本文選題：不對稱兩嵌段共聚物 + 增容�。� 參考：《寧波大學(xué)》2017年碩士論文

【摘要】：本論文主要探究了不對稱兩嵌段共聚物聚苯乙烯-b-聚甲基丙烯酸甲酯(PS-b-PMMA)增容聚甲基丙烯酸環(huán)己酯/聚甲基丙烯酸甲酯(PCHMA/PMMA)二元不相容共混體系的相形貌調(diào)控機理。通過本研究,深入探究了加工過程中共混順序,均聚物分子量,不對稱兩嵌段共聚物嵌段比,共混體系粘度,加工過程中膠束的遷移擴散行為以及不對稱兩嵌段共聚物增容動力學(xué)與熱力學(xué)之間的關(guān)系,研究這些因素之間的內(nèi)在規(guī)律對于共混物相形貌的調(diào)控及力學(xué)性能的影響,用自洽場理論模型計算和“干-濕”刷理論進(jìn)行解釋和驗證不對稱嵌段共聚物增容對于共混物相形貌調(diào)控的實質(zhì)機理。本文所進(jìn)行的研究工作如下:1、論文第2章,以聚甲基丙烯酸環(huán)己酯/聚甲基丙烯酸甲酯(PCHMA/PMMA)的不相容共混體系為研究對象,研究了加工過程中共混順序?qū)Σ粚ΨQ兩嵌段共聚物PS-b-PMMA增容PCHMA/PMMA共混體系界面與膠束的競爭關(guān)系,從而探究出共混順序?qū)τ诓幌嗳莨不煳锵嘈蚊驳挠绊�。研究表�?在最優(yōu)共混步驟下加入不對稱兩嵌段共聚物SM1(NPS/NPMMA=1:9)和SM2(NPS/NPMMA=9:1),并減小共混物體系中均聚物PMMA分子量可以顯著改善共混物中的相形態(tài)和相尺寸,促使不對稱嵌段共聚物在兩相界面,提高了增容效率。這跟分散相體系粘度和共混時所形成的膠束熱力學(xué)狀態(tài)的穩(wěn)定性有關(guān)。增加PMMA分子量會改變不對稱嵌段共聚物在兩相界面之間的曲率,從而造成在界面的嵌段共聚物不穩(wěn)定,又會擴散至PMMA相內(nèi)部形成膠束,從而形成不同的分散相膠束化相形貌。2、在明確了共混順序?qū)τ诓粚ΨQ兩嵌段共聚物PS-b-PMMA增容PCHMA/PMMA共混體系相形貌的影響之后,在論文的第3章,研究了不對稱兩嵌段共聚物嵌段比和均聚物分子量對于共混物相形貌的調(diào)控機理。研究發(fā)現(xiàn),較為對稱嵌段比例結(jié)構(gòu)的不對稱兩嵌段共聚物SM4(NPS/NPMMA=6:4)增容效果好,相尺寸小,在分散相PMMA分子量低的情況下嵌段共聚物基本都在界面上。不對稱兩嵌段共聚物SM1和SM2由于鏈段結(jié)構(gòu)和比例的影響更容易在體相形成膠束,SM3(NPS/NPMMA=8:2)介于兩者之間。自洽場理論模型的計算也很好解釋了這個現(xiàn)象。并且通過調(diào)控均聚物分子量改變內(nèi)外圍的乳化效果,改變鏈段之間的溶脹程度可以影響嵌段共聚物在界面的利用率,同時也影響著不對稱嵌段共聚物在界面的穩(wěn)定性,對于共混物相形貌的調(diào)控具有深刻的意義。不僅如此,研究還發(fā)現(xiàn)擁有膠束的共混物相形貌也同時反映出共混物性能的變化。不對稱兩嵌段共聚物增容,尤其是兩者1:9和9:1嵌段比的SM1和SM2嵌段共聚物非但沒能增強材料的拉伸性能,反而由于膠束的存在降低了共混體系的拉伸強度。3、為證實不對稱兩嵌段共聚物PS-b-PMMA在PCHMA/PMMA共混體系中所形成膠束的擴散遷移以及界面嵌段共聚物的熱力學(xué)穩(wěn)定性對于共混體系相形貌的影響。在論文的第4章,我們研究了不對稱兩嵌段共聚物PS-b-PMMA的膠束遷移擴散行為以及增容PCHMA/PMMA共混體系動力學(xué)與熱力學(xué)的關(guān)系。研究發(fā)現(xiàn),膠束的熱力學(xué)穩(wěn)定性因素也是影響膠束擴散的一個至關(guān)因素,嵌段越長,與該嵌段相容的相與其形成的“濕刷”程度越大,此時鏈段相互作用力越大,鏈段相互摩擦力越強,嵌段的鏈段運動困難,分子量大的嵌段共聚物在體相的擴散速率慢,而分子量小的嵌段共聚物在體相擴散速率快。研究還發(fā)現(xiàn)不對稱兩嵌段共聚物對不相容共混體系增容動力學(xué)與熱力學(xué)因素都存在著影響,并且受不對稱兩嵌段共聚物嵌段比和共混體系分子量的影響。在分散相低分子量的情況下,不對稱兩嵌段共聚物SM1,SM2和SM3增容的PCHMA/PMMA不相容共混體系的動力學(xué)勢壘較高,熱力學(xué)因素起主要影響作用,較為對稱的SM4增容的情況下動力學(xué)與熱力學(xué)勢壘相差不大,熱力學(xué)影響因素并不明顯;而在分散相高分子量的情況下,SM1,SM2,SM3和SM4增容的PCHMA/PMMA不相容共混體系的熱力學(xué)勢壘較低,依舊起主要影響作用,此時加工過程中動力學(xué)因素對不對稱兩嵌段共聚物增容PCHMA/PMMA不相容共混體系的影響并不是很大。
[Abstract]:In this paper, the mechanism of phase morphology regulation of asymmetric two block copolymer polystyrene -b- polymethyl methacrylate (PS-b-PMMA) Compatibilization of two element incompatible blends of poly (cyclohexyl methacrylate) / polymethyl methacrylate (PCHMA/PMMA) was investigated. The mass ratio of the asymmetric two block copolymer, the viscosity of the blend system, the migration and diffusion behavior of the micelles in the process and the relationship between the compatibilization kinetics and the thermodynamics of the asymmetric two block copolymers, and the influence of the inherent laws between these factors on the control and mechanical properties of the blend phase shape and the mechanical properties of the blends, using the self consistent field theory model Calculation and "dry wet" brush theory are used to explain and verify the essential mechanism of asymmetric block copolymer compatibilization. The research work in this paper is as follows: 1, the second chapter of this paper is the research object of the incompatible blend system of cyclohexyl methacrylate / polymethyl methacrylate (PCHMA/PMMA). In the process, the competition relationship between the PCHMA/PMMA blend interface and the micelle of the asymmetric two block copolymer PS-b-PMMA was added to explore the influence of the blending order on the phase appearance of the incompatible blends. The study showed that the asymmetric two block copolymer SM1 (NPS/NPMMA=1:9) and SM2 (NPS/NPMMA) were added under the optimal blending procedure. =9:1), and reducing the PMMA molecular weight of the homopolymer in the blends can significantly improve the phase state and phase size in the blends, prompting the asymmetric block copolymers to increase the compatibilization efficiency at the two-phase interface. This is related to the stability of the micelle thermodynamic state formed when the viscosity of the dispersed phase system and the blend formed. The increase of the molecular weight of the PMMA will change. The curvature of the asymmetric block copolymer at the two phase interface leads to the instability of the block copolymer at the interface and the diffusion of the micelles into the PMMA phase, thus forming a different dispersed phase micellization phase appearance.2. In the clear blending order, the phase appearance of the asymmetric two block copolymer PS-b-PMMA Compatibilization of the PCHMA/PMMA blends In the third chapter of the paper, the regulation mechanism of the asymmetric two block block ratio and the molecular weight of homopolymer on the phase morphology of the blends is studied. It is found that the asymmetric two block copolymer SM4 (NPS/NPMMA=6:4) has good compatibilization effect, small phase size and low molecular weight of PMMA in dispersed phase. The lower block copolymers are basically at the interface. Asymmetric two block copolymers SM1 and SM2 are more likely to form micelles in bulk due to the influence of the chain structure and proportion. The SM3 (NPS/NPMMA=8:2) is between the two. The calculation of the self consistent field theoretical model also explains this phenomenon well. And the internal and external milk is changed by regulating the molecular weight of the homopolymer. The effect and the degree of swelling between the segments can affect the utilization of the block copolymer at the interface, and also affect the stability of the asymmetric block copolymer at the interface. It is of great significance to the control of the phase appearance of the blends. The changes in performance. The compatibilization of asymmetric two block copolymers, especially the SM1 and SM2 block copolymers of both 1:9 And 9:1 block ratios, does not enhance the tensile properties of the materials, but reduces the tensile strength.3 of the blends due to the presence of micelles, which proves that the asymmetric two block copolymers are formed in the PCHMA/PMMA blends. The influence of the diffusion and migration of micelles and the thermodynamic stability of the interface block copolymers on the phase morphology of the blends. In the fourth chapter of the paper, we studied the micellar migration and diffusion behavior of the asymmetric two block copolymer PS-b-PMMA and the relationship between the kinetics of the compatibilization of the PCHMA/PMMA blends and the thermal mechanics. The stability factor is also a crucial factor affecting the diffusion of micelles. The longer the block is, the greater the degree of "wet brush" which is compatible with the block, the greater the interaction force of the chain segment, the stronger the interaction force of the chain segment, the difficulty of the segment chain movement and the slow diffusion rate of the block copolymer with large molecular weight in the body phase, and the molecule of the molecule. It is also found that asymmetric two block copolymers have an influence on the compatibilization kinetics and thermodynamic factors of incompatible blends, and are influenced by the ratio of the asymmetrical two block copolymers and the molecular weight of the blends. Under the condition of the low molecular weight of the dispersed phase, asymmetric two inlay. The dynamic potential barrier of the SM1, SM2 and SM3 Compatibilization of the PCHMA/PMMA incompatible blend system is higher, and the thermodynamic factors play a major role. In the case of the more symmetrical SM4 compatibilization, there is little difference between the kinetics and the thermodynamic barrier, and the thermodynamic factors are not obvious. In the case of the dispersed phase high molecular weight, SM1, SM2, SM3 and SM4 increase. The PCHMA/PMMA incompatible blend system has a lower thermodynamic barrier and still plays a major role. In this process, the influence of dynamic factors on the compatibilization of asymmetric two block copolymer on PCHMA/PMMA incompatible blends is not very significant.

【學(xué)位授予單位】：寧波大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O631

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本文編號：1891545