Dibenzylideneacetone modified hydrophobic butyl rubber damping composite material and preparation method therefor

Abstract

The present invention belongs to the field of polymer-based damping materials. Disclosed are a dibenzylideneacetone modified hydrophobic butyl rubber damping composite material and a preparation metho

Description

[0002] The present disclosure relates to a dibenzylidene acetone modified hydrophobic Isobutylene isoprene rubber damping composite and a preparation method thereof, belonging to the field of polymer-based damping materials. BACKGROUND

[0003] At present, many new materials and technologies have been continuously applied to damping and shock-absorption, among which polymer materials, especially rubber damping and shock-absorption materials, have attracted more and more attention because of their excellent performance. The use of rubber damping materials could minimize mechanical noise and vibration, improve work efficiency and enhance product quality. Some commonly used asphalt-based damping pads for vehicles will emit carcinogens such as naphthalene, anthracene, and phenanthrene during use, and show relatively poor damping effect, and thus could not meet people's requirements for the comfort, health, and quiet travel experience. Polymer-based damping materials have a greatly reduced emission of toxic substances in cars, and a desirable damping effect at ambient temperature and above. Furthermore, the polymer-based damping materials could be prepared from renewable raw materials, and thereby have advantages such as sustainable development, safety, health, and environmental friendliness.

[0004] Water exists in every corner of nature, but in some fields, it is not desirable to have water for a long time, and thus hydrophobic materials are needed. Hydrophobic materials are widely used and appear in all aspects of life, including aerospace, military industry, transportation, agriculture, construction, medical treatment, daily textiles and other aspects, and have a very broad prospect. The hydrophobic materials generally have a contact angle of above 90°, and its preparation mainly involves two methods. One is to add substances with low surface energy, such as long alkyl chain-containing substances or fluorine-containing substances, to the materials. The other is to construct rough surfaces with a micro-nano structure. However, these two methods for preparing hydrophobic materials each have advantages and disadvantages. Generally, a main method for industrial production of hydrophobic materials is to add hydrophobic masterbatch, that is, to add substances with low surface energy, but the hydrophobic materials prepared by this method has an average level of hydrophobic effect, which could only meet the general hydrophobic requirements; the hydrophobic materials prepared by constructing rough interfaces have better hydrophobic effect, but the preparation process is relatively complicated and the rough interfaces are easy to be destroyed, which greatly reduces the hydrophobic effect, requiring regular replacement and thus causing high cost. Currently, the desirable preparation method for producing hydrophobic materials is a combination of the two processes, in which the two processes play a synergistic effect, that is, the preparation method not only includes constructing a rough surface, but also includes covering its surface with a substance having low surface energy. However, the process of this method has not yet reached the capacity of complete industrialization and large-scale production. [00051 For traditional asphalt-based or viscoelastic damping materials, due to polar functional groups, isobutylene isoprene rubber is generally a hydrophilic material, and thus it often absorbs moisture during use, and moreover, it has a poor thermal stability, resulting in short service life of traditional damping materials. Therefore, it is imperative to develop a damping material with good moisture resistance and high thermal stability. However, there are few references to study the hydrophobicity of damping materials. Bo Chen from Beijing University of Chemical Technology (Bo Chen, Research on organosilicone-modified polybutadiene polyurethane damping material and performance thereof [D], Beijing University of Chemical Technology, 2017) disclosed a method for preparing a PU damping material, including selecting hydroxyl-terminated polydimethylsiloxane (HTPDMS) and Hydroxyl-terminated polybutadiene (HTPB) as a blended soft segment; subjecting the soft segment and diphenylmethane diisocyanate (MDI) to block copolymerization, and conducting prepolymer process or pouring process to prepare the PU damping material with an increased surface hydrophobicity by using dipropylene glycol (DPG) and glycerol (GLY) as chain extenders; and further disclosed a method for preparing a polyurethane damping elastomer, which includes selecting heptamethyltrisiloxane grafted hydroxyl-terminated polybutadiene (HTMS-g-HTPB) and poly(tetramethylene ether glycol) (PTMEG2000) as a mixed segment, then subjecting the mixed segment, diphenylmethane diisocyanate (MDI) and chain extender dipropylene glycol (DPG) to prepolymer process to prepare the polyurethane damping elastomer. By adjusting the ratio between the two phases of the soft segment, with the increase of HMTS-g-HTPB content, the mechanical performance of the materials is comprehensively improved, and the hydrophobic ability of the surface thereof is enhanced. Yu Zang et al. (Yu Zang, Tianyang Lei, Aoki Toshiki, et al., Research on graft-modified polyesters with fluorinated acrylate macromer[J]. Journal of Qiqihar University (Natural Science Edition), 2020,36(03):77-80) have studied the effect of methyl methacrylate and methylacrylic acid octyl ester grafted with fluorinated branch chains on the hydrophilicity of the material, and found that the material after graft modification has an increased contact angle of 128.8°, and is changed from a hydrophilic material to a hydrophobic material. Although the two methods could improve the hydrophobic performance of damping materials, the preparation thereof has a very complicated process and a relatively high cost, which limits industrial application. SUMMARY

[0006] The present disclosure aims to provide a method for preparing a dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite. By adding a bio-based phenolic resin, and activating and modifying isobutylene isoprene rubber (IIR) with NaH while introducing rigid benzene ring groups, the method makes it possible to broaden the damping temperature range and improve the damping factor of the IIR, results in a green and environmentally friendly hydrophobic damping composite, and has simple operations.

[0007] The present disclosure provides the following technical solutions.

[0008] In a first aspect, the present disclosure provides a method for preparing a dibenzylidene acetone modified hydrophobic IIR damping composite, comprising the following steps:

[0009] (1) adding IIR and NaH in a proportion to a torque rheometer, and conducting reaction in the torque rheometer for 10 min to 15 min to obtain a reactant; then adding dibenzylidene acetone into the reactant, continuing the reaction for another 10 min to 15 min to obtain a rubber material, and taking out the rubber material after the reaction;

[0010] (2) plasticizing the rubber material obtained in step (1) on a two-roller mixer, adding stearic acid, zinc oxide, tetramethylthiuram (TMTD), tetramethylthiuram disuofide (DM), sulfur, lignin-based phenolic resin, and montmorillonite filler in sequence and mixing to be uniform to obtain a mixed material, subjecting the mixed material to formation of a triangular bag, thin pass, cutting and standing for removing air bubbles to obtain a raw rubber; and

[0011] (3) vulcanizing the raw rubber obtained in step (2) on a flat vulcanizer to obtain the 3 dibenzylidene acetone modified hydrophobic Isobutylene isoprene rubber damping composite.

[0012] In some embodiments, wherein in step (1), in parts by mass, the IIR is in an amount of 100 parts, the dibenzylidene acetone is in an amount of 5 parts to 20 parts, and the NaH is in an amount of 5 parts to 20 parts.

[0013] In some embodiments, under the condition that the IIR in step (1) is in an amount of 100 parts, in step (2), in parts by mass, the montmorillonite filler is in an amount of 20 parts to 40 parts, the lignin-based phenolic resin is in an amount of 10 parts to 20 parts, the stearic acid is in an amount of 1 part to 3 parts, the zinc oxide is in an amount of 3 parts to 7 parts, the TMTD is in an amount of 1 part to 4 parts, the DM is in an amount of 0.5 parts to 2 parts, and the sulfur is in an amount of 1 part to 4 parts.

[0014] In some embodiments, in step (2), the standing for removing air bubbles is performed for 24 h to 36 h.

[0015] In some embodiments, in step (3), the vulcanizing is performed at a temperature of 140°C to 160°C and a pressure of 10 MPa to 16 MPa.

[0016] In some embodiments, in step (1), the torque rheometer is replaced by an internal mixer.

[0017] In some embodiments, raw materials used in the method are solvent-free.

[0018] In a second aspect, the present disclosure further provides a dibenzylidene acetone modified hydrophobic IIR composite, which is prepared by the method as described in the above solutions.

[0019] In some embodiments, the dibenzylidene acetone modified hydrophobic IIR damping composite has a high temperature damping temperature range of not less than 70°C.

[0020] In some embodiments, the dibenzylidene acetone modified hydrophobic IIR damping composite has a damping factor at a temperature of 70°C of 0.37 or 0.35.

[0021] In some embodiments, the dibenzylidene acetone modified hydrophobic IIR damping composite has a water contact angle of 94.6°, 97.8°, 101.9°, or 103.1°.

[0022] In some embodiments, the dibenzylidene acetone modified hydrophobic IIR damping composite comprises both an unsaturated double bond functional group and a rigid benzene ring group that are introduced into a main chain of a macromolecule.

[0023] Some embodiments of the present disclosure have the following benefits.

[0024] Synthesis of biomass-based phenolic resin by replacing part of petroleum raw materials with lignin could not only make full use of renewable resources, but also reduce environmental pollution. Synthesis of phenolic resin by replacing phenol with lignin has become an important direction in addressing the problems of environment friendliness and reproducibility of resins.

[0025] The rubber is chemically modified during the processing, which has an advantage that the reaction could be carried out in a general rubber processing equipment (such as a torque rheometer and an internal mixer), is a solvent-free modification method and has features of simple preparation process and low requirements for experimental equipment.

[0026] The HR damping composite according to the present disclosure addresses the problem of poor damping effect of traditional asphalt-based damping materials at ambient temperature or above, and has a wide damping temperature range and an improved damping factor. A new type of hydrophobic IIR is provided, which broadens the application field of the damping composite. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] FIG. 1 shows a relationship curve of land versus temperature (T) of pure IIR.

[0028] FIG. 2 is a diagram showing a water contact angle of IIR after adding 10 parts of ligninbased phenolic resins in Comparative Example 1.

[0029] FIG. 3 is a diagram showing a water contact angle of IIR after adding 20 parts of ligninbased phenolic resins in Comparative Example 2.

[0030] FIG. 4 shows relationship curves of land versustemperature (T) of damping rubber after adding lignin-based phenolic resin, where 1 corresponds to Comparative Example 1, and 2 corresponds to Comparative Example 2.

[0031] FIG. 5 is a diagram showing a water contact angle of IIR after adding 15 parts of dibenzylidene acetone in Example 3.

[0032] FIG. 6 shows relationship curves of land versus temperature (T) of damping rubbers prepared according to Examples 1 to 4.

[0033] FIG. 7 shows Fourier transform infrared (FTIR) spectra of the damping composites with different additives, where 1 represents a spectrum of pure IIR, 2 represents a spectrum of the damping composite prepared with addition of the filler and biomass-based phenolic resin in Comparative Example 1; 3 represents a spectrum of the damping composite prepared with addition of NaH and dibenzylidene acetone in Example 1; and 4 represents a spectrum of the damping composite in Comparative Example 4 prepared with addition of dibenzylidene acetone, and without NaH. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0034] In the present disclosure, IIR (100 parts) and NaH (5 parts to 20 parts) were added to a torque rheometer, and subjected to reaction for 10 min to 15 min to obtain a reactant. After that, the dibenzylidene acetone was added into the reactant and the reaction was then continued for another 10 min to 15 min to obtain a rubber material, and after the reaction was completed, the rubber material was then taken out. The rubber material was plasticized on a two-roller mixer, and stearic acid (1 part to 3 parts), zinc oxide (3 parts to 7 parts), TMTD (1 part to 4 parts), DM (0.5 parts to 2 part), sulfur (1 part to 4 parts), lignin-based phenolic resin (10 parts to 20 parts), and montmorillonite filler (20 parts to 40 parts) were added thereto in sequence and mixed to be uniform to obtain a mixed material. The mixed material was subjected to formation of a triangular bag, thin pass, cutting and standing for 24 h to 36 h for removing air bubbles to obtain a raw rubber. The raw rubber was vulcanized on a flat vulcanizer at a vulcanizing temperature (140°C to 160°C) and a vulcanizing pressure (10 MPa to 16 MPa) to obtain a hydrophobic isobutylene isoprene rubber damping composite with a wide temperature range.

[0035] The present disclosure will be further described in detail below in conjunction with specific examples, and these examples are only intended to explain, not limit the present disclosure. Throughout this specification, “an embodiment”, “embodiments”, “an example” or “examples” means that a particular feature, structure, or characteristic described in the embodiment or example is included in at least one example of the present disclosure. Thus, the phrases “an embodiment”, “embodiments”, “an example” or “examples” appealing in various places throughout this specification are not necessarily to refer to the same embodiment or example.

[0036] FIG. 1 shows a relationship curve of tan5 versus temperature (T) of pure IIR. From FIG. 1, it can be seen that the pure IIR has a poor damping effect at ambient temperature or above.

[0037] Comparative Example 1

[0038] 100 parts of IIR, 10 parts of lignin-based phenolic resin, 30 parts of montmorillonite filler, 2 parts of stearic acid, 5 parts of zinc oxide, 2 parts of TMTD, 1 part of DM, and 2 parts of sulfur were provided.

[0039] IIR was plasticized on a two-roller mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-based phenolic resin, and montmorillonite filler were added thereto in sequence and mixed to be uniform to obtain a mixed material. The mixed material was subjected to formation of a triangular bag, thin pass, cutting and standing for 24 h for removing air bubbles to obtain a raw rubber. The raw rubber was vulcanized on a flat vulcanizer at a vulcanizing temperature of 160°C and a vulcanizing pressure of 14 MPa for 16 min to obtain an IIR damping composite with a wide temperature range.

[0040] The modified IIR prepared in Comparative Example 1 has a high temperature damping range of greater than 60°C and a damping factor of 0.33 at 60°C, as shown in curve 1 of FIG. 4. The IIR damping composite has a water contact angle of 86.9°, exhibiting no hydrophobic property, as shown in FIG. 2.

[0041] Comparative Example 2

[0042] 100 parts of IIR, 20 parts of lignin-based phenolic resin, 30 parts of montmorillonite filler, 2 parts of stearic acid, 5 parts of zinc oxide, 2 parts of TMTD, 1 part of DM, and 2 parts of sulfur were provided.

[0043] IIR was plasticized on a two-roller mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-based phenolic resin, and montmorillonite filler were added thereto in sequence and mixed to be uniform to obtain a mixed material. The mixed material was subjected to formation of a triangular bag, thin pass, cutting and standing for 24 h for removing air bubbles to obtain a raw rubber. The raw rubber was vulcanized on a flat vulcanizer at a vulcanizing temperature of 160°C and a vulcanizing pressure of 14 MPa for 16 min to obtain an IIR damping composite with a wide temperature range.

[0044] The modified IIR prepared in Comparative Example 2 has a high temperature damping range of greater than 60°C and a damping factor of 0.31 at 60°C, as shown in curve 2 of FIG. 4. The IIR damping composite has a water contact angle of 80.2°, exhibiting no hydrophobic property, as shown in FIG. 3.

[0045] It can be seen from FIGs. 2 and 3 that after adding lignin-based phenolic resin, the damping composite exhibits no hydrophobic property because the molecular chain of the lignin-based phenolic resin contains a certain amount of hydroxyl groups.

[0046] Example 1

[0047] 100 parts of IIR, 5 parts of dibenzylidene acetone, 5 parts of NaH, 10 parts of lignin-based phenolic resin, 30 parts of montmorillonite filler, 2 parts of stearic acid, 5 parts of zinc oxide, 2 parts of TMTD, 1 part of DM, and 2 parts of sulfur were provided.

[0048] IIR and NaH were added to a torque rheometer, and subjected to reaction for 10 min to obtain a reactant. After that, dibenzylidene acetone was added into the reactant and the reaction was then continued for another 10 min to obtain a rubber material, and after the reaction was completed, the rubber material was then taken out. The rubber material was plasticized on a two-roller mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-based phenolic resin, and montmorillonite filler were added therein in sequence and mixed to be uniform to obtain a mixed material. The mixed material was subjected to formation of a triangular bag, thin pass, cutting and standing for 24 h for removing air bubbles to obtain a raw rubber. Finally, the raw rubber was vulcanized on a flat vulcanizer at a vulcanizing temperature of 160°C and a vulcanizing pressure of 14 MPa to obtain a hydrophobic isobutylene isoprene rubber damping composite with a wide temperature range.

[0049] The modified IIR prepared in Example 1 has a high temperature damping range of not less than 70°C and a damping factor of 0.30 at 70°C, as shown in curve 1 of FIG. 6. The hydrophobic isobutylene isoprene rubber damping composite has a water contact angle of 94.6°.

[0050] Example!

[0051] 100 parts of IIR, 10 parts of dibenzylidene acetone, 10 parts of NaH, 10 parts of ligninbased phenolic resin, 30 parts of montmorillonite filler, 2 pails of stearic acid, 5 parts of zinc oxide, 2 parts of TMTD, 1 part of DM, and 2 parts of sulfur were provided.

[0052] IIR and NaH were added to a torque rheometer, and subjected to reaction for 10 min to obtain a reactant. After that, dibenzylidene acetone was added into the reactant, and the reaction was then continued for another 10 min to obtain a rubber material, and after the reaction was completed, the rubber material was then taken out. The rubber material was plasticized on a two-roller mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-based phenolic resin, and montmorillonite filler were added therein in sequence and mixed to be uniform to obtain a mixed material. The mixed material was subjected to formation of a triangular bag, thin pass, cutting and standing for 24 h for removing air bubbles to obtain a raw rubber. Finally, the raw rubber was vulcanized on a flat vulcanizer at a vulcanizing temperature of 160°C and a vulcanizing pressure of 14 MPa to obtain a hydrophobic isobutylene isoprene rubber damping composite with a wide temperature range.

[0053] The modified IIR prepared in Example 2 has a high temperature damping range of greater than 70°C and a damping factor of 0.35 at 70°C, as shown in curve 2 of FIG. 6. The hydrophobic isobutylene isoprene rubber damping composite has a water contact angle of 97.8°.

[0054] Examples

[0055] 100 parts of IIR, 15 parts of dibenzylidene acetone, 15 parts of NaH, 10 parts of ligninbased phenolic resin, 30 parts of montmorillonite filler, 2 parts of stearic acid, 5 parts of zinc oxide, 2 parts of TMTD, 1 part of DM, and 2 parts of sulfur were provided.

[0056] IIR and NaH were added to a torque rheometer, and subjected to reaction for 10 min to obtain a reactant. After that, dibenzylidene acetone was added into the reactant, and the reaction was then continued for another 10 min to obtain a rubber material, and after the reaction was completed, the rubber material was then taken out. The rubber material was plasticized on a two-roller mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-based phenolic resin, and montmorillonite filler were added therein in sequence and mixed to be uniform to obtain a mixed material. The mixed material was subjected to formation of a triangular bag, thin pass, cutting and standing for 24 h for removing air bubbles to obtain a raw rubber. Finally, the raw rubber was vulcanized on a flat vulcanizer at a vulcanizing temperature of 160°C and a vulcanizing pressure of 14 MPa to obtain a hydrophobic isobutylene isoprene rubber damping composite with a wide temperature range.

[0057] The modified IIR prepared in Example 3 has a high temperature damping range of greater than 70°C and a damping factor of 0.37 at 70°C, as shown in curve 3 of FIG. 6. The hydrophobic isobutylene isoprene rubber damping composite has a water contact angle of 101.9°.

[0058] Example 4

[0059] 100 parts of IIR, 20 parts of dibenzylidene acetone, 20 parts of NaH, 10 parts of ligninbased phenolic resin, 30 parts of montmorillonite filler, 2 parts of stearic acid, 5 parts of zinc oxide, 2 parts of TMTD, 1 part of DM, and 2 parts of sulfur were provided.

[0060] IIR and NaH were added to a torque rheometer, and subjected to reaction ed for 10 min to obtain a reactant. After that, dibenzylidene acetone was added into the reactant, and the reaction was then continued for another 10 min to obtain a rubber material, and after the reaction was completed, the rubber material was then taken out. The rubber material was plasticized on a two-roller mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-based phenolic resin, and montmorillonite filler were added therein in sequence and mixed to be uniform to obtain a mixed material. The mixed material was subjected to formation of a triangular bag, thin pass, cutting and standing for 24 h for removing air bubbles to obtain a raw rubber. Finally, the raw rubber was vulcanized on a flat vulcanizer at a vulcanizing temperature of 160°C and a vulcanizing pressure of 14 MPa to obtain a hydrophobic isobutylene isoprene rubber damping composite with a wide temperature range.

[0061] The modified IIR prepared in Example 4 has a high temperature damping range of greater than 70°C and a damping factor of 0.35 at 70°C, as shown in curve 4 of FIG. 6. The hydrophobic isobutylene isoprene rubber damping composite has a water contact angle of 103.1° as shown in FIG. 5.

[0062] It can be seen from FIG. 5 that a large number of rigid groups of benzene rings are introduced on the main chain of IIR by addition of lignin-based phenolic resin in conjunction with activation and modification of IIR by NaH, and the damping composite has hydrophobic property due to the existence of a large number of aromatic groups of benzene rings.

[0063] As can be seen from FIG. 6, with the increase of dibenzylidene acetone in the NaH activated and modified IIR, the damping temperature range and damping factor of the damping composite are improved. In Example 3, 15 parts of dibenzylidene acetone was added, and the obtained damping composite has a damping factor being high up to 0.37 at 75°C. By addition of lignin-based phenolic resin and modification of IIR by introducing rigid groups of benzene rings through activation by NaH, the damping performance of the IIR is enhanced, the damping temperature range thereof is widened, and the damping composite is endowed with hydrophobic property.

[0064] Comparative Example 3

[0065] 100 parts of IIR, 10 parts of NaH, 10 parts of lignin-based phenolic resin, 30 parts of montmorillonite filler, 2 parts of stearic acid, 5 parts of zinc oxide, 2 parts of TMTD, 1 part of DM, and 2 parts of sulfur were provided.

[0066] IIR and NaH were added to a torque rheometer, and subjected to reaction ed for 10 min, and a resulting rubber material after the reaction was then taken out. The resulting rubber material was plasticized on a two-roller mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, ligninbased phenolic resin, and montmorillonite filler were added therein in sequence and mixed to be uniform to obtain a mixed material. The mixed material was subjected to formation of a triangular bag, thin pass, cutting and standing for 24 h for removing air bubbles to obtain a raw rubber. Finally, the raw rubber was vulcanized on a flat vulcanizer at a vulcanizing temperature of 160°C and a vulcanizing pressure of 14 MPa to obtain an IIR damping composite with a wide temperature range.

[0067] The modified IIR prepared in Comparative Example 3 has a high temperature damping range of not less than 60°C and a damping factor of 0.31 at 60°C. The IIR damping composite has a water contact angle of 82.4°.

[0068] Comparative Example 4

[0069] lOOpartsof IIR, 10 parts of dibenzylidene acetone, 10 parts of lignin-based phenolic resin, 30 parts of montmorillonite filler, 2 parts of stearic acid, 5 parts of zinc oxide, 2 parts of TMTD, 1 part of DM, and 2 parts of sulfur were provided.

[0070] IIR and NaH were added to a torque rheometer, and subjected to reaction for 10 min, and a resulting rubber material after the reaction was then taken out. The rubber material was plasticized on a two-roller mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-based phenolic resin, and montmorillonite filler were added therein in sequence and mixed to be uniform to obtain a mixed material. The mixed material was subjected to formation of a triangular bag, thin pass, cutting and standing for 24 h for removing air bubbles to obtain a raw rubber. Finally, the raw rubber was vulcanized on a flat vulcanizer at a vulcanizing temperature of 160°C and a vulcanizing pressure of 14 MPa to obtain an IIR damping composite with a wide temperature range.

[0071] The modified IIR prepared in Example 4 has a high temperature damping range of greater than 70°C and a damping factor of 0.35 at 70°C, as shown in curve 4 of FIG. 6. The IIR damping composite has a water contact angle of 103.1° as shown in FIG. 5.

[0072] The hydrophobic damping IIRs with a wide temperature range prepared in Examples 1 to 4 and Comparative Examples 1 to 3 of the present disclosure are compared with the IIR only added with lignin-based phenolic resin and filler. The specific performance results are shown in FIGs. 1 to 7 and Table 1.

[0073] Table 1 Formula Tensile strength / MPa Elongation at break / % Modulus at 100% / MPa Modulus at 300% / MPa Static contact angle / 0 Comparative Example 1 6.3 1608 0.44 0.77 86.9 Comparative Example 2 3.1 1540 0.48 0.61 80.2 Example 1 7.3 1340 1.41 2.3 94.6 Example 2 7.9 1500 1.37 2.33 97.8 Example 3 8.5 1720 1.21 1.87 101.9 Example 4 7.8 1740 1.33 1.89 103.1 Comparative Example 3 (with NaOH, without dibenzylidene acetone) 4.8 1480 0.57 1.03 82.4

[0074] It can be seen from Table 1 and FIG. 4 that the damping composites prepared with the addition of lignin-based phenolic resin has improved tensile strength and breaking strength. The addition of lignin-based phenolic resin could improve the damping performance of IIR composites. The molecular chain of lignin-based phenolic resin contains a large number of polar hydroxyl groups, which obviously enhance the internal friction force of molecular chain movement after entering the rubber matrix. Lignin-based phenolic resin and IIR interpenetrate each other, thus forming a certain interpenetrating network structure.

[0075] It can be seen from FIG. 7 that the comparison between curve 1 and curve 2 shows that the addition of lignin-based phenolic resin and montmorillonite filler does not change the main chain structure of IIR. Curve 3 represents the damping composite prepared with activation of IIR by NaH and addition of benzylidene acetone; curve 4 represents the damping composite prepared only with addition of dibenzylidene acetone, without activation of the double bond in IIR by NaH; by comparison, it can be found that the unsaturated double bond functional group and the rigid benzene ring group are introduced into the main chain of the macromolecule.

[0076] Although the above-mentioned embodiments have described the present disclosure in detail, it should be understood that these embodiments are only part of and not all of the embodiments of the present disclosure. Other embodiments may be obtained by those skilled in the art without creative effort according to the above embodiments, which should be deemed as 11 falling within the scope of the present disclosure.

Claims

1. A method for preparing a dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite, comprising the following steps:(1) adding isobutylene isoprene rubber and NaH in a proportion to a torque rheometer, and conducting reaction in the torque rheometer for 10 min to 15 min to obtain a reactant; then adding dibenzylidene acetone into the reactant, continuing the reaction for another 10 min to 15 min to obtain a rubber material, and taking out the rubber material after the reaction;(2) plasticizing the rubber material obtained in step (1) on a two-roller mixer, adding stearic acid, zinc oxide, tetramethylthiuram, tetramethylthiuram disuofide, sulfur, lignin-based phenolic resin, and montmorillonite filler in sequence and mixing to be uniform to obtain a mixed material, and subjecting the mixed material to formation of a triangular bag, thin pass, cutting and standing for removing air bubbles to obtain a raw rubber; and(3) vulcanizing the raw rubber obtained in step (2) on a flat vulcanizer to obtain the dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite.

2. The method of claim 1, wherein in step (1), in parts by mass, the isobutylene isoprene rubber is in an amount of 100 parts, the dibenzylidene acetone is in an amount of 5 parts to 20 parts, and the NaH is in an amount of 5 parts to 20 parts.

3. The method of claim 1, wherein under the condition that in step (1) the isobutylene isoprene rubber is in an amount of 100 parts, in step (2), in parts by mass, the montmorillonite filler is in an amount of 20 parts to 40 parts, the lignin-based phenolic resin is in an amount of 10 parts to 20 parts, the stearic acid is in an amount of 1 part to 3 parts, the zinc oxide is in an amount of 3 parts to 7 parts, the tctramcthylthiuram is in an amount of 1 pail to 4 parts, the tctramcthylthiuram disuofide is in an amount of 0.5 parts to 2 parts, and the sulfur is in an amount of 1 part to 4 parts.

4. The method of claim 1, wherein in step (2), the standing for removing air bubbles is performed for 24 h to 36 h.

5. The method of claim 1, wherein in step (3), the vulcanizing is performed at a temperature of140°C to 160°C and a pressure of 10 MPa to 16 MPa.

6. The method of claim 1, wherein in step (1), the torque rheometer is replaced by an internal mixer.

7. The method of claim 1, wherein raw materials used in the method are solvent-free.

8. A dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite, which is prepared by the method of any one of claims 1 to 7.

9. The dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite of claim 8, wherein the dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite has a high temperature damping temperature range of not less than 70°C.

10. The dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite of claim 8 or 9, wherein the dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite has a damping factor at a temperature of 70°C of 0.37 or 0.35.

11. The dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite of claim 8 or 9, wherein the dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite has a water contact angle of 94.6°, 97.8°, 101.9°, or 103.1°.

12. The dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite of claim 8, wherein the dibenzylidene acetone modified hydrophobic isobutylene isoprene rubber damping composite comprises both an unsaturated double bond functional group and a rigid benzene ring group that are introduced into a main chain of a macromolecule.PCT / CN2024 / 078251A. CLASSIFICATION OF SUBJECT MATTERC08L23 / 26(2006.01)i; C08L61 / 06(2006.01)i; C08K3 / 34(2006.01)iAccording to International Patent Classification (IPC) or to both national classification and IPCB. FIELDS SEARCHEDMinimum documentation searched (classification system followed by classification symbols)JLJr L-. ■ L,-- LI OILj , L^UOIN.Documentation searched other than minimum documentation to the extent that such documents are included in the fields searchedElectronic data base consulted during the international search (name of data base and, where practicable, search terms used) CNABS, VEN, CNTXT, ENTXT, ENTXTC, VCN, CNKI, ISI: TSIf K, —XWM, 22¥IE TO Pffl, butyl, rubber, dibenzylideneacetone, NaH, sodium, hydride, phenolicDOCUMENTS CONSIDERED TO BE RELEVANTCategory* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. PX CN 116444906 A (CHANGZHOU HAODA TECHNOLOGY CO., LTD. et al.) 18 July 2023 (2023-07-18) entire document 1-12 A CN 106751058 A (SHAANXI JUJIEHAN CHEMICAL CO., LTD.) 31 May 2017 (2017-05-31) entire document 1-12 A CN 112457544 A (JIANGSU UNIVERSITY et al.) 09 March 2021 (2021-03-09) entire document 1-12 A JP 2007231244 A (YOKOHAMA RUBBER CO., LTD.) 13 September 2007 (2007-09-13) entire document 1-12| | Further documents are listed in the continuation of Box C.annex.* Special categories of cited documents: “T” later document published after the international filing date or priority “A” document defining the general state of the art which is not considered date and not in conflict with the application but cited to understand the to be of particular relevance principle or theory underlying the invention “D” document cited by the applicant in die international application “X” document of particular relevance; the claimed invention cannot be ■SE” earlier application orpatent but published on or after the international considered novel or cannot be considered to involve an inventive step filing date when the document is taken alone •SL” document which may throw doubts on priority claim(s) or which is “Y” document of particular relevance; the claimed invention cannot be cited to establish the publication date of another citation or other considered to involve an inventive step when the document is special reason (as specified) combined with one or more other such documents, such combination “O” document referring to an oral disclosure, use, exhibition or other being obvious to a person skilled in the art means document member of the same patent family “P” document published prior to the international filing date but later than the priority date claimed Date of the actual completion of the international search 17 April 2024 Date of mailing of the international search report 18 April 2024 Name and mailing address of the ISA / CN China National Intellectual Property Administration (ISA / CN) China No. 6, Xitucheng Road, Jimenqiao, Haidian District, Beijing 100088 Authorized officer Telephone No.Form PCT / ISA / 210 (second sheet) (July 2022)INTERNATIONAL SEARCH REPORT Information on patent family membersInternational application No.PCT / CN2024 / 07825IPatent document cited in search report Publication date (day / month / year) Patent family member)s) Publication date (day / month / year) CN 116444906 A 18 July 2023 None CN 106751058 A 31 May 2017 None CN 112457544 A 09 March 2021 None JP 2007231244 A 13 September 2007 EP 1777237 Al 25 April 2007 EP 1777237 Bl 18 June 2008 US 2007093607 Al 26 April 2007 US 7589155 B2 15 September 2009 DE 602006001500 DI 31 July 2008 JP 4122033 B2 23 July 2008

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