本文選題：尼龍6 + 氯化鈣��； 參考：《貴州大學(xué)》2015年碩士論文

【摘要】：課題組在前期工作中,采用DSC和XRD等表征手段對(duì)絡(luò)合劑(CaCl_2和LiCl)改性PA6的結(jié)晶行為進(jìn)行了研究,但對(duì)CaCl_2和LiCl使PA6結(jié)晶受限的機(jī)理知之甚少。并且當(dāng)PA6結(jié)晶受限嚴(yán)重時(shí),結(jié)晶熱流較小,導(dǎo)致DSC測(cè)試誤差較大。所以本文采用流變學(xué)方法研究了不同絡(luò)合劑(CaCl_2和LiCl)改性PA6的結(jié)晶行為和結(jié)晶受限的機(jī)理。并且進(jìn)一步研究了尼龍6/彈性體/氯化鈣復(fù)合材料和尼龍6/環(huán)氧樹(shù)脂/氯化鈣復(fù)合材料的結(jié)晶性能與流變性能。具體的研究?jī)?nèi)容如下:首先研究了不同含量下CaCl_2和LiCl對(duì)PA6的結(jié)晶性能與流變性能的影響,并利用紅外、DSC、XRD和流變學(xué)等表征方法對(duì)其結(jié)晶行為及受限機(jī)理進(jìn)行了研究,結(jié)果表明:隨著CaCl_2和LiCl含量的增加,PA6的成核及增長(zhǎng)溫度均向低溫方向移動(dòng),成核密度和成核速率也逐漸減小。復(fù)合材料的總結(jié)晶度顯著下降,γ型結(jié)晶度逐漸減低,α型結(jié)晶度呈先增加后減低的趨勢(shì),γ晶與α晶發(fā)生轉(zhuǎn)變,PA6結(jié)晶受限。這主要因?yàn)橐环矫鍯aCl_2和LiCl與PA6中的羰基上的氧原子發(fā)生了絡(luò)合反應(yīng),破壞了使PA6易結(jié)晶的氫鍵。另一方面是因?yàn)镃aCl_2和LiCl與PA6絡(luò)合后形成的纏結(jié)度更高更穩(wěn)定絡(luò)合物,導(dǎo)致鏈段運(yùn)動(dòng)的流動(dòng)阻力增大,松弛困難,在PA6結(jié)晶時(shí)排入晶格困難,結(jié)晶受到限制。比較不同絡(luò)合劑(CaCl_2和LiCl)改性PA6后復(fù)合材料的力學(xué)性能發(fā)現(xiàn),LiCl比CaCl_2使PA6結(jié)晶受限更嚴(yán)重,力學(xué)性能提高更顯著。其次,本文利用POE-g-MAH作為增韌劑來(lái)改性低熔點(diǎn)PA6,研究發(fā)現(xiàn):POE-g-MAH的加入對(duì)PA6結(jié)晶熔融行為影響較小,當(dāng)j(POE-g-MAH)=10~15phr時(shí),可得到?jīng)_擊強(qiáng)度較好,而拉伸強(qiáng)度下降較少的PA6/CaCl_2/POE-g-MAH復(fù)合材料。另外,本文固定了增韌劑POE-g-MAH含量,研究了CaCl_2含量對(duì)PA6/POE-g-MAH/CaCl_2復(fù)合材料結(jié)晶性能與流變性能的影響。研究表明:CaCl_2與PA6的絡(luò)合反應(yīng)破壞了PA6中的極性酰胺基團(tuán),釋放出游離的N-H,從而使得絡(luò)合后的PA6極性降低,與POE-g-MAH界面張力減弱,復(fù)合體系的相容性變好,CaCl_2在體系中起到了增容劑的效果。在研究CaCl_2對(duì)PA6/POE-g-MAH和PA6/POE體系增容效果時(shí)發(fā)現(xiàn),當(dāng)CaCl_2含量較高時(shí),增容效果顯著,在一定程度上,可以利用POE代替POE-g-MAH作為增韌劑來(lái)改性低熔點(diǎn)尼龍。最后,本文利用環(huán)氧樹(shù)脂(E51)改性低熔點(diǎn)PA6后發(fā)現(xiàn),E51與PA6分子間的氨基、羧基和酰胺基的擴(kuò)鏈反應(yīng)會(huì)限制PA6的結(jié)晶,使得復(fù)合材料的熔點(diǎn)降低,結(jié)晶不完善程度增大,而當(dāng)PA6結(jié)晶受限嚴(yán)重時(shí),DSC已不能表征PA6/CaCl_2/E51復(fù)合材料的結(jié)晶熔融行為。在線(xiàn)性粘彈區(qū),復(fù)合材料損耗模量(G’’)呈先增大后減小的趨勢(shì),當(dāng)j(E51)=3 phr時(shí)達(dá)到極值。另外,本文研究了當(dāng)j(E51)=3 phr時(shí),Ca Cl_2含量對(duì)PA6/E51/CaCl_2復(fù)合材料流變性能的影響,研究發(fā)現(xiàn):CaCl_2的加入會(huì)限制E51和PA6的擴(kuò)鏈反應(yīng),從而導(dǎo)致儲(chǔ)能模量(G’)和G’’呈下降趨勢(shì),然而隨著CaCl_2含量的增加,CaCl_2與PA6的絡(luò)合反應(yīng)程度增大,纏結(jié)程度增大,鏈段運(yùn)動(dòng)的流動(dòng)阻力增加,隨之G’和G’’增大。綜合得知,利用適量的E51和CaCl_2對(duì)PA6進(jìn)行改性,可以有效的降低PA6的熔點(diǎn),并提高復(fù)合材料的力學(xué)性能與流變性能,當(dāng)E51含量為3 phr,CaCl_2含量為6 phr時(shí)可以制備熔點(diǎn)較低、力學(xué)性能和流變性能較好的復(fù)合材料。綜合得知,流變學(xué)方法可以較好的反映PA6在結(jié)晶受限時(shí)的結(jié)晶行為,它比DSC更準(zhǔn)確和敏感。另外,在研究多相體系微觀(guān)結(jié)構(gòu)的演化和PA6結(jié)晶受限機(jī)理時(shí),它不失為一個(gè)較有效的方法。
[Abstract]:In previous research work, using DSC and XRD techniques of complexing agents (CaCl_2 and LiCl) crystallization behavior of modified PA6 were studied on CaCl_2 and LiCl, but the mechanism of crystallization of PA6 limited poorlyunderstood. And when the crystallization of PA6 is restricted seriously, resulting in DSC crystallization heat flux is small, the big test error the rheological research. So this article uses different complexing agent methods (CaCl_2 and LiCl) mechanism of crystallization behavior and limited modification of PA6. And further study of nylon 6/ elastomer / calcium chloride composite and nylon 6/ / epoxy resin composite calcium chloride crystallization properties and rheological properties. The specific contents are as follows first: To study the effect of different content of CaCl_2 and LiCl on PA6 crystallization properties and rheological properties, and the use of DSC, infrared, XRD and rheological characterization methods were studied on the crystallization behavior and restriction mechanism, results Show that with the increase of CaCl_2 and LiCl content, nuclear and growth temperature shifts to lower temperature PA6, nucleation density and nucleation rate also decreased. The composite total crystallinity decreased significantly, gamma crystallinity decreased and the crystallinity is alpha trend reduced after the first increase, gamma the crystal and alpha crystal change, PA6. This is mainly because the confined crystallization occurred in the complexation reaction of carbonyl oxygen atoms on the one hand CaCl_2 and LiCl and PA6 in the destruction of the PA6 crystallization of the hydrogen bond. On the other hand because of the formation of CaCl_2 and LiCl and PA6 complex after the entanglement degree higher and more stable complexes, resulting in the flow resistance of segmental motion increases, relaxation is difficult, difficult into the lattice in PA6 crystallization, crystallization is limited. Comparison of complexing agents (CaCl_2 and LiCl) found that the mechanical properties of the composite modified PA6, LiCl than CaCl_2 to the crystallization of PA6 is restricted more serious, mechanical properties Can be improved more significantly. Secondly, this paper uses POE-g-MAH as toughening agent modified low melting point PA6, results show that the addition of POE-g-MAH PA6 on the crystallization and melting behavior has little effect, when J (POE-g-MAH) =10~15phr, can obtain better impact strength, and the tensile strength decreased PA6/CaCl_2/POE-g-MAH composite less. In addition, this paper fixed the toughening agent POE-g-MAH content, the effects of CaCl_2 content on the crystallization properties of PA6/POE-g-MAH/CaCl_2 composites and rheological properties. Research shows that the complexation of CaCl_2 and PA6 destroyed the polar amide group PA6, free N-H, so that the complexation of PA6 polarity decreased, and POE-g-MAH decreased the interfacial tension of composites good compatibility, CaCl_2 plays a compatibilizer effect in the system. In the PA6/POE-g-MAH PA6/POE system and compatibilization effect on CaCl_2, when the CaCl_2 content is high When the compatibilization effect, to a certain extent, can use POE instead of POE-g-MAH as toughening agent of modified low melting nylon. Finally, using epoxy resin (E51) modified low melting point PA6 and found that E51 and PA6 molecules of amino, crystalline chain extension reaction of carboxyl and amide groups will limit PA6 the composite material, low melting point, crystallization degree increases, and when the crystallization of PA6 is restricted seriously, crystallization and melting behavior of DSC has not been able to characterization of PA6/CaCl_2/E51 composite materials. In the linear viscoelastic region, loss modulus of composites (G ') was first increased and then decreased, reached the maximum when J (E51) =3 phr. In addition, this paper studied when J (E51) =3 phr, Ca Cl_2 study found that the effect of content on rheological properties of PA6/E51/CaCl_2 composites: the chain extension reaction by the addition of CaCl_2 E51 and PA6, which leads to the storage modulus (G') and 'G' decreased The trend, however, with the increase of CaCl_2 content, CaCl_2 and PA6 complexation reaction degree increases, increasing the degree of entanglement, increase the flow resistance of segmental motion, then G 'and G' 'comprehensive increases. That of PA6 was modified by the amount of E51 and CaCl_2, can effectively reduce the melting point of PA6, and improve the mechanical properties and rheological properties of the composites, when the content of E51 is 3 phr, the content of CaCl_2 6 phr can be prepared with low melting point, the mechanical properties of the composites and good rheology. The comprehensive rheological method that can reflect the PA6 crystallization behavior in the limit of crystallization, it is more accurate than DSC and sensitive. In addition, in the study of evolution and crystallization mechanism of multiphase PA6 restricted the microscopic structure of the system, it is a more effective method.

【學(xué)位授予單位】：貴州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TB33

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