CN109233015B - High-performance damping material for support, preparation method and rubber damping support - Google Patents
High-performance damping material for support, preparation method and rubber damping support Download PDFInfo
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- E04H9/00—Buildings, groups of buildings or shelters adapted to withstand or provide protection against abnormal external influences, e.g. war-like action, earthquake or extreme climate
- E04H9/02—Buildings, groups of buildings or shelters adapted to withstand or provide protection against abnormal external influences, e.g. war-like action, earthquake or extreme climate withstanding earthquake or sinking of ground
- E04H9/021—Bearing, supporting or connecting constructions specially adapted for such buildings
- E04H9/022—Bearing, supporting or connecting constructions specially adapted for such buildings and comprising laminated structures of alternating elastomeric and rigid layers
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Abstract
The invention relates to a high-performance damping material for a support and a preparation method thereof, belonging to the technical field of rubber. The high-performance damping material disclosed by the invention takes the nitrile rubber as a matrix, takes the organic clay, hindered phenol antioxidant, phenolic resin and the like as functional additives, prepares the organic clay rubber composite material with excellent mechanical property and damping property by a specific method, and can be used as a lead core replacement material in a seismic isolation support. The invention also relates to a rubber shock absorption support which takes the high-performance damping material as a core material and the laminated rubber as a support and can be used for shock absorption supports in the fields of bridges, buildings and the like.
Description
Technical Field
The invention relates to the technical field of rubber, in particular to a high-performance damping material for a support, a preparation method and a rubber damping support thereof.
Background
Earthquakes are natural disasters which are extremely sudden and difficult to predict, and the high frequency of earthquakes greatly harms human society. China is in the middle of two most active seismic zones in the world and is one of the countries in the world with the most frequent seismic activity and the most serious influence of seismic disasters. Under the action of earthquake, the destruction of the building is the most direct cause of economic loss and casualties, so the most effective measure for relieving earthquake disasters is to improve the earthquake resistance of the building.
Compared with the traditional rigid shock-proof technology, the rubber shock-proof support based on 'basic shock insulation' has more excellent shock absorption effect. The principle is that a shock insulation system which is safe and reliable enough is arranged between the upper structure of the building and the foundation to increase the deformation capacity and the hysteresis damping of the structure, effectively isolate or consume the seismic energy, reduce the seismic response of the structure and protect the safety of the upper structure. In recent years, the seismic isolation support serving as an important element of 'foundation seismic isolation' has become a preferred scheme of important buildings and bridges with high seismic resistance and seismic isolation requirements in the world nowadays. The main functions of the system are to support the weight of buildings and bridges, to change the dynamic characteristics of structural systems, and to prolong the vibration period of buildings and bridges, so as to reduce the earthquake reaction.
At present, the common laminated rubber support and the lead core rubber support are two supports which are most widely applied. The common laminated rubber support is generally made of natural rubber, and the natural rubber has the characteristics of high flexibility, high elasticity and high strength, so that the support is endowed with good vertical bearing capacity and horizontal shearing deformation capacity. However, such a mount has poor damping performance and needs to be used in combination with a damper to improve the damping effect. The use of this type of mount is limited due to the expensive cost of the damper. The lead core rubber support is formed by vertically pouring one or more lead rods into a common laminated rubber support, so that the damping performance of the support is improved. However, the equivalent horizontal rigidity of the lead core rubber support is high and often exceeds the standard range, and when an earthquake occurs, the lead core is easy to yield and break, so that the self-recovery capability is reduced. In addition, under the action of normal load and low-cycle vibration, the lead core in the support generates fatigue shearing damage, and the damping performance is reduced. And the lead core can cause serious pollution to the environment.
The phenolic resin is used as a rubber additive, mainly has two functions of tackifying and reinforcing, and improves the processing performance of the material due to small molecular weight, namely plays a role in plasticization. When the phenolic resin is used as a rubber reinforcing agent, a curing agent such as HMTA, paraformaldehyde, trioxymethylene and the like must be added. The reinforcing mechanism of phenolic resin is explained in many ways, but the view is now acknowledged that a network formed by crosslinking phenolic resin and a curing agent such as Hexamethylenetetramine (HMTA) is overlapped with a rubber material network, namely the phenolic resin network and the rubber material network form an interpenetrating network (IPN), so that the effect of reinforcing rubber is achieved.
At present, relatively few researches on lead core replacement materials are conducted at home and abroad. The lead core replacement materials reported in patents of CN201610262851 (lead-like polymer composite material for shock-insulation support and preparation method thereof) of Zhang gang, Guodatong and the like have the advantages that the addition amount of phenolic resin is small, the plasticizing effect is achieved, the stress at definite elongation, the tensile strength and the hardness of the material and the vertical rigidity of the finished support are low, and the standards can only be barely achieved.
Disclosure of Invention
The technical problem to be solved by the invention is that: the novel rubber composite material is provided to replace lead metal in the rubber shock insulation support, has high hardness, high tensile strength and high stress at definite elongation, has mechanical properties close to that of the lead metal, and simultaneously has good damping performance; the second step is as follows: a novel laminated rubber material for a support is provided, which has good adhesion with other materials and excellent damping performance.
In order to solve the technical problems, the invention provides a high-performance damping material for a support, a preparation method thereof and a rubber damping support.
The invention aims to provide a high-performance damping material for a support, which is prepared from the following raw materials in parts by weight:
the nitrile rubber is nitrile rubber which is common in the prior art, such as nitrile N240S with the mass content of acrylonitrile of 26%, nitrile N230S with the mass content of acrylonitrile of 34% or nitrile N220S with the mass content of acrylonitrile of 41%.
The high-performance damping material takes the nitrile rubber as a matrix, and organic clay with a nanosheet structure is added. The organic clay is obtained by cation modification, and the interlayer of the montmorillonite is changed from hydrophilicity to lipophilicity through modification.
The modification method adopts a common method in the prior art, and specifically comprises the following steps: adding sodium montmorillonite into deionized water, stirring, and standing to completely swell; in addition, adding the intercalating agent into deionized water to dissolve to obtain an intercalating agent solution; heating the montmorillonite aqueous solution, preserving heat and stirring, then dropwise adding the intercalation agent solution into the montmorillonite aqueous solution, reacting, cooling and standing; removing supernatant to obtain white precipitate, washing with deionized water, and vacuum filtering; and drying the obtained white precipitate to obtain the organoclay.
Wherein the intercalating agent is commonly used in the prior art, such as organic quaternary phosphonium salt, pyridinium salt, organic hydrochloride intercalating agent and the like.
The preferable organic clay modification steps are as follows: adding 10.0g of sodium montmorillonite into 400ml of deionized water, magnetically stirring for 1h, and standing for 24h until complete swelling; in addition, 4.00g of intercalator octadecyl trimethyl ammonium bromide is added into 100ml of deionized water to be dissolved to obtain an intercalator solution; putting the round-bottom flask filled with the montmorillonite aqueous solution into a water bath at 80 ℃, preserving the temperature, stirring, dropwise adding the intercalator solution into the round-bottom flask, reacting for 5h within 35min, cooling and standing; removing supernatant to obtain white precipitate, washing with deionized water, and vacuum filtering for several times until filtrate is 1% AgNO3Detecting the solution without light yellow precipitate; and transferring the obtained white precipitate into a beaker, and drying for 2 hours at the temperature of 80 ℃ to obtain the organoclay.
The organic micromolecule-hindered phenol antioxidant with high damping performance is added into the formula. After the hindered phenol antioxidant is added, the mechanical property of the material is greatly improved, and simultaneously, the damping property of the material can be improved by one level, and the damping temperature range of the material is widened. The hindered phenolic antioxidant in the present invention may be selected from the hindered phenolic antioxidants known in the art, preferably pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (hindered phenol AO60), 3, 9-bis {1, 1-dimethyl-2 [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) acrylonitrile ] ethyl-2, 4, 6, 8-tetraoxaspiro (5, 5) -undecane ] (hindered phenol AO80), at least one of di-tert-butylhydroxytoluene (hindered phenol BHT), 1, 3, 5-trimethyl 2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene ] (KY-1300), and more preferably hindered phenol AO 80.
The short fiber in the invention can be selected from the short fibers existing in the prior art, preferably at least one of nylon 66 fiber, polyester short fiber and aramid short fiber, and has the length of 0.5-13mm, preferably 2-8 mm.
The phenolic resin in the invention can adopt the existing phenolic resin in the prior art, and preferably adopts a reinforced phenolic resin. The oil modified phenolic resin can improve the compatibility with rubber, improve the solubility in the rubber, and simultaneously can improve the processability of the material without being cured when the material is added. The invention uses the phenolic resin as a necessary additive to reinforce the material through the crosslinking action of the phenolic resin and the curing agent, thereby greatly improving the mechanical property of the material.
The curing agent is added in the formula, so that the phenolic resin is cured, and the rubber is reinforced, so that the physical and mechanical properties of the material are improved. The curing agent in the invention can be selected from the curing agents existing in the prior art, preferably at least one of Hexamethylenetetramine (HMTA), methylol urea (MMU), Propylene Carbonate (PC), sodium carbonate and magnesium hydroxide, and more preferably HMTA.
The above formulation contains a conventional accelerator for rubber processing, preferably at least one of N-cyclohexyl-2-benzothiazolesulfenamide (accelerator CZ), N '-diphenylguanidine (accelerator D), and 4, 4' -dithiodimorpholine (accelerator DTDM), and more preferably accelerator CZ.
The above formulation contains a vulcanizing agent which is generally used in rubber processing, and sulfur is preferred.
The formula can also comprise a common active agent in rubber processing, such as the common active agent, and the common active agent is added in a common amount, wherein the active agent accounts for 100 parts by weight of the nitrile rubber, preferably 2.5-11 parts by weight, and more preferably 5-8 parts by weight. The active agent is preferably at least one of zinc oxide and stearic acid; the preferred amounts are: 100 parts of nitrile rubber, 2-8 parts of zinc oxide and 0.5-3 parts of stearic acid; more preferably 4-6 parts of zinc oxide and 1-2 parts of stearic acid.
The invention also aims to provide a preparation method of the high-performance damping material for the support, which comprises the steps of weighing the components according to the using amount, mixing, and vulcanizing to obtain the high-performance damping material.
In the preparation process of the high-performance damping material, the mixing, mixing and vulcanizing processes of the raw material components can adopt the common rubber processing process in the prior art. The equipment used is also the equipment in the rubber processing in the prior art, such as a high-speed stirring mixer, a kneader, an internal mixer, an open mill, a vulcanizer and the like.
The specific process steps comprise the following steps:
plasticating the nitrile rubber, adding the organic clay, uniformly mixing, then carrying out hot refining, taking out pieces, mixing, sequentially adding components including phenolic resin, hindered phenol oxidizing agent, short fiber, curing agent, vulcanizing agent and accelerant, uniformly mixing, and finally vulcanizing to obtain the high-performance damping material.
Preferably comprising the steps of:
plasticizing nitrile rubber in a double-roller open mill at room temperature, adding organic clay, uniformly mixing, then mixing by using a hot roller open mill at the mixing temperature of 80-100 ℃, so that the nitrile rubber is in an obvious molten state at the temperature, performing molten thermal mixing for 5-15 min, taking out the nitrile rubber after uniform mixing, and cooling to room temperature; mixing on an open mill, and uniformly mixing the components including phenolic resin, hindered phenol oxidizing agent, short fiber, curing agent, vulcanizing agent, accelerator and activator in sequence to obtain nitrile rubber compound; and finally vulcanizing the rubber compound at 140-160 ℃ and 12-18 MPa according to the positive vulcanization time of the rubber compound to obtain the high-performance damping material.
The invention also aims to provide a rubber shock-insulation support which comprises a core material and laminated rubber, wherein the support uses a high-performance damping material as the core material; the laminated adhesive is used as a support and is prepared from the following raw materials in parts by weight:
the laminated adhesive takes the smoked sheet adhesive No. 1 as a base body.
C in the invention5/9Petroleum resin having a softening point of 100 ℃. The petroleum resin is prepared by copolymerizing diolefin containing five carbon atoms and diolefin containing nine carbon atoms, has good compatibility with rubber matrix, and is small organic molecule with molecular weight less than 3000。
The short fiber for the laminating adhesive can be selected from the short fibers existing in the prior art, the length of the short fiber is 1-10mm, and the short fiber is preferably at least one of nylon 66 fiber, polyester short fiber and aramid short fiber.
The above formulation contains an antioxidant which is generally used in rubber processing, preferably at least one of N-isopropyl-N' -phenyl-p-phenylenediamine (antioxidant 4010NA), 2-mercaptobenzimidazole (antioxidant MB) and 2, 2, 4-trimethyl-1, 2-dihydroquinoline (antioxidant RD), and more preferably antioxidant 4010 NA.
The above formulation contains a conventional accelerator for rubber processing, preferably at least one of N-cyclohexyl-2-benzothiazolesulfenamide (accelerator CZ), N '-diphenylguanidine (accelerator D), and 4, 4' -dithiodimorpholine (accelerator DTDM), and more preferably accelerator CZ.
The above formulation contains a vulcanizing agent which is generally used in rubber processing, and sulfur is preferred.
The above formulation may also contain conventional active agents for rubber processing, such as conventional active agents, in conventional amounts. The preferred active agent may be at least one of zinc oxide and stearic acid; the preferred amounts are: taking the No. 1 tobacco flake adhesive as 100 parts by weight, 1-6 parts of zinc oxide and 1-3 parts of stearic acid; more preferably 2-4 parts of zinc oxide and 1-2 parts of stearic acid.
The above formulation contains carbon black which is generally used in rubber processing, preferably at least one of carbon black N220, carbon black N330 and carbon black N660, and more preferably carbon black N660.
The above formulation may further comprise a plasticizer which is generally used in rubber processing, for example, a conventional plasticizer may be added in a conventional amount. The preferred plasticizer may be at least one of Si69 and an aromatic oil; the preferred amounts are: based on 100 parts by weight of No. 1 smoked sheet rubber, 3-9 parts by weight of Si 691-8 parts by weight of aromatic oil, more preferably 4-6 parts by weight of Si 692-5 parts by weight of aromatic oil.
The preparation method of the lamination adhesive comprises the following steps:
plasticating the tobacco flake adhesive No. 1, and sequentially adding an activating agent, an anti-aging agent, short fibers and C5/9Petroleum resin, vulcanizing agent, carbon black and plasticizerAnd mixing the components including the accelerator uniformly, and finally vulcanizing to obtain the laminated rubber.
Preferably comprising the steps of:
the No. 1 tobacco sheet rubber is plasticated in a double-roller open mill on an open mill at room temperature, and sequentially added with an activating agent, an anti-aging agent, short fibers and C5/9The method comprises the following steps of uniformly mixing components including petroleum resin, a vulcanizing agent, carbon black, a plasticizer and an accelerator, taking out sheets, cooling to room temperature, standing for 8 hours for later use, cutting the mixed rubber into rubber sheets with the specification of 295 × 415 × 7mm, sequentially stacking the rubber sheets in a sequence of one steel sheet layer by one rubber sheet layer, wherein the thickness of the steel sheet is 4mm, 9 steel sheets and 10 rubber sheet layers are calculated to obtain blanks, putting the blanks into a preheated mold, vulcanizing at the temperature of 140 ℃ under the pressure of 15MPa for 2 hours, and obtaining the laminated rubber support.
And assembling the obtained high-performance damping material core material and the laminated rubber support to obtain the rubber damping support of the lead-like polymer composite material core material.
The steel base plate of the bottom surface and the top surface (embedded in the pier top and the beam bottom surface) of the rubber shock absorption support is embedded compactly, and the base plate and the support are smoothly and closely attached. And then the top plate and the bottom plate are bolted on the embedded steel plates on the bottom surface of the beam body and the top surface of the abutment by welding or anchoring bolts.
The invention has the beneficial effects that:
according to the invention, the novel high-polymer composite material is prepared by adding organic clay into nitrile rubber by using a melting intercalation method and simultaneously adding hindered phenol antioxidant, phenolic reinforcing resin and short fibers, and the high-performance damping material has similar mechanical property and damping property with lead metal. The stress of the modified organic clay under small strain is obviously improved by adding the modified organic clay; the mechanical property of the material is greatly improved by adding the phenolic resin and the short fibers, and the phenolic resin and the curing agent are used together to reinforce the material; the addition of hindered phenol antioxidant widens the damping temperature range of the material and further improves the damping performance of the material.
The petroleum resin is added into the laminated adhesive, so that the damping performance of the material and the bonding performance with other materials can be effectively improved; the addition of short fibers can improve the strength of the material.
Compared with a lead core support, the rubber damping support obtained by the invention has good comprehensive performance and wide application prospect.
Drawings
FIG. 1 is a schematic structural diagram of a rubber support with a lead core and a lead-like polymer composite material. The figures in the drawings are marked with the following meanings: 1-connecting a steel plate; 2-upper sealing plate; 3-connecting bolts; 4-middle laminated rubber; 5-a steel plate; 6-a cleavage bond; 7-lead core; 8-lower sealing plate; 9-lower connecting steel plate.
FIG. 2 is a tan-temp. graph of the high performance damping material core material in examples 4-6.
FIG. 2 is a graph of tan-temp for the core rod materials of examples 4-6, and the data of Table 6 is obtained by analyzing FIG. 2.
Detailed Description
The raw materials used in the invention are as follows:
nitrile rubber, manufactured by JSR corporation of japan;
smoked sheet adhesive No. 1, produced by Hainan Natural rubber industry group Ltd
Hindered phenol AO80, manufactured by Asahi Denka of Japan;
phenolic resin, manufactured by Shanghai Australian Industrial Co., Ltd;
short fiber, the main component of which is meta-aramid fiber, the length of the fiber is 2 plus or minus 0.5mm, and the short fiber is produced by Shanghai Shuyi new material company Limited;
the short fiber has the model of NF66-3, the main component of the short fiber is nylon 66, the fiber length is 3 +/-0.5 mm, and the short fiber is produced by Heilongjiang Hongyu short fiber new material company Limited;
organic clay, which is modified in a laboratory, uses octadecyl trimethyl ammonium bromide as an intercalating agent to carry out organic treatment on sodium montmorillonite;
octadecyl trimethyl ammonium bromide, manufactured by Nanjing chemical reagents, Inc.;
other rubber compounding agents such as stearic acid, zinc oxide, an accelerator, aromatic oil, an anti-aging agent and the like, and is produced by Shenghua rubber and plastic products Limited company.
The invention will be further illustrated by the following examples, but the invention is not limited to these examples, according to the formulation and process for preparing the high performance damping material for pedestals of the invention.
Examples 1 to 3
The preparation process of the core material comprises the following steps: the high performance damping material for the mount was prepared according to the formulation of table 1.
TABLE 1 nitrile rubber formulation
| Formulation of | Example 1 | Example 2 | Example 3 | Comparative |
| Nitrile rubber | ||||
| 100 portions of | 100 | 100 | 100 | |
| |
100 | 100 | 100 | 100 |
| Phenolic resin | 20 | 30 | 40 | 15 |
| |
2 | 3 | 4 | 0 |
| Nylon short fiber | 10 | 15 | 20 | 10 |
| Hindered phenol AO80 | 40 | 40 | 40 | 40 |
| Zinc oxide | 4 | 5 | 6 | 5 |
| Stearic acid | 1 | 1.5 | 2 | 1 |
| |
2 | 2.5 | 3 | 2 |
| Accelerant CZ | 1 | 1.6 | 3 | 1.6 |
The modification method of the organic clay comprises the following steps: adding 10.0g of sodium montmorillonite into 400ml of deionized water, magnetically stirring for 1h, and standing for 24h until complete swelling; in addition, 4.00g of intercalator octadecyl trimethyl ammonium bromide is added into 100ml of deionized water to be dissolved to obtain an intercalator solution; putting the round-bottom flask filled with the montmorillonite aqueous solution into a water bath at 80 ℃, preserving the temperature, stirring, dropwise adding the intercalator solution into the round-bottom flask, reacting for 5h within 35min, cooling and standing; removing supernatant to obtain white precipitate, washing with deionized water, and vacuum filtering for several times until filtrate is detected to have no light yellow precipitate by AgNO3 solution with mass percent of 1%; and transferring the obtained white precipitate into a beaker, and drying for 2 hours at the temperature of 80 ℃ to obtain the organoclay.
The preparation process of the high-performance damping material for the support comprises the following steps: the proportion of the nitrile rubber/the organic clay/the hindered phenol AO 80/the phenolic resin is 100/100/40/20, 100/100/40/30 and 100/100/40/40, the nitrile rubber is plasticated in a double-roller open mill at room temperature, then the organic clay is added, the mixture is evenly blended and then is blended by a hot roller open mill, the blending temperature is 100 ℃, the mixture is in an obvious molten state at the temperature, the molten state is heated for 10min, and after the mixture is evenly blended, the mixture is taken out and cooled to the room temperature; and mixing on an open mill, and sequentially adding the phenolic resin, the hindered phenol, the short fiber, the activator, the vulcanizing agent, the curing agent and the accelerator, and uniformly mixing to obtain the nitrile rubber compound. Finally, vulcanizing the rubber compound at 150 ℃ and 15MPa according to the normal vulcanization time of the rubber compound to obtain a high-performance damping material, namely nitrile rubber/organic clay/hindered phenol AO 80/phenolic resin: 100/100/40/20, nitrile rubber/organoclay/hindered phenol AO 80/phenolic resin: 100/100/40/30, nitrile rubber/organoclay/hindered phenol AO 80/phenolic resin: 100/100/40/40. (successively denoted as example 1/2/3)
7 g of the nitrile rubber compound samples obtained in examples 1 to 3 were weighed out separately and the scorch time T10 and the positive vulcanization time T90 were measured on a vulcanizer. And vulcanizing the laminated rubber compound on a flat vulcanizing machine according to the temperature of 150 ℃ multiplied by T90, wherein the vulcanization pressure is 15MPa, and obtaining the cross-linked high-performance damping material for the support.
The preparation process of the support laminated adhesive comprises the following steps: laminating adhesive is prepared according to the following formula
Weighing smoked sheet rubber No. 1 and formulation auxiliary according to the formulation, plasticating smoked sheet rubber No. 1 in a double-roller open mill on an open mill at room temperature, and sequentially adding activator, anti-aging agent, short fiber and C5/9The rubber support is prepared by the steps of uniformly mixing petroleum resin, a vulcanizing agent, carbon black, a plasticizer and an accelerator, taking out pieces, cooling to room temperature, standing for 8 hours, cutting the mixed rubber into rubber sheets with the specification of 295 × 415 × 7mm, sequentially stacking the rubber sheets according to the sequence of one steel sheet layer by one rubber sheet layer, obtaining blanks with the thickness of 4mm, 9 steel sheets and 10 rubber sheet layers in total, putting the blanks into a preheated mold, vulcanizing at the temperature of 145 ℃ under the pressure of 15MPa for 2 hours, and obtaining the rubber support.
And respectively assembling the obtained lead-like polymer composite core material with the laminated rubber support to obtain the lead-like polymer composite core material damping support.
The performance of the novel composite material for the core material is tested, and the performance of the prepared high-performance damping material is shown in Table 2.
TABLE 2 examples 1-3 high-performance damping materials for supports and comparative examples
The performance of the shock-absorbing support made of the lead-like polymer composite material core material is tested, and the performance of the support is shown in table 3.
TABLE 3 Properties of the supports of examples 1-3 and of the comparative example
As can be seen from Table 2, the materials in examples 1-3 are reinforced with phenolic resin and curing agent, and the comparative example uses 15 parts of phenolic resin and no curing agent. The hardness, stress under small strain and tensile strength of the high-performance damping material for the support adopting the curing agent are obviously improved compared with those of the material without the curing agent.
As can be seen from table 3, the damping mount made of the materials in embodiments 1 to 3 has high vertical stiffness due to high hardness, and the stress under small strain is significantly increased, which is close to the stress at definite elongation of pure lead, and increases the equivalent horizontal stiffness of the rubber mount during horizontal deformation, so that the rubber mount has excellent compression resistance. With the increase of the parts of the phenolic resin, a stronger cross-linked network is formed in the composite material, the mechanical property of the material is stronger, and the vertical rigidity of the support is improved accordingly.
The national standard requires that the standard requirement of the vertical rigidity of the finished product support is 678 x (1 +/-30%) KN/mm, the standard requirement of the equivalent horizontal rigidity is 1.4 x (1 +/-15%) KN/mm, the standard requirement of the equivalent damping ratio is 22.3 x (1 +/-15%), and as can be seen from the table 3, all the performances of the rubber damping support are within the standard range, and the performance requirement of the bridge support is met.
Examples 4 to 6
The preparation process of the core material comprises the following steps: the high performance damping material for the mount was prepared according to the formulation of table 4.
TABLE 4 nitrile rubber formulations
| Formulation of | Example 4 | Example 5 | Example 6 |
| |
100 portions of | 100 | 100 |
| |
100 | 100 | 100 |
| Phenolic resin | 30 | 30 | 30 |
| |
2 | 3 | 4 |
| Nylon short fiber | 10 | 10 | 10 |
| Hindered phenol AO80 | 20 | 30 | 40 |
| Zinc oxide | 5 | 5 | 5 |
| Stearic acid | 1 | 1 | 1 |
| |
2 | 2 | 2 |
| Accelerant CZ | 1.6 | 1.6 | 1.6 |
The modification method of the organic clay comprises the following steps: adding 10.0g of sodium montmorillonite into 400ml of deionized water, magnetically stirring for 1h, and standing for 24h until complete swelling; in addition, 4.00g of intercalator octadecyl trimethyl ammonium bromide is added into 100ml of deionized water to be dissolved to obtain an intercalator solution; putting the round-bottom flask filled with the montmorillonite aqueous solution into a water bath at 80 ℃, preserving the temperature, stirring, dropwise adding the intercalator solution into the round-bottom flask, reacting for 5h within 35min, cooling and standing; removing supernatant to obtain white precipitate, washing with deionized water, and vacuum filtering for several times until filtrate is detected to have no light yellow precipitate by AgNO3 solution with mass percent of 1%; and transferring the obtained white precipitate into a beaker, and drying for 2 hours at the temperature of 80 ℃ to obtain the organoclay.
The preparation process of the high-performance damping material for the support comprises the following steps: the proportion of the nitrile rubber/the organic clay/the hindered phenol AO 80/the phenolic resin is 100/100/20/30, 100/100/30/30 and 100/100/40/30, the nitrile rubber is plasticated in a double-roller open mill at room temperature, then the organic clay is added, the mixture is evenly blended and then is blended by a hot roller open mill, the blending temperature is 100 ℃, the mixture is in an obvious molten state at the temperature, the molten state is heated for 10min, and after the mixture is evenly blended, the mixture is taken out and cooled to the room temperature; and mixing on an open mill, and sequentially adding the phenolic resin, the hindered phenol, the short fiber, the activator, the vulcanizing agent, the curing agent and the accelerator, and uniformly mixing to obtain the nitrile rubber compound. Finally, vulcanizing the rubber compound at 150 ℃ and 15MPa according to the normal vulcanization time of the rubber compound to obtain a high-performance damping material, namely nitrile rubber/organic clay/hindered phenol AO 80/phenolic resin: 100/100/20/30, nitrile rubber/organoclay/hindered phenol AO 80/phenolic resin: 100/100/30/30, nitrile rubber/organoclay/hindered phenol AO 80/phenolic resin: 100/100/40/30. (successively denoted as example 4/5/6)
A sample of 7 g of the nitrile rubber mixtures obtained in examples 4 to 6 was weighed out in each case and the scorch time T10 and the positive vulcanization time T90 were determined on a vulcanizer. And vulcanizing the laminated rubber compound on a flat vulcanizing machine according to the temperature of 150 ℃ multiplied by T90, wherein the vulcanization pressure is 15MPa, and obtaining the cross-linked high-performance damping material for the support.
The preparation process of the support laminated adhesive comprises the following steps: the lamination adhesive was prepared according to the following formulation.
Weighing smoked sheet rubber No. 1 and formulation auxiliary according to the formulation, plasticating smoked sheet rubber No. 1 in a double-roller open mill on an open mill at room temperature, and sequentially adding activator, anti-aging agent, short fiber and C5/9The rubber support is prepared by the steps of uniformly mixing petroleum resin, a vulcanizing agent, carbon black, a plasticizer and an accelerator, taking out pieces, cooling to room temperature, standing for 8 hours, cutting the mixed rubber into rubber sheets with the specification of 295 × 415 × 7mm, sequentially stacking the rubber sheets according to the sequence of one steel sheet layer by one rubber sheet layer, obtaining blanks with the thickness of 4mm, 9 steel sheets and 10 rubber sheet layers in total, putting the blanks into a preheated mold, vulcanizing at the temperature of 145 ℃ under the pressure of 15MPa for 2 hours, and obtaining the rubber support.
And respectively assembling the obtained lead-like polymer composite core material with the laminated rubber support to obtain the lead-like polymer composite core material damping support.
The performance of the novel composite material for the core material is tested, and the performance of the prepared high-performance damping material is shown in Table 5.
TABLE 5 examples 4-6 physico-mechanical properties of high performance damping materials for pedestals
The performance of the novel composite material for the core material is tested, and the performance of the prepared high-performance damping material is shown in Table 6.
TABLE 6 damping Properties of high Performance damping materials for pedestals of examples 4-6
The performance of the shock-absorbing support made of the lead-like polymer composite material core material is tested, and the performance of the support is shown in table 7.
TABLE 7 EXAMPLES 4-6 Stand Performance
From table 5, it can be seen that the high-performance damping material for the support has high hardness, the prepared rubber core material has high vertical stiffness in the vertical direction, the stress is obviously improved under the action of small strain, the stress is close to the stress at definite elongation of pure lead, the equivalent horizontal stiffness of the rubber support during horizontal deformation can be increased, and the rubber support has excellent pressure resistance.
As can be seen from Table 6, with the increase of the dosage of the hindered phenol AO80, the tan peak value is increased, the damping temperature range of the material is increased, the temperature range is close to the room temperature, and the tan is more than or equal to 0.3 in the range, which indicates that the prepared rubber material has excellent damping, shock absorption and shock isolation performances near the normal temperature region.
As can be seen from Table 7, the national standards require 678X (1 + -30%) KN/mm for vertical stiffness, 1.4X (1 + -15%) KN/mm for equivalent horizontal stiffness, and 22.3X (1 + -15%) for equivalent damping ratio. All performances of the high-performance damping material for the support are within a standard range, and the requirements on the performance of the bridge support are met.
Examples 7 to 9
The preparation process of the core material comprises the following steps: a high performance damping material for the mount was prepared according to the formulation of Table 8.
TABLE 8 nitrile rubber formulations
| Formulation of | Example 7 | Example 8 | Example 9 |
| |
100 portions of | 100 | 100 |
| Organic clay | 60 | 100 | 150 |
| Phenolic resin | 30 | 30 | 30 |
| |
2 | 3 | 4 |
| Nylon short fiber | 10 | 10 | 10 |
| AO80 | 40 | 40 | 40 |
| Zinc oxide | 5 | 5 | 5 |
| Stearic acid | 1 | 1 | 1 |
| |
2 | 2 | 2 |
| Accelerant CZ | 1.6 | 1.6 | 1.6 |
The modification method of the organic clay comprises the following steps: adding 10.0g of sodium montmorillonite into 400ml of deionized water, magnetically stirring for 1h, and standing for 24h until complete swelling; in addition, 4.00g of intercalator octadecyl trimethyl ammonium bromide is added into 100ml of deionized water to be dissolved to obtain an intercalator solution; putting the round-bottom flask filled with the montmorillonite aqueous solution into a water bath at 80 ℃, preserving the temperature, stirring, dropwise adding the intercalator solution into the round-bottom flask, reacting for 5h within 35min, cooling and standing; removing supernatant to obtain white precipitate, washing with deionized water, and vacuum filtering for several times until filtrate is detected to have no light yellow precipitate by AgNO3 solution with mass percent of 1%; and transferring the obtained white precipitate into a beaker, and drying for 2 hours at the temperature of 80 ℃ to obtain the organoclay.
The preparation process of the high-performance damping material for the support comprises the following steps: the proportion of the nitrile rubber/the organic clay/the hindered phenol AO 80/the phenolic resin is 100/60/40/30, 100/100/40/30 and 100/150/40/30, the nitrile rubber is plasticated in a double-roller open mill at room temperature, then the organic clay is added, the mixture is evenly blended and then is blended by a hot roller open mill, the blending temperature is 100 ℃, the mixture is in an obvious molten state at the temperature, the molten state is heated for 10min, and after the mixture is evenly blended, the mixture is taken out and cooled to the room temperature; and mixing on an open mill, and sequentially adding the phenolic resin, the hindered phenol, the short fiber, the activator, the vulcanizing agent, the curing agent and the accelerator, and uniformly mixing to obtain the nitrile rubber compound. Finally, vulcanizing the rubber compound at 150 ℃ and 15MPa according to the normal vulcanization time of the rubber compound to obtain a high-performance damping material, namely nitrile rubber/organic clay/hindered phenol AO 80/phenolic resin: 100/60/30/40, nitrile rubber/organoclay/hindered phenol AO 80/phenolic resin: 100/100/30/40, nitrile rubber/organoclay/hindered phenol AO 80/phenolic resin: 100/150/30/40. (successively denoted as example 7/8/9)
A sample of 7 g of nitrile rubber compound was weighed out on a vulkameter for the scorch time T10 and the positive vulcanization time T90. And vulcanizing the laminated rubber compound on a flat vulcanizing machine according to the temperature of 150 ℃ multiplied by T90, wherein the vulcanization pressure is 15MPa, and obtaining the cross-linked high-performance damping material for the support.
The preparation process of the laminating adhesive comprises the following steps: the support lamination adhesive was prepared according to the following formulation.
Weighing the smoked sheet rubber No. 1 and the formula auxiliary agents according to the formula, plasticating the smoked sheet rubber No. 1 in a double-roller open mill on an open mill at room temperature, sequentially adding an active agent, an anti-aging agent, short fibers, petroleum resin, a vulcanizing agent, carbon black, a plasticizer and an accelerator, uniformly mixing, taking out the smoked sheet, cooling to room temperature, and standing for 8 hours for later use. Cutting the rubber compound into films with the specification of 295X 415X 7mm, and then sequentially stacking the films in the sequence of one steel plate and one film, wherein the thickness of the steel plate is 4mm, and the total of 9 steel plates and 10 film layers are used for preparing blanks. And putting the blank into a preheated mold, and vulcanizing the blank for 2 hours at the temperature of 145 ℃ under the pressure of 15MPa to obtain the rubber support.
And respectively assembling the obtained lead-like polymer composite core material with support laminated glue to obtain the lead-like polymer composite core material damping support.
The performance of the novel composite material for the core material is tested, and the performance of the prepared high-performance damping material is shown in Table 9.
TABLE 9 examples 7-9 physical and mechanical Properties of high Performance damping materials for pedestals
The performance of the shock-absorbing support made of the lead-like polymer composite core material is tested, and the performance of the support is shown in table 10.
TABLE 10 support Properties of examples 7-9
It can be seen from table 9 that the high-performance damping material for the support has high hardness, the prepared rubber core material has high vertical stiffness in the vertical direction, the stress is remarkably improved under the action of small strain, the stress is close to the stress at definite elongation of pure lead, the equivalent horizontal stiffness of the rubber damping support during horizontal deformation can be increased, and the rubber damping support has excellent pressure resistance.
As can be seen from Table 10, the national standards require 678X (1 + -30%) KN/mm for vertical stiffness, 1.4X (1 + -15%) KN/mm for equivalent horizontal stiffness, and 22.3X (1 + -15%) for equivalent damping ratio. All properties of the prepared rubber damping support are within a standard range, and the performance requirements of the bridge support are met.
Claims (14)
1. A high-performance damping material for a support is characterized by being prepared from the following raw materials in parts by weight:
100 parts of nitrile rubber;
60-150 parts of organic clay;
20-50 parts of phenolic resin;
10-100 parts of hindered phenol antioxidant;
10-50 parts of short fibers;
1-10 parts of a curing agent;
2-5 parts of a vulcanizing agent;
1-5 parts of an accelerator;
wherein the length of the short fiber is 0.5-13 mm.
2. The high-performance damping material as set forth in claim 1, characterized in that it is prepared from raw materials comprising the following components in parts by weight:
100 parts of nitrile rubber;
80-100 parts of organic clay;
20-50 parts of phenolic resin;
10-50 parts of hindered phenol antioxidant;
10-20 parts of short fibers;
1-5 parts of a curing agent;
2-3 parts of a vulcanizing agent;
1-3 parts of an accelerator;
wherein the length of the short fiber is 2-8 mm.
3. The high performance damping material of claim 1, wherein:
the components comprise 2.5-11 parts of active agent by taking the nitrile rubber as 100 parts by weight.
4. The high performance damping material of claim 3, wherein:
the components comprise 5-8 parts of an active agent by taking 100 parts of nitrile rubber as a raw material.
5. The high performance damping material of claim 3, wherein:
the activator is at least one of zinc oxide and stearic acid, the nitrile rubber accounts for 100 parts by weight, and the zinc oxide accounts for 2-8 parts by weight; 0.5-3 parts of stearic acid.
6. The high performance damping material of claim 5, wherein:
100 parts of nitrile rubber and 4-6 parts of zinc oxide; 1-2 parts of stearic acid.
7. The high performance damping material of any one of claims 1 to 6, wherein:
the hindered phenol antioxidant is at least one selected from tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 3, 9-bis {1, 1-dimethyl-2 [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) acrylonitrile ] ethyl-2, 4, 6, 8-tetraoxaspiro (5, 5) -undecane ], di-tert-butyl hydroxytoluene and 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene ].
8. The high performance damping material of any one of claims 1 to 6, wherein:
the short fiber is at least one of nylon 66 fiber, polyester short fiber and aramid short fiber.
9. The high performance damping material of any one of claims 1 to 6, wherein:
the curing agent is at least one of hexamethylenetetramine, hydroxymethyl urea, propylene carbonate, sodium carbonate and magnesium hydroxide.
10. The high performance damping material of any one of claims 1 to 6, wherein:
the organic clay is obtained by cation modification.
11. The high performance damping material of claim 10, wherein:
the organic clay is modified by a method comprising the following steps:
adding sodium montmorillonite into deionized water, stirring, and standing to completely swell; in addition, adding the intercalating agent into deionized water to dissolve to obtain an intercalating agent solution; heating the montmorillonite aqueous solution, preserving heat and stirring, then dropwise adding the intercalation agent solution into the montmorillonite aqueous solution, reacting, cooling and standing; removing supernatant to obtain white precipitate, washing with deionized water, and vacuum filtering; and drying the obtained white precipitate to obtain the organoclay.
12. A method for preparing a high performance damping material as claimed in any one of claims 1 to 11, comprising:
weighing the components, mixing and vulcanizing.
13. A rubber cushion mount using the high-performance damping material for mount according to any one of claims 1 to 11, comprising a core material and a lamination adhesive,
wherein the support uses a high-performance damping material as the core material;
the laminating adhesive is prepared from the following raw materials in parts by weight:
no. 1 smoked sheet glue 100 parts;
1-4 parts of a vulcanizing agent;
2-9 parts of an active agent;
1-5 parts of an accelerator;
1-5 parts of an anti-aging agent;
3-15 parts of a plasticizer;
20-80 parts of carbon black;
C5/910-60 parts of petroleum resin;
10-60 parts of short fibers;
wherein the length of the short fiber is 1-10 mm.
14. The rubber cushion mount of claim 13 wherein:
the laminating adhesive is prepared from the following raw materials in parts by weight:
no. 1 smoked sheet glue 100 parts;
1.2-3 parts of a vulcanizing agent;
3-6 parts of an active agent;
1.5-2 parts of an accelerator;
2-3 parts of an anti-aging agent;
6-12 parts of a plasticizer;
40-60 parts of carbon black;
C5/910-30 parts of petroleum resin;
10-30 parts of short fibers.
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| US4007233A (en) * | 1973-01-09 | 1977-02-08 | Sumitomo Durez Company, Ltd. | Rubber cement compositions |
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| CN101016392A (en) * | 2007-02-01 | 2007-08-15 | 北京化工大学 | Crosslinking-type rubber-base damping material and preparing method thereof |
| CN101654561B (en) * | 2008-08-22 | 2011-11-02 | 株洲时代新材料科技股份有限公司 | Modified asphalt hot-melt damping material for vehicles and preparation method and construction method thereof |
| CN102115647B (en) * | 2009-12-30 | 2013-08-07 | 上海市合成树脂研究所 | Damping glue for vibration reducing plate and preparation method thereof |
| CN102127252B (en) * | 2010-01-14 | 2012-08-08 | 中国船舶重工集团公司第七一三研究所 | High hardness butadiene-acrylonitrile rubber and preparation method thereof |
| CN104817730B (en) * | 2015-04-10 | 2016-10-05 | 北京化工大学 | Shock mount high-performance rubber composite and preparation method thereof |
| CN106867060B (en) * | 2015-12-14 | 2019-01-22 | 株洲时代新材料科技股份有限公司 | A kind of aseismatic bearing rubber composition and preparation method thereof |
| CN105860493B (en) * | 2016-04-25 | 2018-03-30 | 北京化工大学 | A kind of shock isolating pedestal ekalead polymer composite |
| CN105885131B (en) * | 2016-04-25 | 2017-10-20 | 北京化工大学 | Shock isolating pedestal ekalead polymer composite and preparation method thereof |
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|---|---|---|---|---|
| US2605248A (en) * | 1950-07-07 | 1952-07-29 | Us Rubber Co | Heat-curable mixtures of butadieneacrylonitrile copolymers and phenol-aldehyde resins and method of making |
| GB1045577A (en) * | 1962-10-16 | 1966-10-12 | Dekalin Deutsche Klebstoffwerk | Plastic composition |
| FR1457080A (en) * | 1964-12-04 | 1966-10-28 | B F Goodrich Company Soc | Adhesive glue |
| US4007233A (en) * | 1973-01-09 | 1977-02-08 | Sumitomo Durez Company, Ltd. | Rubber cement compositions |
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