尼龙6与聚乙烯醇共混性能的基础研究与应用.docx

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1、摘要 在高分子的相关学科中，由于高分子共混物的一些比较有潜力的应用价值， 高分子共混物性能研究一直是一个相当重要的领域。事实上，高分子共混物的性 能主要依赖它们的相容性和相行为 s因此，高分子共混物的相容性和相行为的 研究是这二十年来高分子共混物研宄最丰富的成果方向之一 在本研究中，选 用尼龙 6与聚乙烯醇为共混体系进行研究，并通过测试其流变性能、热融性能、 X-射线、红外光谱及机械性能来分析它们的共混性能。而本论文共分两大部分： (1) 研究聚乙烯醇与尼龙 6 纳米复合材料的共混性能 .在纳米尼龙 6 中加 入聚乙烯醇的含量少于丨 6.7%时，发现聚乙烯醇的 a晶型培融峰和 X-射线峰都几

2、乎消失了，并且聚乙烯醇的氧键缔合的羟基官能团峰也看不到了。事实上，聚乙 烯醇与纳米尼龙 6 的扭矩一时间测量和机械性能都证明在纳米尼龙 6 中加入聚乙 烯醇的含量少于 16.7%时，纳米尼龙 6 分子与聚乙烯醇分子是相容的。还有，伴 随着聚乙烯醇的含量的增多，并超过 50%时，扭矩会再次增大，而且 “ 稳定 ” 的共混时间也变长，这些都证明此时纳米尼龙 6 与聚乙烯醇存在相分离。另外， 当聚乙烯醇的量增多时，尼龙 6 中的 a晶型逐渐增多，而 Y晶型逐渐减小，聚乙 烯醇的含量超过 50%时，根据热融曲线和 X-射线衍射，纳米尼龙 6 中的 V晶型 完全看不到了，并转换成了 a晶型。 (2) 研

3、究尼龙 6 与不同醇解度的聚乙烯醇的共混性能。在尼龙 6/a-聚乙烯 醇、尼龙 6/b-聚乙烯醇和尼龙 6/c-聚乙烯醇共混系统中的聚乙稀醇的含量分别少 于或等于 16.7、 33.3 和 50.0%时，我们发现在 DSC热分析曲线中仅仅只有一个 结晶峰，在 XRD衍射曲线聚乙烯醇的晶型几乎消失了，在 FT-丨 R曲线中聚乙烯 醇的缔合的径基官能团也几乎消失了。此外，值得注意的是当聚乙烯醇的減化度 从大约 98 到 95 到 88%时，导致尼龙 6 和聚乙烯醇的 a晶型衍射峰、 DSC曲线 中的双结晶峰和聚乙烯醇中缔合的羟基官能团出现的聚乙烯醇临界含量值从 16.7 到33.3 到 50.0

4、此外，尼龙 6/聚乙烯醇共混机械性能也支持 a-聚乙烯 醇， b 聚乙烯醇和聚乙烯醇的含量分别在少于或等于它们对应的标准值时，聚 乙烯醇分子和尼龙 6分子是相容的。这些尼龙 6与不同醇解度的聚乙烯醇的共混 的有趣的 DSC、 FTlWAXD和机械性能被解释在这篇论文中 关键词：聚乙烯醇，碱化度，尼龙 6,共混，兼容性，尼龙 6 纳米复合材料 Abstract The miscibility and specific interaction in polymer blends have been a topic of intense interest in polymer science due

5、 to their potential application. The properties of polymer blends are greatly dependent on their miscibility and phase behavior. Therefore, the researdi of miscibility and phase behavior of polymer blends has been flie one the major achievonents during these twenty years in polymer blends. In this s

6、tudy, we will choose nylon 6 to blend with polyvinyl alcohol (PVA) and study their blending properties by using flie rheological, thamal, X-ray diffraction, Fourier-fransform infrared mi tensile iopertics. The work in this dissertation is divided into two areas: (1) Blending properties of polyvinyl

7、alcohol and nylon 6-clay (NYC) nanocomposite blids arc systematically investigated. The characteristics of melting endotherm, X-ray dif&action patterns of a form PVA crystals and hydrogen-bonded hydroxyl groups originally associated with the PVA resin almost disappear after blending less than 16.7 w

8、t% of PVA in NYC resins. The torques vs. time measurements and tensile properties of NYC/PVA specimens support the ideas that PVA molecules arc miscible with NYC molecules to some extents in the molecular level as the PVA contents of NYC/PVA specimens are less than 16,7wt%. Moreover, the additional

9、demarcated humps and significantly bereased torques and stabilized9* time values support the presence of separated PVA phases in NYC/PVA specimens as flieir PVA contents are more than 50 wt%. On the other hand, the a form PA crystals continue to grow at the expense of y form PA crystals as the PVA c

10、ontents of NYC/PVA specimens increase, and the characteristics of the y form PA crystals originally shown on the melting endotherm and X-ray dif&action patterns of the NYC resin can barely be seen as the PV contents of NYC/PVA specimens are equal to or more than 50 wt%, (2) Blending properties of th

11、e blends of nylon 6 and polyvinyl alcohol with varying degrees of hydrolysis were systematically investigated. A single crystallization exotherm, nearly disappearance of the characteristics of a form PVA crystals and hydrogen-bonded hydroxyl groups orinally associated with the PVA molecules of PA6xP

12、VAay, PA6xPVAby and PA6xPVAcy specimens are equal to or less than their corresponding critical PVA contents, respectively. It is worth noting that the critical PVA contents of the three PA6xPVAy series specimens increase significantly from 16J to 333 and to 50.0 wt%, respectively as their degrees of

13、 hydrolysis of PVA molecules reduce roughly from 98 to 95 and to 88 mol%, respectively. On the other hand, the tensile properties of the PA6xPVAy series specimens support the ideas that PVA molecules are miscible with PA6 molecules to some extents in the molecular level as their PVA contents are equ

14、al to or less than their corresponding critical PVA contents. Possible reasons accounting for these interesting crystallization exotherms, FTIR? WAXD and tensile properties of the PA6xPVAy series specimens with varying degree of hydrolysis are proposed in this study. Key words： polyvinyl alcohol, de

15、gree of hydrolysis, nylon 6, bending, miscibility, nylon 6 nanocomposite. List of tables Table 2-1. The compositions of NYC/PVA specimens . 24 Table 2-2. Thermal properties of NYC PVA and NYC/PVA Resins . 21 Table 3-1 The compositions of PA6/PVA specimens prepared in this study . 53 Table 3-2 Therma

16、l properties of PA6 PVA and PA6XPVAY Resins . 55 vi List of figures Figure 1-1 the hydrogen bonding in intermolecular.14 Figure 1-2 the hydrogen bonding in intramolecular.15 Figure 2-1 Plots of torque vs. time of NYC (A), PVA (), NY 7PVA| ( ), NYC5PVA1 ( ), NYC3PVA, ( ), NYC2PVA, ( ), NYC1PVA1 ( ),

17、NYCjPVA2( ),and NYC1PVA3 ( ) specimens . 25 Figure 2-2 WAXS diflfraction patterns of (a) NYC, (b) NYC7PVA1, (c) NYC5PVA1, (d) NYC3PVA,? (e) NYC2PVA, (f) NYCiPVAb (g) NYC|PVA2J (h) NYCIPVAJ and (i) PVA specimens . 26 Figure 2-3 The evaluated d-spacing of clay layers present in NYC/PVA specimens. . 29

18、 Figure 24 DSC thermograms of (a NYC， (b) NYC7PVA1， (c NYC5PVA1， (d) NYC3PVA1, (e) NYC2PVA1, (f) NYCjPVA, (g) NYCIPVA2J (h) NYC1PVA3 and (i) PVA specimens . 30 Figure 2-5 FT-IR spectra of (a) NYC, (b) NYC7PVA1, (c) NYCsPVAr, (d) NYC3PVAlf (e) NYC2PVAl5 (f) NYCtPVAi, (g) NYC,PVA2 h) NYC1PVA3 and (i)

19、PVA specimens determined at 20C .33 Figure 2-6 FT-IR spectra of NYC specimens determined at (a) 30C, (b) 80Ct (c) 130C, (d) 180C, (e) 210Cand (f) 230 C . 34 Figure 2-7 FT-IR spectra of PVA specimens determined at (a) 30C, (b) 80C, (c) 130C,(d)180 C,(e)210 C and(f)230 C . 36 Figure 2-8 FT-IR spectra

20、of NYCsPVAi specimens determined at (a) 30C, (b) 80C,(c) 130C,(d) 180 C,(e)210 C and(f)230 C . 37 Figure 2-9 FT-IR spectra ofNYCiPVAi specimens determined at (a) 30C, (b) 80C, (c) 130C, (d) lSOC, (e)210C and (f)230 C.38 Figure 2-10 Frequency difFa*ence (Av between the absorption bands of hydrogen- b

21、onded hydroxyl and free hydroxyl groups of PVA specimens ) and Frequency difference (AV2) between the absorption bands of hydrogen- bonded amide and free amide groups of NYC specimens () determined at varying temperatures . 39 Figure 2-11 The values of tensile strength () and elongation at break ()

22、of NYC, PVA specimens and NYC/PVA specimens. 43 Figure 3-1 the hy PA67PVAai， e) PA65PVAai, (d) PA63PVAai, (e) PA62PVAa,? (f) PA6iPVAa, (g) PA6|PVAa3and (h) PVAa specimens cooled at 20 C/min . 58 Figure 3-3 DSC cooling thermograms of (a) PA6, (b) PA67PVAbi,(c) PA65PVAbi, (d) PA63PVAb|, (e) PA62PVAb,

23、(f) PA6,PVAbi, (g) PA6jPVAb3and (h) PVAb specimais cooled at 20 C /tnin .58 Figure 3-4 DSC cooling thermograms of (a) PA6, (b) PA67PVACI?(C) PA6sPVAci, (d) PA63PVACJ, (e) PA62PVAc, (f) PA6,PVAC, (g) PA6,PVAc3and (h) PVAC specimens cooled at 20 C/min . 60 Figure 3-5 WAXS diffraction patterns of (a) P

24、A6, (b) PA67PVAai, (c) PAOjPVA3!, (d) PA63PVAa“（ e) PA62PVAai, (f) PASVAY (g) and (h) PVAa specimens. 60 vn Figure 3-6 WAXS diffraction patterns of (a) PA6, (b) PA67PVAbi, (c) PA65PVAbu (d) PA63PVAbi, (e) PA62PVAbi, (f) PA6,PVAbj? (g) PA6(PVAbj and (h) PVAbspecimens . 60 Figure 3-7 WAXS diffraction

25、patterns of PA6, (b) PA6?PVACi, (c) PA65PVAct， (d) PA63PVAc,? (e) PA62PVAC!, (f) PA6|PVAcb (g) PA6IPVAc3 and (h) PVAC specimens. . 61 Figure 3-8 FT-IR spectra of PA6, (b) PAevPVA、，（ c) PA65PVA (d) PA63PVAa, (e) PA62PVAa, (f) PA6iPVAa, (g) PA6,PVAa3 and(h) PVAa specimens determined at 25 C . 64 Figur

26、e 3-9 FT-1R spectra of PA6, (b) PA67PVAbh (c PA65PVAY (d) PA63PVAb|, (e) PA62PVAbl5 (f) PA6,PVAb, (g)PA6tPVAb3 and (h) PVAb specimens determined at 25cC . 65 Figure 3-10 FT-IR spectra of (a) PA6, (b) PA67PVACU (c) PA65PVACI, (d) PA63PVACb (e) PA62PVA、(f) PA61PVA、 (g) PAGiPVAY PA6!PVAC3 and (i) PVAC

27、specimens determined at 25 C . 66 Figure 3-11 FT-IR spectra of PA6 specimens determined at (a) 30C, (b) 80C, (c) 130C, (d) 180C, (e) 21 t and (f) 230 C . 67 Figure 3-12 FT-IR spectra of PVA specimens determined at (a) 30C, (b) 80C, (c) 130C, (d) 18 t, (e) 210Cand (f) 230 C . 68 Figure 3-13 Frequency

28、 difference (Avi) between the absorption bands of hydrogen- bonded amide and free amide groups () and Frequency difference (Avj) between the absorption bands of carbonyl and free carbonyl groups () of PA6 specimens determined at varying temperatures . ,.69 Figure 3-14 Frequency difference (Av) betwe

29、en the absorption bands of hydrogen- bonded hydroxyl and free hydroxyl groups of PVAa (A), PVAb (A), and PVAC (A) specimens determined at varying temperatures . 70 Figure 3-15 The values of tensile strength () and elongation at break () of PA6, PVAa specimens and PA6/PVA3 specimens . 73 Figure 3-16

30、The values of tensile strength () and elongation at break (#) of PA6, PVAb specimens and PA6/PVAb specimens. . 73 Figure 3-17 The valu of tensile sbrength () and elongation at break (#) of PA6, PVAC specimens and PA6/PVAC specimens . 74 Figure 3*18 The values of tensile strength of PA6XP VAay ( ), P

31、A6,PVAby ( ), PA6xPVAcy (0) specimens with varying the PVA contents of PA6xPVAy specimens . 75 Figure 3-19 The values of elongation at break of PAePVAA), PA6xPVAby(A)5 PA6xPVAcy (A) specimens with varying the PVA contents of PA6xPVAy specimens . 76 vm 原创性声明 本人郑重声明：所呈交的论文是本人在导师的指导下独立进行研 究所取得的研究成果。除了文

32、中特别加以标注引用的内容外，本论文 不包含任何其他个人或集体已经发表或撰写的成果作品。对本文的研 究做出重要贡献的个人和集体，均已在文中以明确方式标明。本人完 全意识到本声明的法律后果由本人承担。 论 文 作 者 签 名 ： 朗 4 日期： 年月 2 日 学位论文使用授权说明 学位论文作者完全了解学校有关保留、使用学位论文的规定，即： 按照学校要求提交学位论文的印刷本和电子版本；学校有权保存 学位论文的印刷本和电子版，并提供目录检索与阅览服务；学校可以 允许采用影印、缩印、数字化或其它复制手段保存学位论文 ，在不以 贏利为目的的前提下，学校可以公开学位论文的部分或全部内容。（保 密论文在解密后

33、遵守此规定 ） 作者签名：杉朗 4 指导教师签名 : 日期： 7 么 2 日 期 ： “ t Chapter I Introduction Chapter 1 Introduction 1.1 Reference Review During these twenty years, the miscibility and specific interaction of polymer blends have attracted significant attention in polymer science due to significant potentid application in i

34、ndustry. Here, we choose several papers that have major contribution in this field. In 1979, Coleman et al.ri studied the poly (e -caprolactone) (PCL)/poly(vinyl chloride) blend by using the FouriCT-transfonn infrared specboscopy. The results indicate that there is specific interaction between thrae

35、 polymer segments in both the molten and solid states. Furthermore, the author demonstrated that FTIR different jectroscopy is an excellent technique with which to follow the kinetic of crystallization of PCL in tiiis blend system. From this per, the authors began to study die specific interaction o

36、f polymer blend and thermodynamic properties by using FTIR. Therefore, in 1983, Coleman et al. studied the polymer blend of poly(hydroxy elha: of bisphenol A) (phenoxy) with PCL by using FTIR, indicated that die hydrogoi bonding interaction between the carbonyl group of PCL and the hydroxyl group of

37、 phenoxy. As a result, these two polyma*s are miscible in the amoiphous phase based on differential scanning calorimetry analyses. Moreover, in 1985, Moskala et studied of poly(vinylphenol) blends containing a numb of chemically and structurally dissimilar polyms including the polyesters PCL and pol

38、y(p-propiolactone); poly(vinyl alkyl ether) where tiie alkyl groups are methyl, ethyl and isobutyl respectively; poly(ethiene oxide) (PEO) and poly(vinyl pyrrolidone) (PVP). The authors considered that the frequency difference between the free hydroxjl group and hydrogen bonded hydroxyl group is abl

39、e to roughly estimate the enthalpy of hydrogen bonding and relative strength by using FTIR. In 1985, Natansolm studied the exothermal effect of phase separation in miscible polymer blend based on DSC analyses. The author demonstrated a DSC study of phase separation in several miscible polymer blends

40、. An exothermal effect associated with the phase sqjmation is evidenced and correlated with the interactions i Master Thesis of Hubei University between the componoits. In general, the exothermal peak temperatures and area dqend on the heating rate. This peak temperature extrapolation at zero rate (

41、thermodynamic equilibrium) should give the LCST point (binodal curve) on the phase diagram. Furthermore, at very high heating rate the area of the exothermal peak can be regarded as the demixing heat for the polymer blend and the temperature considered as the spinodal cmve. On the other hand, in 1987, Uriarte et al5 studied the amorphous blends of phenoxy and poly(vinyl