Preparation method and application of hindered phenol quaternary phosphonium salt modified montmorillonite

Abstract

The invention discloses a preparation method and application of hindered phenol quaternary phosphonium salt modified montmorillonite, and belongs to the technical field of damping vibration attenuation materials.The preparation method comprises the steps that 2, 6-butylated hydroxytoluene, N-chlorosuccinimide and triphenylphosphine serve as raw materials, hindered phenol quaternary phosphonium salt is prepared, then the hindered phenol quaternary phosphonium salt is used for modifying montmorillonite, and the hindered phenol quaternary phosphonium salt modified montmorillonite is obtained. A new hindered phenol modified montmorillonite filler is prepared; the hindered phenol modified montmorillonite provided by the invention is applied to preparation of a butyl rubber composite damping material, and the ratio of hindered phenol quaternary phosphonium salt modified montmorillonite to butyl rubber is (2: 1)-(3: 1). According to the invention, the hindered phenol quaternary phosphonium salt modified montmorillonite is introduced into a butyl rubber system as a modified filler, so that on one hand, a wider damping temperature range and better stripping performance can be obtained; on the other hand, the mechanical property of the composite material is improved, and meanwhile the damping performance of the material is improved.

Description

Technical Field

[0001] The invention mainly relates to the technical field of damping and vibration reduction materials, and specifically relates to a preparation method and application of hindered phenol quaternary phosphonium salt modified montmorillonite. Background Art

[0002] Damping and vibration reduction materials are materials that effectively reduce the harm caused by vibration through the properties of the material itself. Its main advantage is that it does not require complex structural design and is simple and convenient to produce and maintain. It reduces vehicle vibration by deforming the material due to external stress. By designing and researching the material formula, it can not only effectively improve the damping and vibration reduction effect of the material, but also optimize the physical and mechanical properties of the material, greatly increasing its service life.

[0003] Butyl rubber is a copolymer of isobutylene and a small amount of isoprene. Its molecular chain structure contains a large number of side methyl groups. The steric hindrance effect of these side methyl groups makes the butyl rubber molecular chain segments have large elastic hysteresis, energy dissipation and damping effects when they move. The macroscopic performance is high damping performance. In addition, butyl rubber has good air tightness, very low unsaturation, stable structure, good heat resistance and aging resistance, so it is widely used in rubber damping products. However, the main problem of butyl rubber at present is that it cannot take into account the wide effective damping temperature range and high damping peak value, so its application field has certain limitations.

[0004] Montmorillonite is a natural layered silicate mineral, whose main chemical composition is Al2O3‧4SiO2‧3H2O. Its crystal structure is formed by two layers of silicon-oxygen tetrahedrons and aluminum (magnesium)-oxygen octahedrons connected by oxygen to form a 2:1 layered structure. It can construct a tiny constrained damping structure in the polymer matrix to cause the dissipation of vibration energy, thereby achieving the effect of enhancing the damping effect, so it is widely used in polymer damping systems. Like other fillers, there is a problem when montmorillonite is added to the polymer system as a filler. It has poor compatibility with polymers and is prone to agglomeration, which not only affects the damping performance of the material, but also affects its mechanical properties. Therefore, it needs to be modified to improve its compatibility with the polymer matrix.

[0005] As an organic polar small molecule, hindered phenol is often modified and added to the rubber system as a functional additive. Adding organic polar small molecules such as hindered phenols to the polymer matrix can form reversible hydrogen bonds with polar side groups in the rubber matrix. When subjected to external stress or vibration, the hydrogen bonds in the material are weakened or broken, and new hydrogen bonds are continuously formed. This process will consume a large amount of energy in the system, convert mechanical energy into internal energy, and improve the damping performance of the composite material. For example: In Chinese patent CN201910493153.7, hindered phenol-modified montmorillonite obtained by modifying montmorillonite with hindered phenol is added to chlorobutyl rubber. In another Chinese patent CN201510706304.4, montmorillonite is modified by 4-allyl-2,6-dimethoxyanisole to obtain 4-allyl-2,6-dimethoxyanisole-modified montmorillonite, which is added to chlorobutyl rubber. The exemplified patent documents all adopt various measures to modify montmorillonite to obtain modified montmorillonite, which is then added to a rubber matrix to improve the damping performance of the rubber. However, the effective damping temperature range and damping performance of the polymer materials obtained in the above patents are limited.

[0006] Therefore, the development of new hindered phenol-modified montmorillonite fillers is of great practical significance for obtaining vibration and noise reduction damping materials with excellent comprehensive performance. Summary of the invention

[0007] The technical solution of the present invention aims at the technical problem that the existing technical solutions are too single, and provides a solution that is significantly different from the existing technology. It mainly provides a preparation method and application of hindered phenol quaternary phosphonium salt modified montmorillonite, which is used to solve the technical problems of the limited effective damping temperature range and damping performance of existing polymer materials raised in the above background technology.

[0008] The technical solution adopted by the present invention to solve the above technical problems is: A method for preparing hindered phenolic quaternary phosphonium salt modified montmorillonite comprises the following steps: (1) dissolving 2,6-di-tert-butyl-p-cresol, N-chlorosuccinimide and a catalyst in a carbon tetrachloride solution under the protection of an inert gas, and reacting to obtain a benzyl hindered phenol; the mass ratio of the 2,6-di-tert-butyl-p-cresol to the N-chlorosuccinimide is 1.429:1; (2) adding triphenylphosphine and the benzyl hindered phenol obtained in step (1) to n-heptane under the protection of an inert gas, and reacting to obtain a hindered phenol quaternary phosphonium salt; the mass ratio of the benzyl hindered phenol to the triphenylphosphine is 1:1.27; (3) dispersing montmorillonite in deionized water, heating and stirring, and then adding the hindered phenol quaternary phosphonium salt prepared in step (2) to react; and then post-treating the product to obtain the hindered phenol quaternary phosphonium salt modified montmorillonite.

[0009] Furthermore, in step (1), the catalyst is at least one of azobisisobutyronitrile and azobisisoheptylnitrile.

[0010] Furthermore, the relationship between the amount of carbon tetrachloride solution used in step (1) and 2,6-di-tert-butyl is that 1 gram of 2,6-di-tert-butyl corresponds to 20 mL of carbon tetrachloride solution.

[0011] Furthermore, in step (1), the reaction temperature is 90-110° C., and the reaction time is 6-12 hours.

[0012] Furthermore, in step (2), the relationship between the amount of n-heptane and the benzyl hindered phenol is that 1 gram of benzyl hindered phenol corresponds to 20 mL of n-heptane.

[0013] Furthermore, in step (2), the reaction temperature is 70-90° C., and the reaction time is 2-6 hours.

[0014] Furthermore, in step (3), the mass ratio of the hindered phenol quaternary phosphonium salt to montmorillonite is 0.599:1.

[0015] Furthermore, in step (3), the heating and stirring temperature is 60-80° C., and the reaction time is 7-9 hours.

[0016] Furthermore, in step (3), the post-treatment step includes: firstly, filtering by suction, washing the filter cake obtained by the filtration with deionized water; then washing with a 50% ethanol solution until no white precipitate is generated when the filtrate reacts with AgNO3; finally, drying at 100°C, and grinding through a 400-mesh sieve to finally obtain hindered phenol quaternary phosphonium salt modified montmorillonite.

[0017] The present invention also provides an application of hindered phenolic quaternary phosphonium salt modified montmorillonite. The hindered phenolic quaternary phosphonium salt modified montmorillonite prepared by the preparation method is applied to prepare a butyl rubber composite damping material, namely, hindered phenolic quaternary phosphonium salt modified montmorillonite composite butyl damping rubber; the hindered phenolic quaternary phosphonium salt modified montmorillonite composite butyl damping rubber comprises the following components in weight ratio: 100 parts of butyl rubber, 200-300 parts of hindered phenolic quaternary phosphonium salt modified montmorillonite, 100-150 parts of polyisobutylene, 30 parts of a reinforcing agent, 30 parts of a tackifier, and 10 parts of carbon black.

[0018] Furthermore, the butyl rubber is one or more of Exxon268, Xinhui 532, and Yanshan IIR1751; And / or, the polyisobutylene is one or more of PB 680, PB1300, and PB2400; And / or, the carbon black is one or more of N330, N774, and N990.

[0019] Further, the reinforcing agent is one or more of fumed silica and precipitated silica; And / or, the tackifier is one or more of petroleum resin, terpene resin, phenolic resin, and epoxy resin.

[0020] Furthermore, the preparation method of the hindered phenolic quaternary phosphonium salt modified montmorillonite composite butyl damping rubber comprises the following steps: (1) Put the proportion of butyl rubber into an internal mixer and mix it at 80-100°C for 10 min; (2) Continue to add the proportion of tackifier, carbon black and reinforcing agent and continue mixing for 20 minutes; (3) Continue to add half of the proportion of hindered phenolic quaternary phosphonium salt modified montmorillonite and liquid polyisobutylene and continue mixing for 20 minutes; (4) Continue to add the remaining half of the hindered phenolic quaternary phosphonium salt-modified montmorillonite and liquid polyisobutylene and continue mixing for 40 minutes; (5) After the material is discharged, it is naturally cooled to room temperature to obtain the hindered phenol quaternary phosphonium salt modified montmorillonite composite butyl damping rubber.

[0021] Compared with the prior art, the present invention has the following beneficial effects: (1) The present invention uses 2,6-di-tert-butyl-p-cresol, N-chlorosuccinimide and triphenylphosphine as raw materials to prepare a hindered phenol quaternary phosphonium salt, and then uses the hindered phenol quaternary phosphonium salt to modify montmorillonite to obtain a new hindered phenol-modified montmorillonite filler. Compared with the existing hindered phenol-modified montmorillonite filler, the hindered phenol selected in the present invention is 2,6-di-tert-butyl-p-cresol. Relative to 2,6-di-tert-butyl-p-phenol, an electron-repelling group such as methyl is introduced at the para position, and the antioxidant effect is significantly increased; when the para position of the phenolic hydroxyl group is a long-chain alkyl, it is beneficial to improve the compatibility.

[0022] (2) The hindered phenol-modified montmorillonite filler provided by the present invention is added to butyl rubber to prepare a composite damping material. On the one hand, the compatibility of the montmorillonite filler and butyl rubber is greatly improved, the bonding strength between the interfaces is enhanced, and the mechanical properties of the composite material are improved; on the other hand, since the interlayer spacing of the montmorillonite is increased after being modified by the hindered phenol quaternary phosphonium salt, the montmorillonite can better bind the polymer molecular chains, thereby improving the damping performance of the material.

[0023] (3) The hindered phenol quaternary phosphonium salt modified montmorillonite provided by the present invention is introduced into the composite damping material system, avoiding the additional addition of antioxidants. At the same time, the hindered phenol can form hydrogen bonds with the polar side groups in the rubber matrix. By adjusting its content, the glass transition temperature of the rubber material can be changed, achieving the effect of adjustable optimal damping temperature range, obtaining a wider damping temperature range and better peeling performance. According to experiments, the damping temperature range of the hindered phenol quaternary phosphonium salt modified montmorillonite composite butyl damping rubber of the present invention can reach 162.9~197.0.

[0024] (4) The hindered phenolic quaternary phosphonium salt-modified montmorillonite composite butyl damping rubber prepared by the present invention is a non-vulcanized rubber composite material. Unlike vulcanized rubber composite materials, the non-vulcanized rubber has self-adhesiveness, which can improve the peel strength of the material, thereby facilitating the damping and vibration reduction effect of the material. According to experiments, the peel strength of the hindered phenolic quaternary phosphonium salt-modified montmorillonite composite butyl damping rubber of the present invention can reach 1.2~1.5.

[0025] (5) The preparation process of the hindered phenol-modified montmorillonite and the preparation process of the hindered phenol-quaternary phosphonium salt-modified montmorillonite composite butyl damping rubber provided by the present invention are both economical and practical, and the preparation process is simple, low-cost, does not require special equipment and harsh conditions, is easy to achieve large-scale production, and has extremely strong practical value.

[0026] The present invention will be explained in detail below with reference to the accompanying drawings and specific embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The synthetic route of the hindered phenolic quaternary phosphonium salt modified montmorillonite in the present invention; Figure 2 The figure is a curve diagram showing the change of loss factor of the butyl damping rubber composite material obtained in the examples and comparative examples of the present invention with temperature. DETAILED DESCRIPTION

[0028] To facilitate understanding of the present invention, the present invention will be described more comprehensively below with reference to the relevant drawings. Several embodiments of the present invention are given in the drawings, but the present invention can be implemented in different forms and is not limited to the embodiments described in the text. On the contrary, these embodiments are provided to make the content disclosed in the present invention more thorough and comprehensive.

[0029] Example 1: Please refer to the attached Figure 1 A method for preparing hindered phenolic quaternary phosphonium salt-modified montmorillonite comprises the following steps: (1) Under the protection of inert gas, 2 g of 2,6-di-tert-butyl-p-cresol, 1.4 g of N-chlorosuccinimide and 0.3 g of azobisisobutyronitrile were dissolved in 40 mL of carbon tetrachloride solution and reacted at 90°C for 6 h. After the reaction, the mixture was extracted three times with dichloromethane, and the obtained organic layer was washed with deionized water until neutral, then washed with saturated brine, dried over anhydrous Na2SO4, and the solvent was recovered by vacuum distillation at 30°C for 12 h to obtain benzyl hindered phenol.

[0030] (2) Under the protection of inert gas, add 2.54 g of triphenylphosphine and 2 g of benzyl hindered phenol into 40 mL of n-heptane and react at 70°C for 2 h. After the reaction, cool and filter, wash with petroleum ether, and dry in vacuum at 30°C for 12 h to obtain hindered phenol quaternary phosphonium salt.

[0031] (3) 60 g of montmorillonite was dispersed in deionized water and heated at 60°C for 4 h, and then 0.072 mol of hindered phenol quaternary phosphonium salt dissolved in solvent was added dropwise, and the reaction was continued for 7 h. After the reaction was completed, the filter cake was filtered and washed with deionized water, and then washed with 50% ethanol solution until no white precipitate was generated when the filtrate reacted with AgNO3 (0.1 mol / L). The filtrate was dried at 100°C and ground through a 400 mesh sieve to obtain hindered phenol quaternary phosphonium salt modified montmorillonite.

[0032] The hindered phenolic quaternary phosphonium salt modified montmorillonite prepared above is used to prepare a butyl rubber composite damping material. The preparation method of the hindered phenolic quaternary phosphonium salt modified montmorillonite composite butyl damping rubber comprises the following steps: (1) First, put 50 g of butyl rubber into an internal mixer and mix it at 80-100°C for 10 min; (2) Continue to add 15 g of terpene resin, 5 g of N330 carbon black, and 15 g of fumed silica, and continue mixing for 20 min; (3) Add 50 g of hindered phenolic quaternary phosphonium salt-modified montmorillonite and 25 g of PB1300 and continue mixing for 20 min; (4) Continue to add the remaining 50 g of hindered phenol quaternary phosphonium salt modified montmorillonite and 25 g of PB1300, and continue mixing for 40 min; (5) After the material is discharged, it is naturally cooled to room temperature to obtain the hindered phenol quaternary phosphonium salt modified montmorillonite composite butyl damping rubber.

[0033] Embodiment 2: A method for preparing hindered phenolic quaternary phosphonium salt-modified montmorillonite, comprising the following steps: (1) The difference from Example 1 is the amount of reactants and the reaction temperature. Under the protection of inert gas, 3 g of 2,6-di-tert-butyl-p-cresol, 2.1 g of N-chlorosuccinimide and 0.3 g of azobisisobutyronitrile were dissolved in 60 mL of carbon tetrachloride solution and reacted at 100°C for 9 h. After the reaction, the mixture was extracted three times with dichloromethane, and the obtained organic layer was washed with deionized water until neutral, then washed with saturated brine, dried over anhydrous Na2SO4, and the solvent was recovered by vacuum distillation, and dried at 30°C for 12 h to obtain benzyl hindered phenol.

[0034] (2) The difference from Example 1 is the amount of reactants and the reaction temperature. Under the protection of inert gas, 3.81 g of triphenylphosphine and 3 g of benzyl hindered phenol were added to 60 mL of n-heptane and reacted at 80°C for 4 h. After the reaction, the mixture was cooled and filtered, washed with petroleum ether, and dried under vacuum at 30°C for 12 h to obtain hindered phenol quaternary phosphonium salt.

[0035] (3) The difference from Example 1 lies in the amount of reactants and the reaction time. 80 g of montmorillonite was dispersed in deionized water and heated at 70°C for 4 h, and then 0.096 mol of hindered phenol quaternary phosphonium salt dissolved in a solvent was added dropwise, and the reaction was continued for 8 h. After the reaction was completed, the filtration was performed, and the filter cake obtained by filtration was washed with deionized water, and then washed with 50% ethanol solution until no white precipitate was generated when the filtrate reacted with AgNO3 (0.1 mol / L), and dried at 100°C and ground through a 400 mesh sieve to obtain hindered phenol quaternary phosphonium salt modified montmorillonite.

[0036] The hindered phenolic quaternary phosphonium salt modified montmorillonite prepared above is used to prepare a butyl rubber composite damping material. The preparation method of the hindered phenolic quaternary phosphonium salt modified montmorillonite composite butyl damping rubber is different from that of Example 1 in the amount of the hindered phenolic quaternary phosphonium salt modified montmorillonite and polyisobutylene and the mixing temperature. It comprises the following steps: (1) First, put 50 g of butyl rubber into an internal mixer and mix at 90°C for 10 min; (2) Continue to add 15 g of terpene resin, 5 g of N330 carbon black, and 15 g of fumed silica, and continue mixing for 20 min; (3) Add 62.5 g of hindered phenolic quaternary phosphonium salt-modified montmorillonite and 31.25 g of PB1300 and continue mixing for 20 min; (4) Continue to add the remaining 62.5 g of hindered phenolic quaternary phosphonium salt modified montmorillonite and 31.25 g of PB1300, and continue mixing for 40 min; (5) After the material is discharged, it is naturally cooled to room temperature to obtain the hindered phenol quaternary phosphonium salt modified montmorillonite composite butyl damping rubber.

[0037] Embodiment 3: A method for preparing hindered phenolic quaternary phosphonium salt-modified montmorillonite, comprising the following steps: (1) The difference from Example 1 is the amount of reactants and the reaction temperature. Under the protection of inert gas, 4 g of 2,6-di-tert-butyl-p-cresol, 2.8 g of N-chlorosuccinimide and 0.3 g of azobisisobutyronitrile were dissolved in 80 mL of carbon tetrachloride solution and reacted at 110°C for 12 h. After the reaction, the mixture was extracted three times with dichloromethane, and the obtained organic layer was washed with deionized water until neutral, then washed with saturated brine, dried over anhydrous Na2SO4, and the solvent was recovered by vacuum distillation, and dried at 30°C for 12 h to obtain benzyl hindered phenol.

[0038] (2) The difference from Example 1 is the amount of reactants and the reaction temperature. Under the protection of inert gas, 5.08 g of triphenylphosphine and 4 g of benzyl hindered phenol were added to 80 mL of n-heptane and reacted at 90° C. for 6 h. After the reaction, the mixture was cooled and filtered, washed with petroleum ether, and dried under vacuum at 30° C. for 12 h to obtain hindered phenol quaternary phosphonium salt.

[0039] (3) The difference from Example 1 lies in the amount of reactants and the reaction time. 100 g of montmorillonite was dispersed in deionized water and heated at 80°C for 4 h, and then 0.012 mol of hindered phenol quaternary phosphonium salt dissolved in a solvent was added dropwise, and the reaction was continued for 9 h. After the reaction was completed, the filtration was performed, and the filter cake obtained by filtration was washed with deionized water, and then washed with 50% ethanol solution until no white precipitate was generated when the filtrate reacted with AgNO3 (0.1 mol / L), and dried at 100°C and ground through a 400 mesh sieve to obtain hindered phenol quaternary phosphonium salt modified montmorillonite.

[0040] The hindered phenolic quaternary phosphonium salt modified montmorillonite prepared above is used to prepare a butyl rubber composite damping material. The preparation method of the hindered phenolic quaternary phosphonium salt modified montmorillonite composite butyl damping rubber is different from that of Example 1 in the amount of the hindered phenolic quaternary phosphonium salt modified montmorillonite and polyisobutylene and the mixing temperature. It comprises the following steps: (1) First, put 50 g of butyl rubber into an internal mixer and mix it at 100°C for 10 min; (2) Continue to add 15 g of terpene resin, 5 g of N330 carbon black, and 15 g of fumed silica, and continue mixing for 20 min; (3) Add 75 g of hindered phenolic quaternary phosphonium salt-modified montmorillonite and 32.5 g of PB1300 and continue mixing for 20 min. (4) Continue to add the remaining 75 g of hindered phenolic quaternary phosphonium salt-modified montmorillonite and 32.5 g of PB1300 and continue mixing for 40 min; (5) After the material is discharged, it is naturally cooled to room temperature to obtain the hindered phenol quaternary phosphonium salt modified montmorillonite composite butyl damping rubber.

[0041] Comparative Example 1 50 g of butyl rubber, 100 g of montmorillonite, 50 g of PB1300, 15 g of terpene resin, 15 g of fumed silica, and 5 g of N330 carbon black were put into an internal mixer and mixed at 80°C for 90 min to obtain a comparative butyl damping rubber composite material.

[0042] Comparative Example 2 The difference from Comparative Example 1 is the amount of montmorillonite and polyisobutylene used and the mixing temperature. 50 g butyl rubber, 125 g montmorillonite, 62.5 g PB1300, 15 g terpene resin, 15 g fumed silica, and 5 g N330 carbon black were put into an internal mixer and mixed at a temperature of 90°C for 90 min to obtain a comparative butyl damping rubber composite material.

[0043] Comparative Example 3 The difference from Comparative Example 1 is the amount of montmorillonite and polyisobutylene used and the mixing temperature. 50 g butyl rubber, 150 g montmorillonite, 75 g PB1300, 15 g terpene resin, 15 g fumed silica, and 5 g N330 carbon black were put into an internal mixer and mixed at a temperature of 100°C for 90 min to obtain a comparative butyl damping rubber composite material.

[0044] The method reported in "Theory and Practice of Polymer / Layered Silicate Nanocomposites" (Qi Zongneng, Shang Wenyu, Chemical Industry Press, 2002) was used: the interlayer spacing of the hindered phenol quaternary phosphonium salt modified montmorillonite prepared in the example and the montmorillonite used in the comparative example was tested by small angle diffraction method; the particle size of the hindered phenol quaternary phosphonium salt modified montmorillonite prepared in the example and the montmorillonite used in the comparative example was observed by scanning electron microscopy, and the results are shown in Table 1; Table 1 Interlayer spacing and particle size data of montmorillonite and hindered phenol quaternary phosphonium salt modified montmorillonite sample Layer spacing Particle size mm Montmorillonite 1.1-1.4 50~100 Hindered phenolic quaternary phosphonium salt modified montmorillonite 1.5-1.9 60~80 As can be seen from Table 1, compared with montmorillonite, the hindered phenol quaternary phosphonium salt modified montmorillonite prepared in the present invention introduces hindered phenol quaternary phosphonium salt on the basis of unmodified montmorillonite, which effectively increases the interlayer spacing of montmorillonite, so that montmorillonite can better bind polymer molecular chains, thereby improving the damping performance of the material.

[0045] The glass transition temperature and damping performance of the butyl damping rubber composite materials prepared in the examples and comparative examples were tested using a DMA-242E dynamic thermal mechanical analyzer produced by NETZSCH, Germany. The results are shown in Table 2. The loss factor of the butyl damping rubber composite material varies with temperature. Figure 2 As shown; The mechanical properties of the butyl damping rubber composite materials prepared in the examples and comparative examples were tested using GB / T 528-2009 and GB / T 2790-1995. The results are shown in Table 2.

[0046] Table 2 Performance test data of rubber materials sample <![CDATA[Peak loss factor tanδ max > Effective damping temperature range (tan>0.3) Tensile strengthMpa Peel strength kN / m Example 1 1.306 162.9 0.142 1.2 Comparative Example 1 1.221 131.1 0.098 0.6 Example 2 1.402 197.0 0.187 1.5 Comparative Example 2 1.272 148.4 0.113 0.9 Example 3 1.269 190.9 0.153 1.4 Comparative Example 3 1.256 148.0 0.108 0.8 As can be seen from Table 2, the present invention prepares a new hindered phenol quaternary phosphonium salt modified montmorillonite and applies it to the butyl damping rubber composite material instead of montmorillonite. On the one hand, the compatibility of montmorillonite and butyl rubber is greatly improved, the bonding strength between the interfaces is improved, and the mechanical properties of the composite material are improved; on the other hand, since the interlayer spacing of montmorillonite is increased after being modified by the hindered phenol quaternary phosphonium salt, the montmorillonite can better bind the polymer molecular chain, thereby improving the damping performance of the material.

[0047] Depend on Figure 2 It can be seen that due to the hydrogen bonding between hindered phenol and polar side groups in the rubber matrix, the glass transition temperature of the rubber material can be changed by adjusting the content of montmorillonite modified by hindered phenol quaternary phosphonium salt, so as to achieve the effect of adjustable temperature range for optimal damping, obtain a wider damping temperature range and a higher loss factor peak.

[0048] The above is an exemplary description of the present invention in conjunction with the accompanying drawings. It is obvious that the specific implementation of the present invention is not limited to the above-mentioned method. As long as such non-substantial improvements are made by adopting the method concept and technical solution of the present invention, or the concept and technical solution of the present invention are directly applied to other occasions without improvement, they are all within the protection scope of the present invention.

Claims

1. A method for preparing hindered phenolic quaternary phosphonium salt-modified montmorillonite, characterized in that: The steps include: (1) dissolving 2,6-di-tert-butyl-p-cresol, N-chlorosuccinimide and a catalyst in a carbon tetrachloride solution under the protection of an inert gas, and reacting to obtain a benzyl hindered phenol; the mass ratio of the 2,6-di-tert-butyl-p-cresol to the N-chlorosuccinimide is 1.429:1; (2) adding triphenylphosphine and the benzyl hindered phenol obtained in step (1) to n-heptane under the protection of an inert gas, and reacting to obtain a hindered phenol quaternary phosphonium salt; the mass ratio of the benzyl hindered phenol to the triphenylphosphine is 1:1.27; (3) dispersing montmorillonite in deionized water, heating and stirring, and then adding the hindered phenol quaternary phosphonium salt prepared in step (2) to react; and then post-treating the product to obtain the hindered phenol quaternary phosphonium salt modified montmorillonite.

2. The method for preparing a hindered phenol quaternary phosphonium salt modified montmorillonite according to claim 1, characterized in that: In step (1), the catalyst is at least one of azobisisobutyronitrile and azobisisoheptanenitrile.

3. The method for preparing a hindered phenol quaternary phosphonium salt modified montmorillonite according to claim 1, characterized in that: In step (1), the relationship between the amount of the carbon tetrachloride solution and 2,6-di-tert-butyl is that 1 gram of 2,6-di-tert-butyl corresponds to 20 mL of carbon tetrachloride solution.

4. The method for preparing a hindered phenol quaternary phosphonium salt modified montmorillonite according to claim 1, characterized in that: In step (1), the reaction temperature is 90-110° C. and the reaction time is 6-12 hours.

5. The method for preparing a hindered phenol quaternary phosphonium salt modified montmorillonite according to claim 1, characterized in that: In step (2), the relationship between the amount of n-heptane and benzyl hindered phenol is that 1 gram of benzyl hindered phenol corresponds to 20 mL of n-heptane.

6. The method for preparing a hindered phenol quaternary phosphonium salt modified montmorillonite according to claim 1, characterized in that: In step (2), the reaction temperature is 70-90° C. and the reaction time is 2-6 hours.

7. The method for preparing a hindered phenol quaternary phosphonium salt modified montmorillonite according to claim 1, characterized in that: In step (3), the mass ratio of the hindered phenol quaternary phosphonium salt to montmorillonite is 0.599:

1.

8. The method for preparing a hindered phenol quaternary phosphonium salt modified montmorillonite according to claim 1, characterized in that: In step (3), the temperature of heating and stirring is 60-80° C., and the reaction time is 7-9 hours.

9. The method for preparing a hindered phenol quaternary phosphonium salt modified montmorillonite according to claim 1, characterized in that: In step (3), the post-treatment step includes: firstly, filtering by suction, washing the filter cake obtained by the filtration with deionized water; then washing with a 50% ethanol solution until no white precipitate is generated when the filtrate reacts with AgNO3; finally, drying at 100°C, and grinding through a 400-mesh sieve to finally obtain hindered phenol quaternary phosphonium salt modified montmorillonite.

10. A hindered phenolic quaternary phosphonium salt modified montmorillonite, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 9.

11. An application of hindered phenolic quaternary phosphonium salt modified montmorillonite, characterized in that: The hindered phenol quaternary phosphonium salt modified montmorillonite described in claim 10 is used to prepare a butyl rubber composite damping material, which is a hindered phenol quaternary phosphonium salt modified montmorillonite composite butyl damping rubber; the hindered phenol quaternary phosphonium salt modified montmorillonite composite butyl damping rubber comprises the following ingredients in weight ratio: 100 parts of butyl rubber, 200-300 parts of hindered phenol quaternary phosphonium salt modified montmorillonite, 100-150 parts of polyisobutylene, 30 parts of a reinforcing agent, 30 parts of a tackifier, and 10 parts of carbon black.

12. The use of a hindered phenolic quaternary phosphonium salt modified montmorillonite according to claim 11, characterized in that: The butyl rubber is one or more of Exxon268, Xinhui 532, and Yanshan IIR1751; And / or, the polyisobutylene is one or more of PB 680, PB1300, and PB2400; And / or, the carbon black is one or more of N330, N774, and N990.

13. The use of a hindered phenolic quaternary phosphonium salt modified montmorillonite according to claim 11, characterized in that: The reinforcing agent is one or more of fumed silica and precipitated silica; And / or, the tackifier is one or more of petroleum resin, terpene resin, phenolic resin, and epoxy resin.

14. The use of a hindered phenolic quaternary phosphonium salt modified montmorillonite according to claim 11, characterized in that: The preparation method of the hindered phenol quaternary phosphonium salt modified montmorillonite composite butyl damping rubber comprises the following steps: (1) Put the proportion of butyl rubber into an internal mixer and mix it at 80-100°C for 10 min; (2) Continue to add the proportion of tackifier, carbon black and reinforcing agent and continue mixing for 20 minutes; (3) Continue to add half of the proportion of hindered phenolic quaternary phosphonium salt modified montmorillonite and liquid polyisobutylene and continue mixing for 20 minutes; (4) Continue to add the remaining half of the hindered phenolic quaternary phosphonium salt-modified montmorillonite and liquid polyisobutylene and continue mixing for 40 minutes; (5) After the material is discharged, it is naturally cooled to room temperature to obtain the hindered phenol quaternary phosphonium salt modified montmorillonite composite butyl damping rubber.

15. A hindered phenolic quaternary phosphonium salt-modified montmorillonite composite butyl damping rubber, characterized in that: Prepared by the preparation method described in claim 14.

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