WO2024230271A1 - 一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料及其制备方法 - Google Patents

一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料及其制备方法 Download PDF

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WO2024230271A1
WO2024230271A1 PCT/CN2024/078251 CN2024078251W WO2024230271A1 WO 2024230271 A1 WO2024230271 A1 WO 2024230271A1 CN 2024078251 W CN2024078251 W CN 2024078251W WO 2024230271 A1 WO2024230271 A1 WO 2024230271A1
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butyl rubber
parts
dibenzylideneacetone
composite material
damping
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PCT/CN2024/078251
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English (en)
French (fr)
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袁新华
陈泽宇
胡振国
贾宇菲
杨华
倪侃
费宏伟
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Changzhou Haoda Technology Co Ltd
Jiangsu University
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Changzhou Haoda Technology Co Ltd
Jiangsu University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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  • the present application relates to a dibenzylideneacetone modified hydrophobic butyl rubber damping composite material and a preparation method thereof, belonging to the field of polymer-based damping materials.
  • hydrophobic materials have a wide range of applications and appear in all aspects of life, including aerospace, military industry, transportation, agriculture, construction, medical treatment, daily textiles, etc., and the prospects are very broad.
  • the contact angle of hydrophobic materials is generally above 90°, and their preparation mainly revolves around two aspects. On the one hand, low surface energy substances are added to the material, such as substances containing long alkyl chains or fluorine-containing substances, and on the other hand, a rough surface with a micro-nano structure is prepared.
  • these two methods of preparing hydrophobic materials have advantages and disadvantages.
  • hydrophobic materials mainly involves adding hydrophobic masterbatch, that is, adding low surface energy substances, but the hydrophobic effect of this method is general and can only meet general hydrophobic requirements.
  • the method of preparing hydrophobic materials by constructing a rough interface although the prepared hydrophobic material has a better effect, the preparation process is relatively cumbersome, and the rough interface is easily damaged, which greatly reduces the hydrophobic effect and needs to be replaced regularly, so the cost is relatively high.
  • the ideal preparation method for producing hydrophobic materials generally combines the two aspects to play a synergistic role, that is, not only constructing a rough surface, but also covering its surface with low surface energy substances, but the process is relatively speaking, and has not yet reached the capacity of full industrialization and large-scale production.
  • HTMS-g-HTPB heptamethyl trisiloxane grafted terminal hydroxyl polybutadiene
  • PTMEG2000 polytetramethylene ether diol
  • MDI diphenylmethane diisocyanate
  • DPG chain extender dipropylene glycol
  • the purpose of the present application is to provide a method for preparing a dibenzylideneacetone modified hydrophobic butyl rubber damping composite material, by adding a bio-based phenolic resin, activating the modified butyl rubber with NaH and introducing a rigid group benzene ring, so as to broaden the damping temperature range of the butyl rubber, improve the damping performance, and prepare a green and environmentally friendly hydrophobic damping composite material with simple operation.
  • the present application provides a method for preparing a dibenzylideneacetone modified hydrophobic butyl rubber damping composite material, comprising the following steps:
  • step (2) plasticizing the rubber obtained in step (1) on a two-roll mixer, adding stearic acid, zinc oxide, tetramethylthiuram TMTD, tetramethylthiuram disulfide DM, sulfur, lignin-modified phenolic resin, and montmorillonite filler in sequence, blending evenly, making triangle packages, thinning, putting down sheets, and leaving them to remove bubbles, thereby obtaining raw rubber;
  • step (3) vulcanizing the raw rubber obtained in step (2) on a flat vulcanizer to obtain a dibenzylideneacetone modified hydrophobic butyl rubber damping composite material.
  • the butyl rubber is 100 parts, the dibenzylideneacetone is 5 to 20 parts, and the NaH is 5 to 20 parts by mass.
  • step (2) when in step (1), the butyl rubber is 100 parts, the substances in step (2) are calculated by weight as follows: montmorillonite filler is 20-40 parts, lignin modified phenolic resin is 10-20 parts, stearic acid is 1-3 parts, zinc oxide is 3-7 parts, TMTD is 1-4 parts, DM is 0.5-2 parts, and sulfur is 1-4 parts.
  • the time for removing bubbles is 24 to 36 hours.
  • the vulcanization temperature is 140-160° C.
  • the vulcanization pressure is 10-16 MPa.
  • step (1) the torque rheometer is replaced by an internal mixer.
  • the raw materials of the preparation method are free of solvent.
  • the present application also provides a dibenzylideneacetone modified hydrophobic butyl rubber damping composite material, which is prepared by the preparation method described in the above technical solution.
  • the high temperature damping temperature range of the dibenzylideneacetone modified hydrophobic butyl rubber damping composite material is ⁇ 70°C.
  • the 70°C damping factor of the dibenzylideneacetone modified hydrophobic butyl rubber damping composite material is 0.37 or 0.35.
  • the water contact angle of the dibenzylideneacetone modified hydrophobic butyl rubber damping composite material is 94.6°, 97.8°, 101.9° or 103.1°.
  • the dibenzylideneacetone modified hydrophobic butyl rubber damping composite material includes unsaturated double bond functional groups and rigid group benzene rings introduced into the main chain of the macromolecule.
  • lignin to replace part of petroleum raw materials to synthesize biomass-based phenolic resin can not only make full use of renewable resources, but also reduce environmental pollution.
  • Using lignin to replace phenol to synthesize phenolic resin has become an important direction to solve the problems of resin environmental protection and reproducibility.
  • the biggest advantage of chemically modifying the rubber during processing is that the reaction can be carried out in common rubber processing equipment (such as torque rheometer, internal mixer, etc.). It is a solvent-free modification method with simple preparation process and low requirements for experimental equipment.
  • the butyl rubber damping composite material prepared in the present application solves the problem that the traditional asphalt-based damping material has poor damping effect at room temperature and above, broadens the damping temperature range, improves the damping factor, prepares a new type of hydrophobic butyl rubber damping composite material, and further broadens the application field of the damping composite material.
  • Figure 1 is the tan ⁇ T relationship curve of pure butyl rubber
  • FIG2 is a graph showing the water contact angle of butyl rubber after adding 10 parts of lignin-modified phenolic resin to Comparative Example 1;
  • FIG3 is a graph showing the water contact angle of butyl rubber after adding 20 parts of lignin-modified phenolic resin in Comparative Example 2;
  • Figure 4 is a tan ⁇ T relationship curve of the damping rubber with lignin-modified phenolic resin added; 1-Comparative Example 1; 2-Comparative Example 2;
  • FIG5 is a graph showing the contact angle of butyl rubber water after adding 15 parts of dibenzylideneacetone in Example 3;
  • FIG6 is a tan ⁇ -T relationship curve of the damping rubber of Examples 1-4;
  • Figure 7 is an infrared spectra of the damping composite material obtained with different additives, wherein 1 is pure butyl rubber; 2 is comparative example 1 with filler and bio-based phenolic resin added; 3 is example 1 with NaH and dibenzylideneacetone added; and 4 is comparative example 4 with dibenzylideneacetone added but without NaH.
  • butyl rubber (100 parts) and NaH (5-20 parts) are added to a torque rheometer for reaction for 10-15 minutes, and then dibenzylideneacetone (5-20 parts) is added to continue the reaction for 10-15 minutes.
  • the rubber material is taken out; the obtained rubber material is plasticized on a double-roll mixer, and stearic acid (1-3 parts), zinc oxide (3-7 parts), tetramethylthiuram (TMTD) (1-4 parts), tetramethylthiuram disulfide ( DM) (0.5-2 parts), sulfur (1-4 parts), lignin modified phenolic resin (10-20 parts), montmorillonite filler (20-40 parts), blend them evenly, make triangle packages, thin them, put them into sheets, and leave them for 24-36 hours to remove bubbles to obtain raw rubber; finally, the obtained raw rubber is vulcanized on a flat vulcanizer at a vulcanization temperature (140-160°C) and a vulcanization pressure (10-16MPa) to obtain a wide temperature
  • FIG1 is a tan ⁇ T relationship curve of pure butyl rubber
  • the butyl rubber is plasticized on a double-roll mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-modified phenolic resin, and montmorillonite filler are added in sequence, mixed evenly, packed in triangles, thinned, and sliced, and left for 24 hours to remove bubbles to obtain raw rubber; finally, the obtained raw rubber is vulcanized on a flat vulcanizer at a vulcanization temperature of 160°C, a vulcanization pressure of 14 MPa, and a vulcanization time of 16 minutes to obtain a butyl rubber damping composite material with a wide temperature range.
  • the high temperature damping temperature range of the modified butyl rubber prepared in Comparative Example 1 is greater than 60°C, and the damping factor at 60°C is 0.33, as shown in curve 1 of FIG4 .
  • the water contact angle is 86.9°, and no hydrophobic property is shown, as shown in FIG2 .
  • the butyl rubber is plasticized on a double-roll mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-modified phenolic resin, and montmorillonite filler are added in sequence, mixed evenly, packed in triangles, thinned, and sliced, and left for 24 hours to remove bubbles to obtain raw rubber; finally, the obtained raw rubber is vulcanized on a flat vulcanizer at a vulcanization temperature of 160°C, a vulcanization pressure of 14 MPa, and a vulcanization time of 16 minutes to obtain a butyl rubber damping composite material with a wide temperature range.
  • the high-temperature damping temperature range of the modified butyl rubber prepared in Comparative Example 2 is greater than 60°C, and the damping factor at 60°C is 0.31, as shown in Curve 2 of FIG. 4 ; the water contact angle is 80.2°, and no hydrophobic property is shown, as shown in FIG. 3 .
  • the damping composite material does not show hydrophobic properties because the lignin-modified phenolic resin contains a certain amount of hydroxyl groups on the modified resin molecular chain.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • Butyl rubber and NaH were added into a torque rheometer to react for 10 minutes, and then dibenzylideneacetone was added to continue the reaction for 10 minutes. After the reaction was completed, the rubber was taken out; the obtained rubber was plasticized on a two-roll mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-modified phenolic resin, and montmorillonite filler were added in sequence, blended evenly, made into triangular packages, thinly passed, and placed on sheets for 24 hours to remove bubbles to obtain raw rubber; finally, the obtained raw rubber was vulcanized on a flat vulcanizer at a vulcanization temperature of 160°C and a vulcanization pressure of 14 MPa to obtain a wide temperature range hydrophobic butyl rubber damping composite material.
  • the high-temperature damping temperature range of the modified butyl rubber prepared in Example 1 is ⁇ 70° C., and the damping factor at 70° C. is 0.30, as shown in curve 1 of FIG. 6 ; the water contact angle is 94.6°.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • Butyl rubber and NaH were added into a torque rheometer to react for 10 minutes, and then dibenzylideneacetone was added to continue the reaction for 10 minutes. After the reaction was completed, the rubber was taken out; the obtained rubber was plasticized on a two-roll mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-modified phenolic resin, and montmorillonite filler were added in sequence, blended evenly, made into triangular packages, thinly passed, and placed on sheets for 24 hours to remove bubbles to obtain raw rubber; finally, the obtained raw rubber was vulcanized on a flat vulcanizer at a vulcanization temperature of 160°C and a vulcanization pressure of 14 MPa to obtain a wide temperature range hydrophobic butyl rubber damping composite material.
  • the high-temperature damping temperature range of the modified butyl rubber prepared in Example 2 is greater than 70° C., and the damping factor at 70° C. is 0.35, as shown in curve 2 of FIG. 6 ; the water contact angle is 97.8°.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • Butyl rubber and NaH were added into a torque rheometer to react for 10 minutes, and then dibenzylideneacetone was added to continue the reaction for 10 minutes. After the reaction was completed, the rubber was taken out; the obtained rubber was plasticized on a two-roll mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-modified phenolic resin, and montmorillonite filler were added in sequence, blended evenly, made into triangular packages, thinly passed, and placed on sheets for 24 hours to remove bubbles to obtain raw rubber; finally, the obtained raw rubber was vulcanized on a flat vulcanizer at a vulcanization temperature of 160°C and a vulcanization pressure of 14 MPa to obtain a wide temperature range hydrophobic butyl rubber damping composite material.
  • the high-temperature damping temperature range of the modified butyl rubber prepared in Example 3 is greater than 70° C., and the damping factor at 70° C. is 0.37, as shown in curve 3 of FIG. 6 ; the water contact angle is 101.9°.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • Butyl rubber and NaH were added into a torque rheometer to react for 10 minutes, and then dibenzylideneacetone was added to continue the reaction for 10 minutes. After the reaction was completed, the rubber was taken out; the obtained rubber was plasticized on a two-roll mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-modified phenolic resin, and montmorillonite filler were added in sequence, blended evenly, made into triangular packages, thinly passed, and placed on sheets for 24 hours to remove bubbles to obtain raw rubber; finally, the obtained raw rubber was vulcanized on a flat vulcanizer at a vulcanization temperature of 160°C and a vulcanization pressure of 14 MPa to obtain a wide temperature range hydrophobic butyl rubber damping composite material.
  • the high-temperature damping temperature range of the modified butyl rubber prepared in Example 4 is greater than 70° C., and the damping factor at 70° C. is 0.35, as shown in curve 4 of FIG. 6 ; the water contact angle is 103.1°, as shown in FIG. 5 .
  • the damping temperature range and damping factor of the damping composite material are improved.
  • the damping factor can be as high as 0.37 at a temperature of 75°C.
  • Adding lignin-modified phenolic resin in combination with NaH-activated modified butyl rubber with rigid group benzene rings can improve the damping performance of butyl rubber, broaden the damping temperature range, and make the damping composite material hydrophobic.
  • Butyl rubber and NaH were added into a torque rheometer to react for 10 minutes. After the reaction, the rubber was taken out.
  • the obtained rubber was plasticized on a two-roll mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-modified phenolic resin, and montmorillonite filler were added in sequence, blended evenly, made into triangular packages, thinly passed, and placed for 24 hours to remove bubbles to obtain raw rubber. Finally, the obtained raw rubber was vulcanized on a flat vulcanizer at a vulcanization temperature of 160°C and a vulcanization pressure of 14 MPa to obtain a wide temperature range butyl rubber damping composite material.
  • the modified butyl rubber prepared in Comparative Example 3 has a high-temperature damping temperature range of ⁇ 60°C, a damping factor of 0.31 at 60°C, and a water contact angle of 82.4°.
  • Butyl rubber and NaH were added into a torque rheometer to react for 10 minutes. After the reaction, the rubber was taken out.
  • the obtained rubber was plasticized on a two-roll mixer, and stearic acid, zinc oxide, TMTD, DM, sulfur, lignin-modified phenolic resin, and montmorillonite filler were added in sequence, blended evenly, made into triangular packages, thinly passed, and placed for 24 hours to remove bubbles to obtain raw rubber. Finally, the obtained raw rubber was vulcanized on a flat vulcanizer at a vulcanization temperature of 160°C and a vulcanization pressure of 14 MPa to obtain a wide temperature range butyl rubber damping composite material.

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Abstract

本申请属于高分子基阻尼材料领域，公开了一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料及其制备方法。将丁基橡胶、氢化钠、二苄叉丙酮在转矩流变仪中反应一段时间，然后在双辊混炼机上混炼胶料，按顺序加入硬脂酸、氧化锌、二硫化四甲基秋兰姆、二硫化二苯并噻唑、硫磺、木质素改性酚醛树脂、蒙脱土填料直至包辊并混炼均匀，取出放置24～36h除去气泡制得生胶；将所述生胶在平板硫化机上硫化，获得疏水型丁基橡胶阻尼复合材料。本申请加入木质素改性酚醛树脂与无溶剂改性丁基橡胶相结合，绿色环保，操作简单，引入苯环刚性基团，拓宽了丁基橡胶阻尼温域，提高了阻尼因子，并使阻尼材料具有疏水性能，拓宽了丁基橡胶阻尼材料的应用领域。

Description

一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料及其制备方法
本申请要求于2023年05月11日提交中国专利局、申请号为CN202310528702.6、发明名称为“一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料及其制备方法，属于高分子基阻尼材料领域。
背景技术
目前，已有许多新材料和新技术不断应用于阻尼减震，其中高分子材料，尤其是橡胶阻尼减震材料以其优异的性能越来越引起人们的重视。采用橡胶阻尼材料，可以最大限度降低机械噪声和减轻机械震动，提高工作效率，提高产品质量。一些常用的车用沥青基阻尼垫在使用时会散发出萘、蒽、菲等致癌物质，而且阻尼效果比较差，达不到我们所需的舒适、健康、安静的出行体验要求。高分子基阻尼材料极大地减少了车内有毒物质排放，在常温及以上阻尼效果好，同时还可使用可再生原材料，具有可持续发展、安全、健康、环保等优点。
水存在于大自然的每个角落，但在某些领域不希望有水长时间存在，这时就需要疏水材料。疏水材料的应用面相当广泛，出现在生活中的方方面面，可涵盖航天、军工、交通工具、农业、建筑、医疗、日用纺织品等各个方面，前景非常广阔。疏水材料的接触角一般在90°以上，其制备主要围绕两方面，一方面是在材料中加入低表面能的物质，如含有长烷基链的物质或者含氟的物质，另一方面就是制备具有微纳结构的粗糙表面；但这两种制备疏水材料的方法有利有弊，一般目前工业化生产疏水材料的主要是加入疏水母粒，即加入低表面能的物质，但该方法疏水效果一般，只可以满足一般的疏水要求；通过构建粗糙界面制备疏水材料的方法，虽然制备的疏水材料效果较好，但制备过程相对来说比较繁琐，且粗糙界面容易被破坏，使得疏水效果大幅度下降，需要定时更换，因此成本较高；目前，一般生产疏水材料的理想制备方法为两方面结合，起到协同作用，即不仅构建粗糙的表面，还有在其表面覆盖低表面能的物质，但工艺相对来说，还未达到完全工业化，大规模生产的能力。
对于传统的沥青基或粘弹性阻尼材料来说，由于丁基橡胶含有极性官能团，一般为亲水性材料，使用过程中常常会产生吸潮现象，加上热稳定性较差，导致传统的阻尼材料使用寿命通常较短，开发一种具有良好的抗潮性及高热稳定性能的阻尼材料势在必行。但目前针对阻尼材料进行疏水性研究的文献较少。北京化工大学的陈博(陈博.有机硅改性聚丁二烯型聚氨酯阻尼材料及性能研究[D]，北京化工大学，2017)用端羟基的聚二甲基硅氧烷(HTPDMS)和端羟基聚丁二烯(HTPB)作为共混软段与二苯基甲烷二异氰酸酯(MDI)进行嵌段共聚反应，一缩二丙二醇(DPG)和丙三醇(GLY)作为扩链剂，用预聚体法和浇注的方式来制备PU阻尼材料，材料表面疏水性增加，将七甲基三硅氧烷接枝端羟基聚丁二烯(HTMS-g-HTPB)与聚四氢呋喃醚二元醇(PTMEG2000)作为混合链段，之后再与二苯基甲烷二异氰酸酯(MDI)和扩链剂一缩二丙二醇(DPG)通过预聚体法制得聚氨酯阻尼弹性体。通过调节软段两相之间的配比，随着HMTS-g-HTPB含量的升高，材料的力学性能综合提高，表面的疏水能力增强。藏雨(藏雨，雷天阳，青木俊树，等.含氟丙烯酸酯大分子单体接枝改性聚酯的研究[J].齐齐哈尔大学学报(自然科学版)，2020,36(03):77～80)等研究甲基丙烯酸甲酯和甲基丙烯酸十三辛酯接枝含氟支链对材料亲水性的影响，发现经过接枝改性后材料的接触角增大至128.8°，由亲水性材料变为疏水材料。这两种方法虽可提高阻尼材料疏水性能，但阻尼材料制备过于复杂，且价格较高，工业化应用受到限制。
发明内容
本申请的目的是提供一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料的制备方法，通过加入生物基酚醛树脂，用NaH活化改性丁基橡胶的同时引入刚性基团苯环，拓宽丁基橡胶的阻尼温域，提高阻尼性能，制备绿色环保疏水型阻尼复合材料，操作简单。
本申请的技术方案是：
本申请提供一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料的制备方法，包括以下步骤：
(1)按比例将丁基橡胶(IIR)和NaH加入到转矩流变仪中反应10～15min，再加入二苄叉丙酮继续反应10～15min，反应结束后，取出胶料；
(2)将步骤(1)获得的胶料在双辊混炼机上进行塑化，按顺序加入硬脂酸、氧化锌、四甲基秋兰姆TMTD、二硫化四甲基秋兰姆DM、硫磺、木质素改性酚醛树脂、蒙脱土填料，共混均匀，打三角包，薄通，下片，放置去除气泡，制得生胶；
(3)将步骤(2)获得的生胶在平板硫化机上进行硫化，获得二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料。
优选的，步骤(1)中，按质量份数，所述丁基橡胶为100份，二苄叉丙酮5～20份，NaH为5～20份。
优选的，步骤(2)中，当步骤(1)中，丁基橡胶为100份时，步骤(2)中各物质按质量份计，蒙脱土填料为20～40份，木质素改性酚醛树脂为10～20份，硬脂酸为1～3份，氧化锌3～7份，TMTD 1～4份，DM 0.5～2份，硫磺1～4份。
优选的，步骤(2)中，放置去除气泡的时间24～36h。
优选的，步骤(3)中，硫化的温度为140～160℃，硫化的压力为10～16MPa。
优选的，步骤(1)中，转矩流变仪替换为密炼机。
优选的，所述制备方法的原料中无溶剂。
本申请还提供了一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料，是通过上述技术方案所述制备方法制得的。
优选的，所述二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料的高温阻尼温域≥70℃。
优选的，所述二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料的70℃阻尼因子为0.37或0.35。
优选的，所述二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料的水接触角为94.6°、97.8°、101.9°或103.1°。
优选的，所述二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料包括引入到大分子主链上的不饱和双键官能团和刚性基团苯环。
本申请的有益效果为：
用木质素替代部分石油原料合成生物质基酚醛树脂，既可以充分利用可再生资源，又可以减少环境污染。用木质素代替苯酚合成酚醛树脂已成为解决树脂环保和重现性问题的重要方向。
在加工的同时对橡胶进行化学改性，其最大的优点是反应能够在通用的橡胶加工设备(如转矩流变仪、密炼机等)中进行，是一种无溶剂的改性方法，制备工艺简单，实验设备要求低的特点。
本申请制得的丁基橡胶阻尼复合材料解决了传统的沥青基阻尼材料常温及以上阻尼效果不好的问题，拓宽了阻尼温域，提高了阻尼因子，制备了一种新型的疏水型丁基橡胶阻尼复合材料，进一步拓宽了阻尼复合材料应用领域。
附图说明
图1为纯丁基橡胶的tanδ～T关系曲线；
图2为对比例1加入10份木质素改性酚醛树脂后丁基橡胶水接触角图；
图3为对比例2加入20份木质素改性酚醛树脂后丁基橡胶水接触角图；
图4为添加木质素改性酚醛树脂的阻尼橡胶的tanδ～T关系曲线；1-对比例1；2-对比例2；
图5为实施例3加入15份二苄叉丙酮后丁基橡胶水接触角图；
图6为实施例1～4的阻尼橡胶的tanδ～T关系曲线；
图7为不同添加剂下得到的阻尼复合材料的红外光谱图，其中1为纯丁基橡胶；2为对比例1添加填料和生物基酚醛树脂；3为实施例1加NaH和二苄叉丙酮；4为对比例4加二苄叉丙酮，未加NaH。
具体实施方式
本申请将丁基橡胶(100份)和NaH(5～20份)加入到转矩流变仪中反应10～15min，再加入二苄叉丙酮(5～20份)继续反应10～15min，反应结束后，取出胶料；将获得的胶料在双辊混炼机上进行塑化，按顺序加入硬脂酸(1～3份)、氧化锌(3～7份)、四甲基秋兰姆(TMTD)(1～4份)、二硫化四甲基秋兰姆(DM)(0.5～2份)、硫磺(1～4份)、木质素改性酚醛树脂(10～20份)、蒙脱土填料(20～40份)，共混均匀，打三角包，薄通，下片，放置24～36h去除气泡，制得生胶；最后将获得的生胶在平板硫化机上进行硫化，硫化温度(140～160℃)，硫化压力(10～16MPa)，获得宽温域疏水型丁基橡胶阻尼复合材料。
下面结合具体实施例，对本申请作进一步的详细说明，所描述的具体实施例仅用于解释本申请，并不用于限定本申请。在整个说明书中，对“一个实施例”、“实施例”、“一个示例”或“示例”的提及意味着：结合该实施例或示例描述的特定特征、结构或特性被包含在本申请至少一个实施例中。因此，在整个说明书的各个地方出现的短语“一个实施例”、“实施例”、“一个示例”或“示例”不一定都指同一实施例或示例。
图1为纯丁基橡胶的tanδ～T关系曲线；从图1中可以看出，纯丁基橡胶在常温及以上的阻尼效果不佳。
对比例1：
取丁基橡胶100份，木质素改性酚醛树脂10份，蒙脱土填料30份，硬脂酸2份，氧化锌5份，TMTD 2份，DM 1份，硫磺2份。
将丁基橡胶在双辊混炼机上进行塑化，按顺序加入硬脂酸、氧化锌、TMTD、DM、硫磺、木质素改性酚醛树脂、蒙脱土填料，共混均匀，打三角包，薄通，下片，放置24h去除气泡，制得生胶；最后将获得的生胶在平板硫化机上进行硫化，硫化温度160℃，硫化压力14MPa，硫化时间16min，获得宽温域丁基橡胶阻尼复合材料。
对比例1制备出的改性丁基橡胶高温阻尼温域＞60℃，60℃阻尼因子0.33，如图4的曲线1。水接触角为86.9°，并没有表现出疏水性能，如图2。
对比例2：
取丁基橡胶100份，木质素改性酚醛树脂20份，蒙脱土填料30份，硬脂酸2份，氧化锌5份，TMTD 2份，DM 1份，硫磺2份。
将丁基橡胶在双辊混炼机上进行塑化，按顺序加入硬脂酸、氧化锌、TMTD、DM、硫磺、木质素改性酚醛树脂、蒙脱土填料，共混均匀，打三角包，薄通，下片，放置24h去除气泡，制得生胶；最后将获得的生胶在平板硫化机上进行硫化，硫化温度160℃，硫化压力14MPa，硫化时间16min，获得宽温域丁基橡胶阻尼复合材料。
对比例2制备出的改性丁基橡胶高温阻尼温域＞60℃，60℃阻尼因子0.31，如图4的曲线2；水接触角为80.2°，并没有表现出疏水性能，如图3。
从图2、3中可以看出，加入木质素改性酚醛树脂后，由于木质素改性酚醛树脂改性树脂分子链上含有一定量的羟基，阻尼复合材料并没有表现出疏水性能。
实施例1：
取丁基橡胶100份，二苄叉丙酮5份，NaH 5份，木质素改性酚醛树脂10份，蒙脱土填料30份，硬脂酸2份，氧化锌5份，TMTD 2份，DM 1份，硫磺2份。
将丁基橡胶和NaH加入到转矩流变仪中反应10min，再加入二苄叉丙酮继续反应10min，反应结束后，取出胶料；将获得的胶料在双辊混炼机上进行塑化，按顺序加入硬脂酸、氧化锌、TMTD、DM、硫磺、木质素改性酚醛树脂、蒙脱土填料，共混均匀，打三角包，薄通，下片，放置24h去除气泡，制得生胶；最后将获得的生胶在平板硫化机上进行硫化，硫化温度160℃，硫化压力14MPa获得宽温域疏水型丁基橡胶阻尼复合材料。
实施例1制备出的改性丁基橡胶高温阻尼温域≥70℃，70℃阻尼因子0.30，如图6的曲线1；水接触角为94.6°。
实施例2：
取丁基橡胶100份，二苄叉丙酮10份，NaH 10份，木质素改性酚醛树脂10份，蒙脱土填料30份，硬脂酸2份，氧化锌5份，TMTD 2份，DM 1份，硫磺2份。
将丁基橡胶和NaH加入到转矩流变仪中反应10min，再加入二苄叉丙酮继续反应10min，反应结束后，取出胶料；将获得的胶料在双辊混炼机上进行塑化，按顺序加入硬脂酸、氧化锌、TMTD、DM、硫磺、木质素改性酚醛树脂、蒙脱土填料，共混均匀，打三角包，薄通，下片，放置24h去除气泡，制得生胶；最后将获得的生胶在平板硫化机上进行硫化，硫化温度160℃，硫化压力14MPa获得宽温域疏水型丁基橡胶阻尼复合材料。
实施例2制备出的改性丁基橡胶高温阻尼温域＞70℃，70℃阻尼因子0.35，如图6的曲线2；水接触角为97.8°。
实施例3：
取丁基橡胶100份，二苄叉丙酮15份，NaH 15份，木质素改性酚醛树脂10份，蒙脱土填料30份，硬脂酸2份，氧化锌5份，TMTD 2份，DM 1份，硫磺2份。
将丁基橡胶和NaH加入到转矩流变仪中反应10min，再加入二苄叉丙酮继续反应10min，反应结束后，取出胶料；将获得的胶料在双辊混炼机上进行塑化，按顺序加入硬脂酸、氧化锌、TMTD、DM、硫磺、木质素改性酚醛树脂、蒙脱土填料，共混均匀，打三角包，薄通，下片，放置24h去除气泡，制得生胶；最后将获得的生胶在平板硫化机上进行硫化，硫化温度160℃，硫化压力14MPa，获得宽温域疏水型丁基橡胶阻尼复合材料。
实施例3制备出的改性丁基橡胶高温阻尼温域＞70℃，70℃阻尼因子0.37，如图6的曲线3；水接触角为101.9°。
实施例4：
取丁基橡胶100份，二苄叉丙酮20份，NaH 20份，木质素改性酚醛树脂10份，蒙脱土填料30份，硬脂酸2份，氧化锌5份，TMTD 2份，DM 1份，硫磺2份。
将丁基橡胶和NaH加入到转矩流变仪中反应10min，再加入二苄叉丙酮继续反应10min，反应结束后，取出胶料；将获得的胶料在双辊混炼机上进行塑化，按顺序加入硬脂酸、氧化锌、TMTD、DM、硫磺、木质素改性酚醛树脂、蒙脱土填料，共混均匀，打三角包，薄通，下片，放置24h去除气泡，制得生胶；最后将获得的生胶在平板硫化机上进行硫化，硫化温度160℃，硫化压力14MPa，获得宽温域疏水型丁基橡胶阻尼复合材料。
实施例4制备出的改性丁基橡胶高温阻尼温域＞70℃，70℃阻尼因子0.35，如图6的曲线4；水接触角为103.1°，如图5。
从图5中可以看出，加入木质素改性酚醛树脂与NaH活化改性丁基橡胶相结合，在丁基橡胶主链上引入大量刚性基团苯环，由于大量芳香基团苯环的存在，使阻尼复合材料具有疏水性能。
从图6中可以看出，随着NaH活化改性丁基橡胶加入二苄叉丙酮份数的提高，阻尼复合材料的阻尼温域和阻尼因子都有所提高，实施例3中加入15份二苄叉丙酮时，在温度75℃下，阻尼因子可高达0.37。加入木质素改性酚醛树脂与NaH活化引入刚性基团苯环改性丁基橡胶相结合可以提高丁基橡胶阻尼性能，拓宽阻尼温域，并使阻尼复合材料具有疏水性能。
对比例3：
取丁基橡胶100份，NaH 10份，木质素改性酚醛树脂10份，蒙脱土填料30份，硬脂酸2份，氧化锌5份，TMTD 2份，DM 1份，硫磺2份。
将丁基橡胶和NaH加入到转矩流变仪中反应10min，反应结束后，取出胶料；将获得的胶料在双辊混炼机上进行塑化，按顺序加入硬脂酸、氧化锌、TMTD、DM、硫磺、木质素改性酚醛树脂、蒙脱土填料，共混均匀，打三角包，薄通，下片，放置24h去除气泡，制得生胶；最后将获得的生胶在平板硫化机上进行硫化，硫化温度160℃，硫化压力14MPa，获得宽温域丁基橡胶阻尼复合材料。
对比例3制备出的改性丁基橡胶高温阻尼温域≥60℃，60℃阻尼因子0.31，水接触角为82.4°。
对比例4：
取丁基橡胶100份，二卞叉丙酮10份，木质素改性酚醛树脂10份，蒙脱土填料30份，硬脂酸2份，氧化锌5份，TMTD 2份，DM 1份，硫磺2份。
将丁基橡胶和NaH加入到转矩流变仪中反应10min，反应结束后，取出胶料；将获得的胶料在双辊混炼机上进行塑化，按顺序加入硬脂酸、氧化锌、TMTD、DM、硫磺、木质素改性酚醛树脂、蒙脱土填料，共混均匀，打三角包，薄通，下片，放置24h去除气泡，制得生胶；最后将获得的生胶在平板硫化机上进行硫化，硫化温度160℃，硫化压力14MPa，获得宽温域丁基橡胶阻尼复合材料。
将本申请实施例1～4、对比例1～3所述方法制备的宽温域阻尼疏水丁基橡胶与只加入木质素酚醛树脂和填料的丁基橡胶进行对比，具体性能请参阅图1～7及表1。
[根据细则91更正 07.04.2024]
表1
从表1和图4中可以看出，加入木质素改性酚醛树脂后，阻尼复合材料的拉伸强度和断裂强度有所改善。加入木质素改性酚醛树脂能够改善丁基橡胶复合材料的阻尼性能。木质素改性酚醛树脂的分子链含有的大量极性羟基在进入到橡胶基质后，明显增强了分子链运动的内摩擦作用力。木质素改性酚醛树脂与丁基橡胶相互贯穿，具有一定的互穿网络结构。
从图7中可以看出，曲线1和曲线2对比发现，加入木质素改性酚醛树脂和蒙脱土填料并没有改变丁基橡胶的主链结构；曲线3为使用NaH活化丁基橡胶引入二苄叉丙酮，曲线4只加入二苄叉丙酮，没有使用NaH进行活化丁基橡胶中的双键，对比可以发现不饱和双键官能团和刚性基团苯环引入到大分子主链上。
尽管上述实施例对本申请做出了详尽的描述，但它仅仅是本申请一部分实施例而不是全部实施例，人们还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本申请保护范围。

Claims (12)

  1. 一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料的制备方法，其特征在于，包括如下步骤：
    (1)按比例将丁基橡胶和NaH加入到转矩流变仪中反应10～15min，再加入二苄叉丙酮继续反应10～15min，反应结束后，取出胶料；
    (2)将步骤(1)获得的胶料在双辊混炼机上进行塑化，按顺序加入硬脂酸、氧化锌、四甲基秋兰姆、二硫化四甲基秋兰姆、硫磺、木质素改性酚醛树脂、蒙脱土填料，共混均匀，打三角包，薄通，下片，放置去除气泡，制得生胶；
    (3)将步骤(2)获得的生胶在平板硫化机上进行硫化，获得二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料。
  2. 如权利要求1所述的制备方法，其特征在于：步骤(1)中，按质量份数，所述丁基橡胶为100份，二苄叉丙酮5～20份，NaH为5～20份。
  3. 如权利要求1所述的制备方法，其特征在于：当步骤(1)中，丁基橡胶为100份时，步骤(2)中各物质按质量份计，蒙脱土填料为20～40份，木质素改性酚醛树脂为10～20份，硬脂酸为1～3份，氧化锌3～7份，四甲基秋兰姆1～4份，二硫化四甲基秋兰姆0.5～2份，硫磺1～4份。
  4. 如权利要求1所述的制备方法，其特征在于：步骤(2)中，放置去除气泡的时间24～36h。
  5. 如权利要求1所述的制备方法，其特征在于：步骤(3)中，硫化的温度为140～160℃，硫化的压力为10～16MPa。
  6. 如权利要求1所述的制备方法，其特征在于：步骤(1)中，转矩流变仪替换为密炼机。
  7. 如权利要求1所述的制备方法，其特征在于：所述制备方法的原料中无溶剂。
  8. 一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料，其特征在于，是通过权利要求1～7任一项所述制备方法制得的。
  9. 如权利要求8所述的二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料，其特征在于，所述二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料的高温阻尼温域≥70℃。
  10. 如权利要求8或9所述的二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料，其特征在于，所述二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料的70℃阻尼因子为0.37或0.35。
  11. 如权利要求8或9所述的二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料，其特征在于，所述二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料的水接触角为94.6°、97.8°、101.9°或103.1°。
  12. 如权利要求8所述的二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料，其特征在于，所述二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料包括引入到大分子主链上的不饱和双键官能团和刚性基团苯环。
PCT/CN2024/078251 2023-05-11 2024-02-23 一种二苄叉丙酮改性疏水型丁基橡胶阻尼复合材料及其制备方法 Ceased WO2024230271A1 (zh)

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