JP3780090B2 - Rubber with silanol - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rubber having silanol that can be used as a high-damping rubber or the like.
[0002]
[Prior art]
Earthquake is a kind of vibration phenomenon. Therefore, buildings that slip away or slip away from the energy of the earthquake will not break. However, because every structure has its own vibration response characteristics against earthquake motion, it is possible to reduce the effects of earthquakes on buildings by allowing them to adapt well considering the characteristics of the earthquake motion and the characteristics of the structure. It becomes. Insulating the building and the ground as one of the building design methods for the seismic motion currently in progress, putting soft springs to prevent the ground movement from being transmitted directly to the building, and inputting the seismic energy to the building There is a way to prevent it. Seismic isolation laminated rubber is known as this soft spring. The base isolation laminate rubber, a building large load stable at all times Men圧100 kgf / cm ² or so, to support long-term. And it is required to have the ability to return shocking ground motion to a constant and gentle deformation by softly deforming during a large earthquake. Therefore, natural rubber rich in rubber-like elasticity that is soft and hardly causes creep is used as an optimum material.
[0003]
The laminated rubber currently used is usually a natural rubber-based seismic isolation laminated rubber. Natural rubber-based seismic isolation laminated rubber is obtained by adding compounding agents such as a filler and a vulcanizing agent to natural rubber, and these compounding agents are compounded using rubber elasticity. In addition, a separate damper is used together to further attenuate the earthquake motion, and it is possible to suppress excessive displacement of the seismic isolation laminated rubber by energy consumption during an earthquake.
[0004]
Hysteretic dampers and viscous dampers are commonly used dampers. In addition, among the natural rubber-based seismic isolation laminated rubber, a lot of adopted ones are laminated with lead plugs composed of laminated rubber and vulcanized and bonded laminated rubber and high-purity lead plugs, which are alternately laminated steel plates and natural rubber. There is rubber (LRB). In the event of an earthquake, the lead plug is enclosed in the center of the laminated rubber, so that it is integrated with the laminated rubber to cause plastic deformation. Therefore, LRB is also a compact seismic isolation device that has all the functions necessary for the seismic isolation system in the entire device.
[0005]
Lead metal has the characteristics that it undergoes plastic deformation at a lower stress than other general metals, and that fatigue reduction does not appear clearly due to the property of recrystallization. As a result, the LRB is a seismic isolation bearing that integrates the features of the seismic isolation rubber necessary for the base isolation structure and the damper function, and is a hybrid seismic isolation bearing that combines the characteristics of laminated rubber and the mechanical properties of lead. I can say that. However, since metallic lead is not a harmless metal, other useful materials are required.
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel organic-inorganic hybrid rubber having characteristics such as high attenuation.
[0007]
[Means for Solving the Problems]
The rubber having silanol of the present invention comprises a rubber main body made of at least one selected from SBR, NBR, BR, EPM, EPDM, CR, butyl rubber, halogenated butyl rubber and natural rubber , and a side chain bonded to the rubber main body. Moreover, the side chain is characterized by comprising a pyridinium salt of silanol. The rubber having silanol of the present invention stretches like a cocoon in an unvulcanized state and has high damping characteristics when blended with ordinary rubber.
[0008]
In the rubber having silanol of the present invention , the rubber body is composed of at least one selected from SBR, NBR, BR, EPM, EPDM, CR, butyl rubber, halogenated butyl rubber, and natural rubber.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The rubber having silanol of the present invention has a rubber main body and a side chain bonded to the rubber main body. The side chain consists of a pyridinium salt of silanol. The rubber body is made of at least one selected from SBR, NBR, BR, ethylene propylene rubber (EPM, EPDM), neoprene rubber (CR), butyl rubber, halogenated butyl rubber, and natural rubber. As for natural rubber, silanol can be introduced if vinyl pyridine is bonded in a predetermined amount or more by graft polymerization.
[0010]
Silanol can be obtained, for example, by binding silanol obtained by acid treatment of sodium silicate silicate or water glass as a pyridinium salt to a pyridine ring protruding from the side chain of the rubber body. This silanol is bonded to the end of the side chain of the rubber body. More specifically, the pyridine ring present in the side chain of the synthetic rubber modified with vinylpyridine is quaternized with an alkyl halide and reacted with the quaternary salt to bind to the quaternary salt. It can be formed by substitution bonding of halogen with silanol. This quaternary chlorination treatment of the pyridine ring can be easily performed in a solution state by using a latex- like synthetic rubber.
[0011]
The amount of silanol contained in the rubber body is preferably in the range of 20-30.
The amount of silanol depends on the amount of vinylpyridine copolymerized with the synthetic rubber. In order to synthesize a seismic isolation rubber, it is preferable to use a vinylpyridine-modified synthetic rubber in which about 2% of vinylpyridine is copolymerized.
When the amount of pyridine ring bonds is insufficient, it is possible to make up for the shortage by graft polymerization of vinyl pyridine on rubber.
[0012]
In order to bond silanol to the pyridine ring in the rubber body, first, the pyridine ring is quaternized. This quaternary chloride is formed by reacting an alkyl halide with a pyridine ring. This reaction can be obtained, for example, by adding an alkyl halide solution to a rubber latex containing a pyridine ring. Examples of the alkyl halide include ethyl bromide, propyl bromide, butyl bromide, butyl chloride, propyl chloride and the like.
[0013]
Next, by adding an acid-treated silicate to the latex in which the quaternary salt has been formed and substituting the silanol for the halogen of the quaternary salt, the rubber is isolated. Can be easily formed with a solution.
The rubber containing silanol has a characteristic of exhibiting anti-deformability as an elastic body that is soft and has high elongation when silanol plays a role of cross-linking between molecules when uncrosslinked. Even after the crosslinking treatment, as will be described later, it has a breaking strength and a hysteresis loss value that are higher than those of natural rubber. However, there is a problem with setability alone.
[0014]
Comparing the physical properties of vulcanized rubber containing 60% natural rubber with this silanol-containing rubber and vinylpyridine-modified synthetic rubber that does not contain silanol, as shown in the tensile test in FIG. When blended in rubber (marked with ●), the elongation at break and breaking strength are higher than those of pyridine-modified synthetic rubber (■) containing no silanol. Further, when the elongation of the above-described tensile-return test is pulled to 150% and then the hysteresis loss value calculated from the area in the loop drawn when the tension is relaxed is compared, FIG. As shown, although there is a slight difference, it seems to be almost the same, and it shows that both have a large and high attenuation compared to the hysteresis loss value in the case of natural rubber alone (see the case of NR10 in FIG. 7 described later). .
[0015]
Comparing the results of this tensile-return test performed three times in succession (FIG. 3 rubber with silanol, FIG. 4 pyridine-modified synthetic rubber not containing silanol), the hysteresis loss value (the area drawn by the loop) is the first to second. ) Decreases, but the silanol-containing one has a lower hysteresis loss peak value as shown in FIG. 3 than the case of not containing silanol in FIG. 4 and is more resistant to repeated deformation (as shown in FIG. 3). It is understood that the physical properties of rubber can be improved by introducing silanol.
[0016]
The rubber having silanol (corresponding to LATEX in FIGS. 5 and 6) was vulcanized at a different blending ratio to natural rubber (corresponding to NR in FIGS. 5 and 6) blended with carbon black, and the breaking strength was examined. The results are shown in FIGS. 5 and 6, it can be seen that the lower curves do not include rubber having silanol, and that the tensile strength is greatly improved in each compounding ratio by adding rubber having silanol.
[0017]
Therefore, the results of the tensile-return test for each sample in which the blending ratio of the rubber (LATEX) having silanol to the natural rubber (NR) containing carbon black was changed from 0:10 to 10: 0 are shown in FIGS. As shown in FIG. As shown in FIG. 7, only in the case of natural rubber not containing rubber having silanol, a loop with a narrow area is shown below, which is a low value. Based on the result, the hysteresis loss value was calculated. The value of the calculation result is shown in the bar graph of FIG.
[0018]
In the case of natural rubber (NR) alone, the hysteresis loss value was about 70 and did not reach 100, but all of those blended with rubber having a silanol (LATEX) exceeded the hysteresis loss value of 150 and showed a high damping property. Of these, the best value was obtained when the blending ratio of natural rubber (NR) and silanol-containing rubber (LATEX) was 6: 4. Further, the hysteresis loss value of rubber blended with rubber having silanol at a ratio other than the above is almost the same as shown in the bar graph of FIG. 10 with some errors.
[0019]
Therefore, as shown in FIG. 10, it is shown that the rubber itself having silanol (example of LATEX 10: 0) also has a high damping property. For this reason, since the damping property of the rubber itself having silanol is recognized, the rubber having silanol can be expected to be used as a new seismic isolation rubber.
Accordingly, the hysteresis loss value of the third time is shown by performing the third tensile-return test for each sample cross-linked by changing the compounding ratio (LATEX: NR) of the rubber having the silanol and the natural rubber to 150% and FIG. It is shown in the bar graph. The rubber compounded in the ratios of LATEX: NR = 4: 6 and LATEX: NR = 6: 4, 4: 6 showed good values exceeding 60. Moreover, the thing with little compounding quantity of the rubber | gum which has silanol also showed the value close to 50. Further, the bar graph at the left end of FIG. 11 is a value only for natural rubber, and those blended with other rubbers having each silanol are higher than those at the left end, and the hysteresis loss is higher than that of natural rubber by blending rubber with silanol. The value is shown.
[0020]
Similarly, when a rubber not containing silanol and a rubber containing silanol were blended with natural rubber, the one blended with a rubber having silanol showed a higher hysteresis loss value.
In general, it is considered that a set having a large hysteresis loss is poor in setability. Therefore, the bar graph of FIG. 12 shows the degree of compression set for the samples having the above-described blending ratios. According to this, the setability was almost the same as that of the control when the blend ratio of the rubber having silanol was 10%.
[0021]
Therefore, the rubber having silanol of the present invention can be used as a high damping rubber for seismic isolation rubber.
[0022]
【Example】
Hereinafter, specific examples will be described.
Example 1
Commercially available water glass No. 3 (15.65 g) was diluted with deionized water (1000 ml) to prepare a 0.08 mol / L silicate solution. To this silicate solution (50 g), 2N aqueous sulfuric acid solution (1 to 1.3 ml) was added dropwise to adjust the pH of the solution to 6 to 7, and the solution was transferred to a separatory funnel. Tetrahydrofuran (20 ml) and sodium chloride (10 g) were added to the solution in the separatory funnel, and the separatory funnel was shaken. Thereafter, the separatory funnel was allowed to stand and separated into two layers, and then the upper organic layer was separated. This separation operation was repeated 5 times.
[0023]
A solution obtained by dissolving 0.70 g of an alkyl halide (n-propyl bromide) in 10 ml of chloroform was added dropwise to 140 g of vinylpyridine-modified SBR (vinylpyridine content: 2%) to form pyridine as a quaternary salt. The tetrahydrofuran solution containing silanol prepared above was added to the quaternized chlorinated reaction solution to cause the reaction, 4 ml of sulfuric acid was added to salt out, the precipitate was dried for 2 days, and the solid of SBR rubber having silanol was solidified. A product was made.
[0024]
20 g of carbon black SEAST600 was added to a mixture of 5 g of SBR rubber having silanol and 45 g of natural rubber (in the case of 1: 9, each sample was prepared by changing the blending ratio to a predetermined percentage and making the total amount of the sample 10). 2.5 g of activated zinc flower, 1 g of vulcanization accelerator, and 1 g of sulfur were blended, and the roll temperature was set to 50 ° C. using a roll manufactured by Chemical Machinery Design Manufacturing Co., Ltd. and kneaded with a roller to form a sheet. The finished rubber was left for one day, then the vulcanization time was calculated by applying JSR type Clastast (160 ° C) made by Imachu Machinery Co., Ltd. and taking into account this time, it was vulcanized by pressing machine (160 ° C). .
[0025]
The obtained samples were subjected to measurement of high elongation and hysteresis loss using an AR-6000 Tensilon universal testing machine manufactured by ORINTEC. The results of the tensile test are shown in FIGS. 5 and 6, and the results of the tensile-return test are shown in FIGS. 7, 8, and 9. The calculated value of hysteresis loss is shown by the bar graph in FIG.
(Example 2)
Water glass No. 3 (15.65 g) was diluted with deionized water (1000 ml) to prepare a 0.08 mol / L silicate solution. To this silicate solution (50 g), 2N aqueous sulfuric acid solution (1 to 1.3 ml) was added dropwise to adjust the pH of the solution to 6 to 7, and the solution was transferred to a separatory funnel. Tetrahydrofuran (20 ml) and sodium chloride (10 g) are added to the solution in the separatory funnel and the separatory funnel is shaken. After separating the separatory funnel into two layers, the upper organic layer was separated.
[0026]
Side chain pyridine copolymerized with SBR by dropwise adding a solution of 0.65 g of alkyl halide (n-propyl bromide) in 10 ml of chloroform to 200 g of vinylpyridine-modified SBR (vinylpyridine content 2%) Was quaternized. After adding the tetrahydrofuran solution containing silicic acid prepared above to the reaction solution subjected to the quaternary chlorination treatment, the quaternary salt and silicic acid are reacted, and 4 ml of sulfuric acid is added to the reaction solution for salting out. The resulting precipitate was dried for 2 days to prepare a silanol-containing SBR rubber solid in which silicic acid was bound to a pyridine quaternary salt.
[0027]
20 g of carbon black SEAST600 was added to a mixture of 5 g of the resulting silanol-containing synthetic rubber and 45 g of natural rubber (in the case of 1: 9, each sample was prepared by changing this blending ratio to a predetermined ratio), and activated zinc white2. 5 g, 1 g of a vulcanization accelerator, and 1 g of sulfur were blended, and the roll temperature was set to 50 ° C. using a roll manufactured by Chemical Machinery Design Manufacturing Co., Ltd. and kneaded with the roll to form a sheet. After the rubber has been kneaded for one day, the vulcanization time is calculated by applying JSR type Clastast (160 ° C) made by Imachu-Machinery Co., Ltd. A sample was prepared. For each of the obtained samples, the tensile-return test for returning to the original tension until 150% elongation was performed three times, and the values of the hysteresis loss calculated for the third hysteresis loop are shown in the bar graph of FIG.
[0028]
In addition, the compression set showing the setability was measured by measuring the change in the sheet thickness of the sample after holding the sheet of each sample in a compression set tester and holding it in a dryer at 70 ° C. for 24 hours. The results are shown in the bar graph of FIG.
[0029]
【The invention's effect】
The rubber having silanol of the present invention is superior in physical property value to hysteresis loss and tensile strength than those of conventional seismic isolation rubber made of natural rubber. Therefore, the rubber having silanol of the present invention is useful for use as a high damping rubber.
[Brief description of the drawings]
FIG. 1 is a graph of SS curves of rubber with and without silanol.
FIG. 2 is a graph of hysteresis loops of rubber with and without silanol.
FIG. 3 is a graph of three tensile-return tests for rubber with silanol.
FIG. 4 is a graph of three tensile-return tests for rubber without silanol.
FIG. 5 is a graph of an SS curve of a vulcanized rubber produced by changing the compounding ratio of rubber having silanol and natural rubber.
FIG. 6 is a graph of SS curves of vulcanized rubber produced by changing the compounding ratio of rubber having silanol and natural rubber.
FIG. 7 is a graph of a hysteresis loop of vulcanized rubber produced by changing the compounding ratio of rubber having silanol and natural rubber.
FIG. 8 is a graph of a hysteresis loop of vulcanized rubber produced by changing the compounding ratio of rubber having silanol and natural rubber.
FIG. 9 is a graph of hysteresis loops of vulcanized rubber produced by changing the compounding ratio of rubber having silanol and natural rubber.
FIG. 10 is a bar graph showing a hysteresis loss value calculated from a hysteresis loop of a vulcanized rubber produced by changing the compounding ratio of rubber having silanol and natural rubber.
FIG. 11 is a bar graph showing the value of hysteresis loss calculated from the hysteresis loop of vulcanized rubber produced by changing the compounding ratio of rubber having silanol and natural rubber.
FIG. 12 is a bar graph showing setability values of vulcanized rubber produced by changing the compounding ratio of rubber having silanol and natural rubber.

Claims (1)

SBR, NBR, BR, EPM, EPDM, CR, butyl rubber, halogenated butyl rubber, natural rubber and at least one rubber main body and a side chain bonded to the rubber main body, the side chain is a silanol pyridinium A rubber with silanol, characterized by consisting of salt.

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