橡膠基復(fù)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(shí)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(xué)性能,耐熱性,和化學(xué)穩(wěn)定性等性能。目前已經(jīng)實(shí)現(xiàn)在輪胎、輸送帶、和膠管等領(lǐng)域的應(yīng)用。超高分子量聚乙烯纖維具有較高的拉伸強(qiáng)度,抗切割以及抗沖擊性等突出的力學(xué)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(yīng)用前景。但是由于具有較高的結(jié)晶度,表面光滑且化學(xué)惰性較強(qiáng),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(duì)基體表面性質(zhì)沒有依賴性,對(duì)環(huán)境沒有污染,是一種簡(jiǎn)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(yīng)用。多巴胺超強(qiáng)粘附性的一個(gè)重要原因就是結(jié)構(gòu)中含有酚羥基和氨基基團(tuán),針對(duì)這個(gè)觀點(diǎn)我們選用了分別含有這兩種基團(tuán)的單體鄰苯二酚和多胺對(duì)多巴胺進(jìn)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(jié)構(gòu),可以與金屬離子發(fā)生配位反應(yīng)在基體表面形成多酚-金屬絡(luò)合層。γ射線對(duì)纖維進(jìn)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(duì)溫度也沒有特殊要求。受上述觀點(diǎn)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(nèi)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(duì)對(duì)位芳綸(PPTA)纖維進(jìn)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(yīng)條件如下:鄰苯二酚/四乙烯五胺(TEPA)組合,摩爾比為3:1,反應(yīng)溶液的pH為9.5。探究了接枝反應(yīng)溫度以及單體的反應(yīng)濃度對(duì)GPTMS的接枝率的影響。接枝引入的環(huán)氧基團(tuán)可以參與橡膠硫化,有效提高了PPTA纖維/橡膠復(fù)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(yù)沉積時(shí)間,相比多巴胺縮短了 1 h,同時(shí)將PPTA纖維與橡膠的界面粘合強(qiáng)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(shí)驗(yàn)方法具有可控,低成本,高效等優(yōu)點(diǎn),有在橡膠工業(yè)領(lǐng)域廣泛應(yīng)用的前景。(2)酚胺仿生修飾的改性方法已經(jīng)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(zhǎng)的PCPA預(yù)沉積時(shí)間限制了這種方法在橡膠工業(yè)的應(yīng)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(jìn)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(yù)沉積時(shí)間縮短到了 1h。之后,利用乙二醇二縮水甘油醚(EGDE)對(duì)PCPA修飾的芳綸纖維進(jìn)行接枝改性引入環(huán)氧基團(tuán)。利用抽出力測(cè)試探究了 EGDE濃度和接枝時(shí)間對(duì)芳綸纖維與橡膠基體的界面粘合強(qiáng)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(yù)沉積時(shí)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(fù)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(shí)間內(nèi)與三價(jià)鐵離子通過絡(luò)合作用在纖維表面形成一個(gè)金屬-多酚的粘附層。然后,在單寧酸/三價(jià)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(tuán)和多硫鍵,將芳綸纖維/橡膠復(fù)合材料的界面粘合強(qiáng)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(gè)方法具有成本低和反應(yīng)時(shí)間短的優(yōu)勢(shì),具有一定工業(yè)化應(yīng)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(xué)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(shí)驗(yàn)方案為共輻射接枝,具體操作是將纖維浸漬到氮?dú)鈿夥諚l件下GMA的甲醇溶液中進(jìn)行共輻射處理。研究了不同單體濃度對(duì)纖維表面接枝率的影響。纖維與橡膠基體的的界面粘合強(qiáng)度隨單體濃度的增加而增大。當(dāng)GMA濃度達(dá)到12 vol%的時(shí)候,PPTA纖維/橡膠復(fù)合材料和UHMWPE纖維/橡膠復(fù)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(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ342.72;TB33
本文編號(hào)：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(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ342.72;TB33
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