橡膠基復合材料用高性能纖維的表面修飾及其粘合性能研究
發(fā)布時間：2018-07-23 12:23
【摘要】：伴隨著高性能橡膠制品的需求量日益增大,高性能纖維骨架材料得到了快速的發(fā)展。芳綸纖維是目前高性能橡膠骨架材料的主要成員之一。相比傳統(tǒng)的骨架材料,芳綸纖維具更優(yōu)異的力學性能,耐熱性,和化學穩(wěn)定性等性能。目前已經實現在輪胎、輸送帶、和膠管等領域的應用。超高分子量聚乙烯纖維具有較高的拉伸強度,抗切割以及抗沖擊性等突出的力學特性,良好的光穩(wěn)定性和耐腐蝕性,在橡膠工業(yè)中也具有一定應用前景。但是由于具有較高的結晶度,表面光滑且化學惰性較強,這兩種纖維與橡膠的界面粘合作用較差。多巴胺仿生修飾方法對基體表面性質沒有依賴性,對環(huán)境沒有污染,是一種簡單而有效的新改性手段。它能夠有效改善芳綸纖維和超高分子量聚乙烯纖維與橡膠基體的界面粘合性能,但昂貴的成本限制了這種纖維改性方法在工業(yè)中的應用。多巴胺超強粘附性的一個重要原因就是結構中含有酚羥基和氨基基團,針對這個觀點我們選用了分別含有這兩種基團的單體鄰苯二酚和多胺對多巴胺進行有效替代,這兩種單體的成本不足多巴胺的百分之一。單寧酸是一種植物多酚,由于富含鄰苯二酚和連苯三酚結構,可以與金屬離子發(fā)生配位反應在基體表面形成多酚-金屬絡合層。γ射線對纖維進行輻照改性使近年來一種較新穎的改性手段,這種手段不需要特定的引發(fā)劑或催化劑,對溫度也沒有特殊要求。受上述觀點啟發(fā),本文探索了三種纖維表面修飾方法來改善纖維與橡膠的界面粘合性能。具體內容如下:(1)通過鄰苯二酚/多胺的共沉積和硅烷偶聯(lián)劑γ-縮水甘油醚氧丙基三甲氧基硅烷(GPTMS)的接枝改性對對位芳綸(PPTA)纖維進行了表面修飾。聚(鄰苯二酚/多胺)(PCPA)在芳綸纖維表面沉積的最佳反應條件如下:鄰苯二酚/四乙烯五胺(TEPA)組合,摩爾比為3:1,反應溶液的pH為9.5。探究了接枝反應溫度以及單體的反應濃度對GPTMS的接枝率的影響。接枝引入的環(huán)氧基團可以參與橡膠硫化,有效提高了PPTA纖維/橡膠復合材料的界面粘合性能。相比多巴胺處理的方法,這種方法有較短的預沉積時間,相比多巴胺縮短了 1 h,同時將PPTA纖維與橡膠的界面粘合強度提升了 83.3%,甚至優(yōu)于多巴胺方法處理的改性效果(67.5%)。除此之外,酚胺的成本不到多巴胺的1%。由于本實驗方法具有可控,低成本,高效等優(yōu)點,有在橡膠工業(yè)領域廣泛應用的前景。(2)酚胺仿生修飾的改性方法已經證明能夠有效改善芳綸纖維與橡膠基體的界面粘合性能,但是較長的PCPA預沉積時間限制了這種方法在橡膠工業(yè)的應用。分別采用紫外輻照和添加氧化劑的方法來加速鄰苯二酚/多胺的氧化自聚合進程以及在芳綸纖維表面的沉積速率。在紫外輻照的條件下,PCPA在纖維表面的預沉積時間縮短到了 1h。之后,利用乙二醇二縮水甘油醚(EGDE)對PCPA修飾的芳綸纖維進行接枝改性引入環(huán)氧基團。利用抽出力測試探究了 EGDE濃度和接枝時間對芳綸纖維與橡膠基體的界面粘合強度的影響。相比未改性PPTA纖維,改性纖維與橡膠的界面抽出力最大提升了 85.6%。添加氧化劑的處理方式,使PCPA預沉積時間縮短到了 30 min。隨后接枝了硅烷偶聯(lián)劑雙-(γ-三乙氧基硅基丙基)四硫化物(Si69),將芳綸纖維/橡膠復合材料的界面抽出力提升了 42%。(3)采用一種綠色環(huán)保而且有效的方法改善了芳綸纖維與橡膠基體的界面粘合性能。單寧酸(TA),一種天然多酚,可以短時間內與三價鐵離子通過絡合作用在纖維表面形成一個金屬-多酚的粘附層。然后,在單寧酸/三價鐵(TA/FeⅢ)修飾的芳綸纖維表面分別接枝了硅烷偶聯(lián)劑Si69和GPTMS。通過在纖維表面引入高活性的環(huán)氧基團和多硫鍵,將芳綸纖維/橡膠復合材料的界面粘合強度分別提升了 73.6%和55.4%。相比我們之前采用的多巴胺仿生修飾的方法,這個方法具有成本低和反應時間短的優(yōu)勢,具有一定工業(yè)化應用前景。此外,這種利用植物多酚改性纖維的方法也符合綠色化學的需求。(4)采用伽馬射線引發(fā)單體甲基丙烯酸縮水甘油酯(GMA)分別在PPTA纖維和UHMWPE纖維表面接枝聚合。選擇的實驗方案為共輻射接枝,具體操作是將纖維浸漬到氮氣氣氛條件下GMA的甲醇溶液中進行共輻射處理。研究了不同單體濃度對纖維表面接枝率的影響。纖維與橡膠基體的的界面粘合強度隨單體濃度的增加而增大。當GMA濃度達到12 vol%的時候,PPTA纖維/橡膠復合材料和UHMWPE纖維/橡膠復合材料的界面抽出力分別提升了 130%和93.6%。
[Abstract]:With the increasing demand for high performance rubber products, high performance fiber skeleton materials have been developed rapidly. Aramid fiber is one of the main members of high performance rubber skeleton materials. Compared with traditional skeleton materials, aramid fiber has better mechanical properties, heat resistance, chemical stability and so on. Ultra high molecular weight polyethylene fiber has high tensile strength, anti cutting and impact resistance and other outstanding mechanical properties, good light stability and corrosion resistance. It has a certain application prospect in the rubber industry. But because of its high crystallinity, the surface is smooth and changed. The interfacial adhesion of the two fibers and rubber is poor. The dopamine biomimetic modification method has no dependence on the surface properties of the matrix and has no pollution to the environment. It is a simple and effective new means of modification. It can effectively improve the interfacial adhesion between the aramid fiber and the UHMWPE fiber and the rubber matrix. But the expensive cost limits the application of this fiber modification method in industry. One important reason for the super strong adhesion of dopamine is that the structure contains phenolic hydroxyl groups and amino groups. In this view we have selected the two groups of monomeric catechol and polyamines to replace the dopamine effectively, these two kinds of monomers. The cost of the body is less than one percent of the dopamine. Tannic acid is a kind of plant polyphenols. Due to the structure of catechol and polyphenols, it can react with metal ions to form a polyphenol metal complex layer on the surface of the matrix. For a specific initiator or catalyst, there is no special requirement for temperature. Inspired by the above viewpoint, three kinds of fiber surface modification methods have been explored to improve the interfacial adhesion of fiber and rubber. The specific contents are as follows: (1) co deposition of catechol / polyamine and silane coupling agent gamma glycidoxypropyl trimethoxysilicon The surface modification of the para aramid (PPTA) fibers by the grafting modification of alkane (GPTMS). The optimum reaction conditions for the deposition of poly (catechol / polyamine) (PCPA) on aramid fiber are as follows: the combination of catechol / four ethylene five amine (TEPA), the molar ratio of 3:1, and the pH of the reaction solution to 9.5. to explore the grafting reaction temperature and the reaction concentration of the monomer to GP The effect of the grafting ratio of TMS. The epoxy group introduced by the graft can participate in rubber vulcanization, effectively improving the interfacial adhesion of the PPTA fiber / rubber composites. Compared with the dopamine treatment method, the method has a shorter deposition time, 1 h shorter than dopamine, and the bonding strength of the PPTA fiber and rubber at the same time. 83.3%, and even better than dopamine treatment modified effect (67.5%). Besides, the 1%. of Phenolamine has the advantages of controllable, low cost and high efficiency. (2) the modification method of Phenolamine biomimetic modification has proved to be able to improve the aramid fiber effectively. The interfacial adhesion with the rubber matrix, but the longer PCPA predeposition time restricts the application of this method to the rubber industry. UV irradiation and the addition of oxidants are used to accelerate the process of the oxidation of catechol / polyamine and the deposition rate on the surface of aramid fiber. Under UV irradiation, PCPA is The predeposition time of the fiber surface was shortened to 1h., and ethylene glycol two glycidyl ether (EGDE) was used to graft the PCPA modified aramid fiber into the epoxy group. The effect of EGDE concentration and grafting time on the bonding strength of the boundary between the aramid fiber and the rubber matrix was investigated by the extraction force test. Compared to the unmodified PPTA fiber, the effect of the EGDE concentration and the grafting time were investigated. The interfacial pulling force of the modified fiber and rubber greatly enhanced the treatment of 85.6%. adding oxidant, shortened the PCPA pre deposition time to 30 min. and then grafted the silane coupling agent, double (gamma triethoxyl silicon propyl) four sulfide (Si69), and increased the interfacial pulling force of the aramid fiber / rubber compound to 42%. (3). A green and effective method improves the interfacial adhesion between the aramid fiber and the rubber matrix. Tannic acid (TA), a natural polyphenol, can form a metal polyphenols adhesion layer on the fiber surface in a short time with trivalent iron ions. Then, the surface of the tannic acid / trivalent iron (TA/Fe III) modified aramid fiber surface. The grafting of silane coupling agent Si69 and GPTMS. respectively by introducing highly active epoxy groups and polysulfide bonds on the surface of the fiber, the interfacial bonding strength of aramid fiber / rubber composites is increased by 73.6% and 55.4%., compared to the dopamine biomimetic modification that we used before. This method has low cost and short reaction time. In addition, the method of using plant polyphenols to modify fiber also meets the requirements of green chemistry. (4) graft copolymerization of PPTA fiber and UHMWPE fiber on the surface of GMA with gamma ray induced monomeric glycidyl methacrylate. Co radiation treatment was carried out in the methanol solution of GMA under nitrogen atmosphere. The effect of different monomer concentration on the grafting ratio of fiber surface was studied. The interfacial adhesion strength of fiber and rubber matrix increased with the increase of monomer concentration. When the concentration of GMA reached 12 vol%, PPTA fiber / rubber composite and UHMWPE The interfacial extraction force of fiber / rubber composites increased by 130% and 93.6%. respectively.
【學位授予單位】：北京化工大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TQ342.72;TB33
本文編號：2139409
[Abstract]:With the increasing demand for high performance rubber products, high performance fiber skeleton materials have been developed rapidly. Aramid fiber is one of the main members of high performance rubber skeleton materials. Compared with traditional skeleton materials, aramid fiber has better mechanical properties, heat resistance, chemical stability and so on. Ultra high molecular weight polyethylene fiber has high tensile strength, anti cutting and impact resistance and other outstanding mechanical properties, good light stability and corrosion resistance. It has a certain application prospect in the rubber industry. But because of its high crystallinity, the surface is smooth and changed. The interfacial adhesion of the two fibers and rubber is poor. The dopamine biomimetic modification method has no dependence on the surface properties of the matrix and has no pollution to the environment. It is a simple and effective new means of modification. It can effectively improve the interfacial adhesion between the aramid fiber and the UHMWPE fiber and the rubber matrix. But the expensive cost limits the application of this fiber modification method in industry. One important reason for the super strong adhesion of dopamine is that the structure contains phenolic hydroxyl groups and amino groups. In this view we have selected the two groups of monomeric catechol and polyamines to replace the dopamine effectively, these two kinds of monomers. The cost of the body is less than one percent of the dopamine. Tannic acid is a kind of plant polyphenols. Due to the structure of catechol and polyphenols, it can react with metal ions to form a polyphenol metal complex layer on the surface of the matrix. For a specific initiator or catalyst, there is no special requirement for temperature. Inspired by the above viewpoint, three kinds of fiber surface modification methods have been explored to improve the interfacial adhesion of fiber and rubber. The specific contents are as follows: (1) co deposition of catechol / polyamine and silane coupling agent gamma glycidoxypropyl trimethoxysilicon The surface modification of the para aramid (PPTA) fibers by the grafting modification of alkane (GPTMS). The optimum reaction conditions for the deposition of poly (catechol / polyamine) (PCPA) on aramid fiber are as follows: the combination of catechol / four ethylene five amine (TEPA), the molar ratio of 3:1, and the pH of the reaction solution to 9.5. to explore the grafting reaction temperature and the reaction concentration of the monomer to GP The effect of the grafting ratio of TMS. The epoxy group introduced by the graft can participate in rubber vulcanization, effectively improving the interfacial adhesion of the PPTA fiber / rubber composites. Compared with the dopamine treatment method, the method has a shorter deposition time, 1 h shorter than dopamine, and the bonding strength of the PPTA fiber and rubber at the same time. 83.3%, and even better than dopamine treatment modified effect (67.5%). Besides, the 1%. of Phenolamine has the advantages of controllable, low cost and high efficiency. (2) the modification method of Phenolamine biomimetic modification has proved to be able to improve the aramid fiber effectively. The interfacial adhesion with the rubber matrix, but the longer PCPA predeposition time restricts the application of this method to the rubber industry. UV irradiation and the addition of oxidants are used to accelerate the process of the oxidation of catechol / polyamine and the deposition rate on the surface of aramid fiber. Under UV irradiation, PCPA is The predeposition time of the fiber surface was shortened to 1h., and ethylene glycol two glycidyl ether (EGDE) was used to graft the PCPA modified aramid fiber into the epoxy group. The effect of EGDE concentration and grafting time on the bonding strength of the boundary between the aramid fiber and the rubber matrix was investigated by the extraction force test. Compared to the unmodified PPTA fiber, the effect of the EGDE concentration and the grafting time were investigated. The interfacial pulling force of the modified fiber and rubber greatly enhanced the treatment of 85.6%. adding oxidant, shortened the PCPA pre deposition time to 30 min. and then grafted the silane coupling agent, double (gamma triethoxyl silicon propyl) four sulfide (Si69), and increased the interfacial pulling force of the aramid fiber / rubber compound to 42%. (3). A green and effective method improves the interfacial adhesion between the aramid fiber and the rubber matrix. Tannic acid (TA), a natural polyphenol, can form a metal polyphenols adhesion layer on the fiber surface in a short time with trivalent iron ions. Then, the surface of the tannic acid / trivalent iron (TA/Fe III) modified aramid fiber surface. The grafting of silane coupling agent Si69 and GPTMS. respectively by introducing highly active epoxy groups and polysulfide bonds on the surface of the fiber, the interfacial bonding strength of aramid fiber / rubber composites is increased by 73.6% and 55.4%., compared to the dopamine biomimetic modification that we used before. This method has low cost and short reaction time. In addition, the method of using plant polyphenols to modify fiber also meets the requirements of green chemistry. (4) graft copolymerization of PPTA fiber and UHMWPE fiber on the surface of GMA with gamma ray induced monomeric glycidyl methacrylate. Co radiation treatment was carried out in the methanol solution of GMA under nitrogen atmosphere. The effect of different monomer concentration on the grafting ratio of fiber surface was studied. The interfacial adhesion strength of fiber and rubber matrix increased with the increase of monomer concentration. When the concentration of GMA reached 12 vol%, PPTA fiber / rubber composite and UHMWPE The interfacial extraction force of fiber / rubber composites increased by 130% and 93.6%. respectively.
【學位授予單位】：北京化工大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TQ342.72;TB33
【參考文獻】
相關期刊論文 前10條
1 凌新龍;郭立富;林海濤;;芳綸纖維的改性研究新進展[J];天津工業(yè)大學學報;2016年04期
2 劉洋;梁國正;;生物酶催化接枝芳綸纖維和復合材料的界面性能[J];材料研究學報;2015年10期
3 王翔;鄭玉嬰;曹寧寧;張延兵;劉陽龍;;馬來酸酐刻蝕芳綸纖維/尼龍6復合材料的制備及性能[J];復合材料學報;2016年08期
4 王非;劉麗超;薛平;;超高分子量聚乙烯纖維制備技術進展[J];塑料;2014年05期
5 朱華;陳剛;;芳綸1313纖維的特點及其在個體防護服裝領域的應用[J];中國安全生產科學技術;2014年05期
6 徐世傳;方永清;;高分散性芳綸短纖維TWAROND3500在礦山輪胎胎側膠中的應用[J];橡膠科技;2014年01期
7 孔海娟;張蕊;周建軍;馬禹;滕翠青;余木火;;芳綸纖維的研究現狀與進展[J];中國材料進展;2013年11期
8 徐世傳;孫徐偉;余鋒;;芳綸短纖維在輪胎性能改進中的應用[J];橡膠科技;2013年05期
9 劉兆峰;俞波;;高強高模聚乙烯纖維產業(yè)化的現狀及思考[J];高科技纖維與應用;2012年06期
10 毛云增;蔡正國;楊曙光;馬敬紅;徐堅;;超高分子質量聚乙烯纖維研究進展[J];中國材料進展;2012年10期
相關碩士學位論文 前3條
1 譚建理;超高分子量聚乙烯纖維/天然橡膠復合材料的制備與性能研究[D];青島科技大學;2014年
2 尤志強;對位芳綸的表面改性研究[D];東華大學;2010年
3 廖穎芳;浸漬處理層與芳綸纖維粘合問題的研究[D];河海大學;2006年
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