has good reinforced effects; Gained mechanical property of vulcanized rubber especially tensile strength and elongation at break has had significantly and has improved.
Embodiment:
The present invention will be described in more detail with embodiment and Comparative Examples, but be not limitation of the present invention.
Rubber-base damping material in the following example and the Comparative Examples, temperature range at-50 ℃ to 150 ℃, under the stretch mode of 1Hz frequency and 3 ℃/min heating rate and 0.1% dynamic stress, test its loss tangent (Tan δ) by the dynamic viscoelasticity spectrum instrument, testing plate size for 20mm length * 5mm wide * 1mm is thick.
Embodiment 1 to 9
The rubber-base damping material of embodiment 1 to 9 preparation, the paracril that all adopts 100 mass parts add the phenols organic molecule shown in the table 1 as functional additive as base rubber, and the mass parts of interpolation also provides in table 1.Concrete preparation method and step are: under (1) room temperature paracril was plasticated in mill 3-5 minute, add the phenols organic molecule then, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, following sheet; (2) with the mixture high-temperature mixing that obtains 5-8 minute, melting temperature such as table 1 were listed, make the abundant fusion of additive, blanking, room temperature cooling; (3) under the room temperature, the mixture that obtains is added various vulcanization system Synergist S-421 95s in mill, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, obtained rubber unvulcanizate; (4) measure vulcanization curve with vulkameter and determine curing time, vulcanize sample on vulcanizing press, curing temperature such as table 1 are listed, obtain the thick sheet crosslinking-type rubber-base damping material sample of 1mm.Embodiment 1 to 9 used vulcanization system is (mass fraction is in 100 parts of paracrils): 2 parts in sulphur; 5 parts in zinc oxide; 2 parts of stearic acid; 0.5 part of altax; 0.5 part of vulkacit D; 0.2 part of TM monex TD.
Comparative Examples 1
Except substituting the damping additive of the present invention with disclosed a kind of amine organic molecule among the patent US6265475, with parent material, the vulcanization system identical and adopt identical operational path with embodiment 7, the hot-rolling melting temperature is controlled to be 130 ℃, the preparation crosslinking-type rubber-base damping material.The damping capacity assessment result of prepared material sees Table 1, and the mechanical property assessment result sees Table 2.
Comparative Examples 2
Except doing the damping additive, use the parent material identical to prepare matrix material with embodiment 7 without the phenols organic molecule.Concrete technology is: under (1) room temperature paracril was plasticated in mill 3-5 minute, add various vulcanization system Synergist S-421 95s then, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, obtained rubber unvulcanizate; (2) measure vulcanization curve with vulkameter and determine curing time, vulcanize sample on vulcanizing press, curing temperature is 160 ℃, obtains the thick sheet crosslinking-type rubber damping material of 1mm.The damping capacity assessment result of prepared material sees Table 1, and the mechanical property assessment result sees Table 2.
Table 1
| Rubber matrix | The phenols organic molecule | Processing condition | Maximum Tan δ | Tan δ is greater than 0.6 temperature range, ℃ | ||||
| Paracril | HP1 | HP2 | HP101 | The high-temperature mixing temperature/℃ | Curing temperature/℃ | |||
| Embodiment 1 | 100 | 20 | 0 | 0 | 140 | 150 | 2.04 | -6.7～11.0 |
| Embodiment 2 | 100 | 40 | 0 | 0 | 140 | 150 | 1.90 | -9.8～11.8 |
| Embodiment 3 | 100 | 60 | 0 | 0 | 140 | 150 | 1.76 | -0.15～15.6 |
| Embodiment 4 | 100 | 80 | 0 | 0 | 140 | 150 | 1.56 | -21.7～9.5 |
| Embodiment 5 | 100 | 0 | 20 | 0 | 130 | 160 | 2.20 | -5.94～15.4 |
| Embodiment 6 | 100 | 0 | 40 | 0 | 130 | 160 | 2.42 | 4.95～27.5 |
| Embodiment 7 | 100 | 0 | 60 | 0 | 130 | 160 | 2.66 | 8.44～32.2 |
| Embodiment 8 | 100 | 0 | 80 | 0 | 130 | 160 | 2.82 | 6.12～30.6 |
| Embodiment 9 | 100 | 0 | 100 | 0 | 130 | 160 | 3.20 | 12.3～38.0 |
| Comparative Examples 1 | 100 | 0 | 0 | 40 | 130 | 160 | 0.79 | -0.3～10.5 |
| Comparative Examples 2 | 100 | 0 | 0 | 0 | - | 160 | 1.82 | -24.0～-15.0 |
Annotate: 1. paracril adopts the product of the N220S trade mark that Japanese JSR company produces, acrylonitrile content 41%; Institute's column data is a mass fraction;
2.HP1: four [β-(3,5-two-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Institute's column data is a mass fraction;
3.HP2:3,9-pair 1,1-dimethyl-2[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] and ethyl-2,4,6,8-four oxa-volution (5,5)-undecanes }; Institute's column data is a mass fraction;
4.HP101: a kind of hindered amine organic molecule, chemical name is: poly--{ [6-[(1,1,3,3 ,-tetramethyl butyl)-imino-]-1,3,5 ,-triazine-2,4-two bases] [2-(2,2,6,6 ,-tetramethyl-piperidyl)-inferior amino-hexa-methylene-[4-(2,2,6, the 6-tetramethyl-piperidyl)-inferior amino]]; Institute's column data is a mass fraction;
From the correlation data of table 1 as can be seen, the maximum loss factor Tan δ of system descends significantly in the Comparative Examples 1, and Tan δ do not have to change greater than 0.6 temperature range substantially, and this additive is unsuitable for the used body material of the present invention.The damping capacity index of Comparative Examples 2 present higher dissipation factor Tan δ, but Tan δ is narrow greater than 0.6 temperature range.And the damping material of the present invention's preparation has very high dissipation factor (Tan δ), from 1.56 to 3.2, Tan δ is able to significantly increase greater than 0.6 temperature range, and, Tan δ moves to the high temperature direction greater than 0.6 temperature range, the second-order transition temperature that shows material raises, and helps the sound wave damping of material low frequency region, and wide warm territory scope and high dissipation factor show that advanced composite material of the present invention has excellent damping capacity.
Table 2
| Shao A hardness | 100% stress at definite elongation, MPa | 300% stress at definite elongation, MPa | Tensile strength, MPa | Elongation at break, % | Tension set/% | |
| Embodiment 1 | 62 | 1.0 | 1.7 | 5.3 | 491 | 2 |
| Embodiment 2 | 68 | 1.6 | 2.5 | 6.8 | 492 | 4 |
| Embodiment 3 | 72 | 1.3 | 2.3 | 5.3 | 427 | 6 |
| Embodiment 4 | 87 | 1.9 | 2.5 | 5.0 | 419 | 7 |
| Embodiment 5 | 57 | 1.1 | 2.0 | 11.0 | 540 | 4 |
| Embodiment 6 | 63 | 1.1 | 1.7 | 15.0 | 610 | 6 |
| Embodiment 7 | 75 | 1.0 | 1.4 | 17.8 | 710 | 6 |
| Embodiment 8 | 86 | 0.9 | 1.3 | 15.8 | 680 | 8 |
| Embodiment 9 | 88 | 0.8 | 1.2 | 14.4 | 650 | 8 |
| Comparative Examples 1 | 72 | 2.8 | 5.3 | 5.5 | 320 | 8 |
| Comparative Examples 2 | 59 | 1.3 | 2.7 | 3.1 | 373 | 4 |
From the correlation data of table 2 as can be seen, damping material of the present invention is not carrying out under the situation of filler reinforcement, the tensile strength of material and elongation at break have obtained considerable raising, and this illustrates that this material not only has excellent damping capacity but also has the good mechanical performance.
Embodiment 10 to 18
Rubber-base damping material for each embodiment 10 to 18 preparation, base rubber is the coprecipitated glue (70/30 of paracril/polyvinyl chloride, mass ratio, polyvinyl chloride (PVC) RESINS is as compatilizer), add the phenols organic molecule shown in the table 3 again, they are as functional additive, and addition also provides in table 3.Concrete preparation method and step are: under (1) room temperature the coprecipitated glue of paracril/polyvinyl chloride was plasticated in mill 3-5 minute, add the phenols small molecules then, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, following sheet; (2) with the mixture high-temperature mixing that obtains 5-8 minute, temperature was listed in table 3, makes the abundant fusion of additive, blanking, room temperature cooling; (3) under the room temperature, the mixture that obtains is added various vulcanization system Synergist S-421 95s in mill, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, obtained rubber unvulcanizate; (4) measure vulcanization curve with vulkameter and determine curing time, vulcanize sample on vulcanizing press, curing temperature such as table 3 are listed, obtain the thick sheet crosslinking-type rubber-base damping material sample of 1mm.Embodiment 10 to 18 used vulcanization systems are (mass fraction is in 100 parts of coprecipitated glue of paracril/polyvinyl chloride): 2 parts in sulphur; 5 parts in zinc oxide; 2 parts of stearic acid; 0.5 part of altax; 0.5 part of vulkacit D; TM monex TD0.2 part.
Comparative Examples 3
Except doing the damping additive, use the parent material identical to prepare matrix material with embodiment 16 without the phenols organic molecule.Concrete preparation method and step are: under (1) room temperature the coprecipitated glue of paracril/polyvinyl chloride was plasticated in mill 3-5 minute, add various vulcanization system Synergist S-421 95s then, the mixing 5-8 of cutter minute, thin-pass, play the triangle bag, make it mixing even, obtain rubber unvulcanizate; (2) measure vulcanization curve with vulkameter and determine curing time, vulcanize sample on vulcanizing press, curing temperature is 150 ℃, obtains the thick sheet crosslinking-type rubber damping material of 1mm.The damping capacity assessment result of prepared material sees Table 3, and the mechanical property assessment result sees Table 4.
Comparative Examples 4
Except substituting the damping additive of the present invention with disclosed a kind of amine organic molecule among the patent US6265475, with parent material, the vulcanization system identical and adopt identical operational path with embodiment 16, the hot-rolling melting temperature is controlled to be 135 ℃, the preparation crosslinking-type rubber-base damping material.The damping capacity assessment result of prepared material sees Table 3, and the mechanical property assessment result sees Table 4.
Table 3
| Rubber matrix | The phenols organic molecule | Processing condition | Maximum Tan δ | Tan δ is greater than 0.6 temperature range, ℃ | ||||
| The coprecipitated glue of paracril/polyvinyl chloride | HP1 | HP2 | HP101 | The high-temperature mixing temperature/℃ | Curing temperature/℃ | |||
| Embodiment 10 | 100 | 10 | 0 | 0 | 145 | 160 | 1.02 | -9.05～12.2 |
| Embodiment 11 | 100 | 30 | 0 | 0 | 145 | 160 | 1.05 | -1.67～17.5 |
| Embodiment 12 | 100 | 50 | 0 | 0 | 145 | 160 | 1.06 | 4.8～27.6 |
| Embodiment 13 | 100 | 70 | 0 | 0 | 145 | 160 | 1.19 | 9.44～29.7 |
| Embodiment 14 | 100 | 0 | 10 | 0 | 135 | 160 | 1.12 | 2.47～21.2 |
| Embodiment 15 | 100 | 0 | 30 | 0 | 135 | 150 | 1.39 | 7.78～30.6 |
| Embodiment 16 | 100 | 0 | 50 | 0 | 135 | 150 | 1.54 | 11.1～35.6 |
| Embodiment 17 | 100 | 0 | 70 | 0 | 135 | 150 | 1.52 | 13.5～41.7 |
| Embodiment 18 | 100 | 0 | 100 | 0 | 135 | 150 | 1.34 | 18.8～48.2 |
| Comparative Examples 3 | 100 | 0 | 0 | 0 | - | 150 | 0.94 | -15.9～11.1 |
| Comparative Examples 4 | 100 | 0 | 0 | 60 | 135 | 150 | 0.54 | - |
Annotate: 1. phenols organic molecule institute column data is a mass fraction;
2. the coprecipitated glue of paracril/polyvinyl chloride is the product of the new rubber of Beijing northization Science and Technology Ltd. trade mark 3470, and wherein the mass ratio of paracril and polyvinyl chloride is 70: 30, and institute's column data is a mass fraction;
From the correlation data of table 3 as can be seen, Comparative Examples 3 is compared with Comparative Examples 4, and the maximum loss factor of Comparative Examples 4 systems descends significantly, and maximum Tan δ does not reach the requirement of damping property index less than 0.6.And the damping material of the present invention's preparation has higher dissipation factor (Tan δ), from 1.02 to 1.54, Tan δ is able to significantly increase greater than 0.6 temperature range, and, Tan δ moves to the high temperature direction greater than 0.6 temperature range, the second-order transition temperature that shows material raises, and helps the sound wave damping of material low frequency region, and wide warm territory scope and high dissipation factor show that advanced composite material of the present invention has good damping capacity.
Table 4
| Shao A hardness | 300% stress at definite elongation, MPa | Tensile strength, MPa | Elongation at break, % | |
| Embodiment 10 | 83 | 7.8 | 14.3 | 370 |
| Embodiment 11 | 90 | 7.3 | 15.0 | 410 |
| Embodiment 12 | 93 | 7.0 | 15.9 | 495 |
| Embodiment 13 | 95 | 6.9 | 16.0 | 390 |
| Embodiment 14 | 85 | 6.8 | 12.1 | 400 |
| Embodiment 15 | 93 | 5.4 | 15.7 | 460 |
| Embodiment 16 | 93 | 5.0 | 18.2 | 480 |
| Embodiment 17 | 95 | 5.2 | 20.1 | 490 |
| Embodiment 18 | 95 | 5.6 | 12.8 | 450 |
| Comparative Examples 3 | 75 | 7.7 | 11.0 | 370 |
| Comparative Examples 4 | 68 | - | 5.1 | 240 |
From the correlation data of table 4 as can be seen, novel damping material of the present invention is not carrying out under the situation of filler reinforcement, the tensile strength of material and elongation at break have obtained certain raising, illustrate that damping material of the present invention not only has good damping performance but also has the good mechanical performance.
Embodiment 19
Rubber-base damping material for embodiment 19 preparations, matrix is a styrene-butadiene rubber(SBR), compatilizer is that (mass ratio of styrene-butadiene rubber(SBR) and brominated phenolic resin is respectively 80/20 to brominated phenolic resin, brominated phenolic resin is used as linking agent simultaneously), add the phenols organic molecule shown in the table 5, they are as functional additive, and addition also provides in table 5.Concrete preparation method and step are: under (1) room temperature styrene-butadiene rubber(SBR) was plasticated in mill 3-5 minute, add the phenols small molecules then, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, following sheet; (2) with the mixture high-temperature mixing that obtains 5-8 minute, temperature was listed in table 5, makes the abundant fusion of additive, blanking, room temperature cooling; (3) under the room temperature, the mixture that obtains is added brominated phenolic resin in mill, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, obtained rubber unvulcanizate; (4) measure vulcanization curve with vulkameter and determine curing time, vulcanize sample on vulcanizing press, curing temperature such as table 3 are listed, obtain the thick sheet crosslinking-type rubber-base damping material sample of 1mm.
Comparative Examples 5
Except doing the damping additive, use the parent material identical to prepare matrix material with embodiment 19 without the phenols organic molecule.Concrete preparation method and step are: under (1) room temperature isoprene-isobutylene rubber was plasticated in mill 3-5 minute, add brominated phenolic resin then, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, obtained rubber unvulcanizate; (2) measure vulcanization curve with vulkameter and determine curing time, vulcanize sample on vulcanizing press, curing temperature is 150 ℃, obtains the thick sheet crosslinking-type rubber damping material of 1mm.The damping capacity assessment result of prepared material sees Table 5.
Embodiment 20
Rubber-base damping material for embodiment 20 preparations, matrix is a paracril, and resol is as compatilizer, and (mass ratio of paracril and resol is respectively 85/15) adds the phenols organic molecule shown in the table 5, they are as functional additive, and addition also provides in table 5.Concrete preparation method and step are: under (1) room temperature paracril was plasticated in mill 3-5 minute, add resol and phenols small molecules then respectively, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, following sheet; (2) with the mixture high-temperature mixing that obtains 5-8 minute, temperature was listed in table 5, makes the abundant fusion of additive, blanking, room temperature cooling; (3) under the room temperature, the mixture that obtains is added various vulcanization system Synergist S-421 95s in mill, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, obtained rubber unvulcanizate; (4) measure vulcanization curve with vulkameter and determine curing time, vulcanize sample on vulcanizing press, curing temperature such as table 3 are listed, obtain the thick sheet crosslinking-type rubber-base damping material sample of 1mm.Embodiment 20 used vulcanization systems are (mass fraction is in 100 parts of nitrile rubber/phenolic rubber unvulcanizates): 2 parts in sulphur; 5 parts in zinc oxide; 2 parts of stearic acid; 0.5 part of altax; 0.5 part of vulkacit D; 0.2 part of TM monex TD.
Comparative Examples 6
Except doing the damping additive, use the parent material identical to prepare matrix material respectively with embodiment 21 without the phenols organic molecule.Concrete preparation method and step are: under (1) room temperature paracril was plasticated in mill 3-5 minute, add resol and various vulcanization system Synergist S-421 95 then, the mixing 5-8 of cutter minute, thin-pass was played the triangle bag, made it mixing even, obtained rubber unvulcanizate; (2) measure vulcanization curve with vulkameter and determine curing time, vulcanize sample on vulcanizing press, curing temperature is 150 ℃, obtains the thick sheet crosslinking-type rubber damping material of 1mm.The damping capacity assessment result of prepared material sees Table 5.
Table 5
| Rubber matrix | Phenols organic molecule HP2, mass fraction | Processing condition | Maximum Tan δ | Tan δ is greater than 0.6 temperature range, ℃ | ||
| The high-temperature mixing temperature/℃ | Curing temperature/℃ | |||||
| Embodiment 19 | 20 parts of 80 parts/brominated phenolic resins of styrene-butadiene rubber(SBR) | 15 | 145 | 150 | 1.78 | -35.5～2.8 |
| Comparative Examples 5 | 0 | - | 150 | 1.85 | -50.0-29.0 | |
| Embodiment 20 | 15 parts in 85 parts/resol of paracril | 60 | 145 | 150 | 2.67 | 17.5～46.5 |
| Comparative Examples 6 | 0 | - | 150 | 1.42 | 6.0～22.0 | |
Annotate: 1. the styrene-butadiene rubber(SBR) employing Jiization organic synthesis rubber plant trade mark is 1502 product;
Brominated phenolic resin adopt Taiyuan City unit too the biochemical industry company limited trade mark be the product of 201-2;
3. the gluing company of the resol employing Wuxi Ming Yang trade mark is 2123 product.
From the correlation data of table 5 as can be seen, the damping material of the present invention's preparation has higher dissipation factor (Tan δ), Tan δ is able to significantly increase greater than 0.6 temperature range, and, Tan δ moves to the high temperature direction greater than 0.6 temperature range, the second-order transition temperature that shows material raises, and helps the sound wave damping of material low frequency region, and wide warm territory scope and high dissipation factor show that advanced composite material of the present invention has good damping performance.
Claims (5)
1. a crosslinking-type rubber-base damping material is a kind of rubber-base composite material that comprises the damping function additive, and it is characterized in that: the damping function additive is the phenols organic molecule, and is selected from a kind of in following two kinds of phenols organic molecules:
(1) 3,9-pair 1,1-dimethyl-2[β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy] and ethyl-2,4,6,8-four oxa-volution (5,5)-undecanes }, structural formula is:
(2) four [β-(3,5-two-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, structural formula is:
And the mass ratio of phenols organic molecule and base rubber is 10-100: 100.
2. according to the crosslinking-type rubber-base damping material of claim 1, it is characterized in that: said base rubber is isoprene-isobutylene rubber, paracril or styrene-butadiene rubber(SBR).
3. according to the crosslinking-type rubber-base damping material of claim 1 or 2, it is characterized in that: in base rubber, add and contain the resin of polar group as organic compatilizer, said organic compatilizer is polyvinyl chloride (PVC) RESINS, polyurethanes resin or resol, and the mass ratio of organic compatilizer and rubber is 10-30: 90-70.
4. according to the crosslinking-type rubber-base damping material of claim 1 or 2 or 3, it is characterized in that: the mass ratio of phenols organic molecule and base rubber is 40-60: 100.
5. the preparation method of a crosslinking-type rubber-base damping material, phenols organic molecule and base rubber is more mixing than room temperature by any quality that provides of claim 1-4, again through after high-temperature mixing, cooling, interpolation sulfuration cooperation system and the sulfuration, obtain crosslinking-type rubber-base damping material, it is characterized in that: the temperature of high-temperature mixing is to be higher than fusing point 5-30 ℃ of phenolic group organic molecule; Curing temperature is to be higher than fusing point 10-30 ℃ of phenolic group organic molecule.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173066B (en) * | 2007-10-19 | 2010-06-30 | 东华大学 | Carboxy nitrile rubber high-performance damping material and method for producing the same |
| CN102838810A (en) * | 2012-07-26 | 2012-12-26 | 上海宝利纳材料科技有限公司 | Butyl rubber high performance material and preparation method thereof |
| CN103589012A (en) * | 2013-11-06 | 2014-02-19 | 北京航材昌盛科技有限公司 | High-strength and high-damping rubber material |
| CN103951924A (en) * | 2014-05-14 | 2014-07-30 | 北京化工大学 | Itaconate based bioengineering rubber damping material and preparation method thereof |
| CN104592654A (en) * | 2015-01-21 | 2015-05-06 | 柳州市颖航汽配有限公司 | Insulated rubber |
| CN105086018A (en) * | 2015-08-06 | 2015-11-25 | 国网智能电网研究院 | Shock absorbing rubber material used for transformer |
| CN108641031A (en) * | 2018-05-17 | 2018-10-12 | 北京化工大学 | A kind of hindered phenol/styrene-acrylic composite emulsion and preparation method thereof |
| CN108948724A (en) * | 2018-08-22 | 2018-12-07 | 清华大学 | A kind of preparation method of high mechanical loss factor thermoplastic urethane foam |
| CN109233015A (en) * | 2017-07-10 | 2019-01-18 | 北京化工大学 | A kind of support high-performance damping material, preparation method and its rubber shock absorption support |
| CN113195245A (en) * | 2018-12-17 | 2021-07-30 | 米其林集团总公司 | Rubber composition based on at least one functionalized elastomer comprising polar functional groups and specific polyphenolic compounds |
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2007
- 2007-02-01 CN CN 200710063460 patent/CN101016392A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173066B (en) * | 2007-10-19 | 2010-06-30 | 东华大学 | Carboxy nitrile rubber high-performance damping material and method for producing the same |
| CN102838810A (en) * | 2012-07-26 | 2012-12-26 | 上海宝利纳材料科技有限公司 | Butyl rubber high performance material and preparation method thereof |
| CN103589012A (en) * | 2013-11-06 | 2014-02-19 | 北京航材昌盛科技有限公司 | High-strength and high-damping rubber material |
| CN103951924A (en) * | 2014-05-14 | 2014-07-30 | 北京化工大学 | Itaconate based bioengineering rubber damping material and preparation method thereof |
| CN104592654A (en) * | 2015-01-21 | 2015-05-06 | 柳州市颖航汽配有限公司 | Insulated rubber |
| CN105086018A (en) * | 2015-08-06 | 2015-11-25 | 国网智能电网研究院 | Shock absorbing rubber material used for transformer |
| CN109233015A (en) * | 2017-07-10 | 2019-01-18 | 北京化工大学 | A kind of support high-performance damping material, preparation method and its rubber shock absorption support |
| CN108641031A (en) * | 2018-05-17 | 2018-10-12 | 北京化工大学 | A kind of hindered phenol/styrene-acrylic composite emulsion and preparation method thereof |
| CN108948724A (en) * | 2018-08-22 | 2018-12-07 | 清华大学 | A kind of preparation method of high mechanical loss factor thermoplastic urethane foam |
| CN113195245A (en) * | 2018-12-17 | 2021-07-30 | 米其林集团总公司 | Rubber composition based on at least one functionalized elastomer comprising polar functional groups and specific polyphenolic compounds |
| CN113195245B (en) * | 2018-12-17 | 2023-08-11 | 米其林集团总公司 | Rubber composition based on at least one functionalized elastomer comprising polar functional groups and a specific polyphenolic compound |
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