基于聚丙烯酸酯類溫敏聚合物的柔性智能紡織品的研究
發(fā)布時間：2018-08-20 20:26
【摘要】：智能紡織品(smart/intelligent textiles)是近幾十年來新崛起的,對人類生活具有變革意義的新型紡織材料。智能紡織品的開發(fā)與應用是各種高新技術在紡織品上的集中體現(xiàn),涉及到紡織與生物、化學、物理、電子領域的交叉與融合,具有較高的研究價值。智能紡織品智能化功能的實現(xiàn)基于智能材料,其中溫度響應性聚合物由于響應不依賴于其它化學助劑,溫度響應速度快而且劇烈,其相關結構的研究成為智能材料領域的一個熱點。在溫度的刺激下,溫敏聚合物具有體積膨脹/收縮,表面親/疏水性轉變的特性。通過物理或者化學方法將溫敏聚合物與紡織品相結合,將賦予傳統(tǒng)紡織品獨特的性能與高附加值,因此溫敏聚合物在智能紡織品領域有很大的應用前景。本文首先合成了具有乙氧基鏈段的聚丙烯酸酯類溫敏聚合物,獲知了聚丙烯酸酯類溫敏聚合物不同分子形態(tài)對溫敏性能的影響,探明了分子形態(tài)、結構與其轉變行為的內在聯(lián)系與規(guī)律。進一步以纖維素為過渡基底,模擬溫敏聚合物在紡織品上的結合狀態(tài),探究了基底對聚合物交聯(lián)薄膜表面形貌、轉變行為的影響,為基于聚丙烯酸酯類溫敏聚合物的智能紡織品的制備與應用奠定了理論基礎。最后通過交聯(lián)反應,將溫敏聚合物固定于棉織物表面,制備獲得了具有智能清潔、舒適調控與抗菌功能的紡織品。(1)采用單體2-甲基-2-丙烯酸-2-(2-甲氧基乙氧基)乙酯(MEO2MA)、聚環(huán)氧乙烷甲基丙烯酸酯(OEGMA300)與末端含有羥基的聚(乙二醇)甲基丙烯酸酯(EGMA360)通過原子轉移自由基聚合(ATRP)合成無規(guī)共聚物聚(2-甲基-2-丙烯酸-2-(2-甲氧基乙氧基)乙酯-共聚-聚環(huán)氧乙烷甲基丙烯酸酯)P(MEO2MAco-OEGMA300)和聚(2-甲基-2-丙烯酸-2-(2-甲氧基乙氧基)乙酯-共聚-聚(乙二醇)甲基丙烯酸酯)P(MEO2MA-co-EGMA360),研究了溫敏聚合物分子形態(tài)以及結構對溫敏性能的影響。溶液性能測試表明,P(MEO2MA-co-OEGMA300)、P(MEO2MAco-EGMA360)水溶液(10 mg/m L)的相轉變溫度(TT)分別為35oC、36oC,且P(MEO2MA-co-EGMA360)水溶液具有更寬的相轉變區(qū)間。薄膜性能測試表明,由于P(MEO2MA-co-EGMA360)側鏈末端含有羥基,因此其膨脹率較高,但是該羥基不具有溫敏性,導致溫敏轉變特性減弱,表現(xiàn)出更寬的轉變區(qū)間,該結果與水溶液中的轉變行為一致。此外,由于基底的限制,溫敏聚合物薄膜的溫敏性能僅能表現(xiàn)為膜厚的改變,在相轉變過程中,水分的排出過程亦僅能在垂直于基底的方向上,以擴散的形式實現(xiàn),從而導致溫敏聚合物薄膜的轉變行為較溶液更遲滯和平緩。(2)為進一步探究基底對聚丙烯酸酯類溫敏聚合物溫敏表面形貌、溫敏性能的影響。首先合成了三甲基硅纖維素(tmsc)并在硅片上旋涂成膜,利用取代反應制備了再生纖維素(rc)薄膜,并進一步通過交聯(lián)反應使p(meo2ma-co-egma360)與rc基底相結合。結果表明,取代度為2.21的tmsc在氯仿溶液中溶解性能好,通過旋涂在硅基底上獲得均一的tmsc薄膜。經取代反應后,tmsc薄膜粗糙度明顯增加,表面生成一層25nm的rc薄膜。轉變溫度以上時,p(meo2ma-co-egma360)交聯(lián)聚合物薄膜相鄰鏈段之間相互靠近,移動過的相應位置由于沒有聚合物的覆蓋,在最低處形成縫隙或者孔洞,導致底層纖維素部分區(qū)域裸露出來。p(meo2ma-co-egma360)交聯(lián)薄膜厚度在30-35oc明顯下降,且表面發(fā)生親疏水性的轉變,這為溫敏聚合物p(meo2ma-co-egma360)在織物上的應用奠定了理論基礎。(3)選用單體摩爾比為17:3的溫敏性共聚物p(meo2ma-co-egma360)與棉織物發(fā)生交聯(lián),制備了具有溫敏性的智能紡織品,測定并分析了其智能清潔以及舒適調控性能。結果表明,聚合物濃度為8%的交聯(lián)整理液經130oc焙烘2min與棉織物反應,獲得的交聯(lián)棉織物平衡溶脹率(esr)、接觸角(ca)以及潤濕時間(wt)在35-40oc之間發(fā)生突變,表明制備獲得的交聯(lián)棉織物具備有較好的溫敏性能。由于p(meo2ma-co-egma360)在轉變溫度以下的親水性,顯著增強了交聯(lián)棉織物清潔性能;溫度超過轉變溫度時,p(meo2ma-co-egma360)薄膜表面由致密的膜結構轉變?yōu)槎嗫捉Y構,因此能夠實現(xiàn)對透氣透濕的調節(jié),提高織物的穿著舒適性。經交聯(lián)反應后,織物耐洗性、耐摩擦牢度在可接受的范圍內,且白度、柔軟度、機械性能沒有受到影響。(4)考慮到聚(n-異丙基丙烯酰胺)pnipam具有生物相容性,且與pegma360的共聚可大大降低其玻璃化轉變溫度(tg)。首先合成一系列不同單體摩爾比的共聚物p(nipam-co-egma360),采用交聯(lián)方法,制備具有智能舒適調控以及抗細菌粘附性能的醫(yī)用紡織品。結果表明,共聚物P(NIPAM-co-EGMA360)隨著單體EGMA360含量的增加,Tg下降,熱穩(wěn)定性降低,TT升高。P(18NIPAMco-2EGMA360)的Tg為0 oC,TT為40 oC,熱穩(wěn)定性優(yōu)良,因此P(18NIPAM-co-2EGMA360)的引入不會影響到交聯(lián)棉織物的柔軟度。P(18NIPAM-co-2EGMA360)交聯(lián)棉織物的轉變區(qū)間為36-39oC�；赑NIPAM的溫敏性,在溫度的刺激下,交聯(lián)棉織物能夠通過改變表面聚合物層的孔隙大小,實現(xiàn)透氣/濕性能的調節(jié),具有智能舒適調控功能。此外由于EGMA360的親水性,在交聯(lián)棉織物表面形成一層親水性的薄膜,抑制交聯(lián)織物表面細菌的吸附。同時,P(NIPAM-co-EGMA360)交聯(lián)棉織物具有良好的耐洗牢度,且溫度響應穩(wěn)定,滿足智能紡織品日常生活中功能穩(wěn)定性的要求。
[Abstract]:Smart / intelligent textiles is a new type of textile material which has been rising in recent decades and is of great significance to human life. Intelligent textiles are based on smart materials. Temperature-responsive polymers respond rapidly and violently because they do not depend on other chemical auxiliaries. Research on their related structures has become a hot spot in the field of smart materials. Temperature-sensitive polymers have volume expansion/expansion under the stimulation of temperature. The combination of thermosensitive polymers with textiles by physical or chemical methods will endow traditional textiles with unique properties and high added value. Thermo-sensitive polymers have a great application prospect in the field of intelligent textiles. The effect of different molecular forms of polyacrylate thermosensitive polymers on the thermosensitive properties was studied. The relationship between molecular morphology, structure and transition behavior was explored. The influence of film surface morphology and transformation behavior laid a theoretical foundation for the preparation and application of smart textiles based on polyacrylate thermosensitive polymers. Finally, the thermosensitive polymers were immobilized on the surface of cotton fabrics by cross-linking reaction, and the smart, clean, comfortable, controlled and antibacterial textiles were prepared. Random Copolymer Poly (2-methyl-2-acrylic acid-2-(2-methoxyethoxy) ethyl ester (MEO2 MA), poly (ethylene oxide methacrylate) (OEGMA300) and poly (ethylene glycol) methacrylate (EGMA360) containing hydroxyl groups were synthesized by atom transfer radical polymerization (ATRP). The effects of molecular morphology and structure of ethane methacrylate P (MEO2 MAco-OEGMA300) and poly (2-methyl-2-acrylic acid-2-(2-methoxyethoxy) ethyl ester-copoly-poly (ethylene glycol) methacrylate P (MEO2 MA-co-EGMA360) on the thermosensitive properties were studied. Solution performance test showed that P (MEO2 MA-co-OEGMA300), P (MEO2 MAco-EGM-EGMA300) and P (MEO2 MA-co-EGM-EGMA360) were sensitive to temperature. The phase transition temperature (TT) of A360 aqueous solution (10 mg/m L) is 35oC, 36oC, and P (MEO2 MA-co-EGMA 360) aqueous solution has a wider phase transition range. The film performance test shows that the expansion rate of P (MEO2 MA-co-EGMA 360) is higher because of the hydroxyl group at the end of the side chain, but the hydroxyl group is not temperature-sensitive, resulting in the weakening of the temperature-sensitive transition characteristics. In addition, due to the limitation of the substrate, the temperature-sensitive properties of the thermosensitive polymer films can only change the thickness of the films. During the phase transition, the water release process can only be carried out in the direction perpendicular to the substrate and in the form of diffusion, which leads to the temperature-sensitive polymerization. (2) To further explore the effect of substrate on the surface morphology and temperature-sensitive properties of polyacrylate thermosensitive polymers, trimethylsilicone cellulose (tmsc) was synthesized and spin-coated on silicon wafer, and regenerated cellulose (rc) films were prepared by substitution reaction. P (meo_2ma-co-egma 360) was combined with RC substrate by overcrosslinking reaction. the results showed that TMSC with substitution degree of 2.21 had good solubility in chloroform solution. homogeneous TMSC films were obtained by spin-coating on silicon substrate. after substitution reaction, the roughness of TMSC films increased significantly, and a 25 nm RC film was formed on the surface of TMSC films. O-egma360 crosslinked polymer film adjacent chains close to each other, the corresponding position of the moving due to no polymer coverage, at the lowest point of the formation of gaps or holes, resulting in the exposed part of the underlying cellulose. P (meo2ma-co-egma360) crosslinked film thickness at 30-35oc decreased significantly, and the surface of hydrophilic transition occurred. It lays a theoretical foundation for the application of temperature-sensitive polymer P (meo2ma-co-egma 360) in fabrics. (3) The temperature-sensitive copolymer P (meo2ma-co-egma 360) with a molar ratio of 17:3 was selected to cross-link with cotton fabrics, and the temperature-sensitive intelligent textiles were prepared. The equilibrium swelling ratio (esr), contact angle (ca) and wetting time (wt) of the cross-linked cotton fabrics obtained by the reaction of the cross-linking finishing solution with 8% complex concentration and the cotton fabrics baked at 130 OC for 2 minutes showed that the cross-linked cotton fabrics had better temperature-sensitive properties, because P (meo2ma-co-egma360) was below the transition temperature. Hydrophilicity, significantly enhance the cleanliness of cross-linked cotton fabrics; when the temperature exceeds the transition temperature, P (meo2ma-co-egma360) film surface from dense membrane structure into porous structure, so it can be achieved to adjust the permeability and moisture permeability, improve the wearing comfort of the fabric. (4) Considering the biocompatibility of poly (n-isopropylacrylamide) P NIPAM and the copolymerization with pegma 360, the glass transition temperature (tg) of poly (n-isopropylacrylamide) P NIPAM can be greatly reduced. The results showed that with the increase of the content of monomer EGMA360, the Tg of copolymer P (NIPAM-co-EGMA360) decreased, the thermal stability decreased, and the TT of copolymer P (18NIPA Mco-2EGMA360) increased. The Tg of P (18NIPA Mco-2EGMA360) was 0 oC, TT was 40 oC, and the thermal stability was excellent. Therefore, the introduction of P (18NIPAM-co-2EGMA360) would not affect the crosslinking. Flexibility of cotton fabrics. The transition range of P (18NIPAM-co-2EGMA360) cotton fabrics is 36-39oC. Based on the temperature sensitivity of PNIPAM, cross-linked cotton fabrics can adjust the air permeability and moisture permeability by changing the pore size of the surface polymer layer under the stimulation of temperature. Moreover, due to the hydrophilicity of EGMA360, it has the function of intelligent and comfortable control. A hydrophilic film was formed on the surface of the cross-linked cotton fabric to inhibit bacterial adsorption on the surface of the cross-linked fabric. At the same time, the P (NIPAM-co-EGMA360) cross-linked cotton fabric has good wash fastness and stable temperature response, which meets the requirements of functional stability in daily life of intelligent textiles.
【學位授予單位】：浙江理工大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TS195.5
本文編號：2194892
[Abstract]:Smart / intelligent textiles is a new type of textile material which has been rising in recent decades and is of great significance to human life. Intelligent textiles are based on smart materials. Temperature-responsive polymers respond rapidly and violently because they do not depend on other chemical auxiliaries. Research on their related structures has become a hot spot in the field of smart materials. Temperature-sensitive polymers have volume expansion/expansion under the stimulation of temperature. The combination of thermosensitive polymers with textiles by physical or chemical methods will endow traditional textiles with unique properties and high added value. Thermo-sensitive polymers have a great application prospect in the field of intelligent textiles. The effect of different molecular forms of polyacrylate thermosensitive polymers on the thermosensitive properties was studied. The relationship between molecular morphology, structure and transition behavior was explored. The influence of film surface morphology and transformation behavior laid a theoretical foundation for the preparation and application of smart textiles based on polyacrylate thermosensitive polymers. Finally, the thermosensitive polymers were immobilized on the surface of cotton fabrics by cross-linking reaction, and the smart, clean, comfortable, controlled and antibacterial textiles were prepared. Random Copolymer Poly (2-methyl-2-acrylic acid-2-(2-methoxyethoxy) ethyl ester (MEO2 MA), poly (ethylene oxide methacrylate) (OEGMA300) and poly (ethylene glycol) methacrylate (EGMA360) containing hydroxyl groups were synthesized by atom transfer radical polymerization (ATRP). The effects of molecular morphology and structure of ethane methacrylate P (MEO2 MAco-OEGMA300) and poly (2-methyl-2-acrylic acid-2-(2-methoxyethoxy) ethyl ester-copoly-poly (ethylene glycol) methacrylate P (MEO2 MA-co-EGMA360) on the thermosensitive properties were studied. Solution performance test showed that P (MEO2 MA-co-OEGMA300), P (MEO2 MAco-EGM-EGMA300) and P (MEO2 MA-co-EGM-EGMA360) were sensitive to temperature. The phase transition temperature (TT) of A360 aqueous solution (10 mg/m L) is 35oC, 36oC, and P (MEO2 MA-co-EGMA 360) aqueous solution has a wider phase transition range. The film performance test shows that the expansion rate of P (MEO2 MA-co-EGMA 360) is higher because of the hydroxyl group at the end of the side chain, but the hydroxyl group is not temperature-sensitive, resulting in the weakening of the temperature-sensitive transition characteristics. In addition, due to the limitation of the substrate, the temperature-sensitive properties of the thermosensitive polymer films can only change the thickness of the films. During the phase transition, the water release process can only be carried out in the direction perpendicular to the substrate and in the form of diffusion, which leads to the temperature-sensitive polymerization. (2) To further explore the effect of substrate on the surface morphology and temperature-sensitive properties of polyacrylate thermosensitive polymers, trimethylsilicone cellulose (tmsc) was synthesized and spin-coated on silicon wafer, and regenerated cellulose (rc) films were prepared by substitution reaction. P (meo_2ma-co-egma 360) was combined with RC substrate by overcrosslinking reaction. the results showed that TMSC with substitution degree of 2.21 had good solubility in chloroform solution. homogeneous TMSC films were obtained by spin-coating on silicon substrate. after substitution reaction, the roughness of TMSC films increased significantly, and a 25 nm RC film was formed on the surface of TMSC films. O-egma360 crosslinked polymer film adjacent chains close to each other, the corresponding position of the moving due to no polymer coverage, at the lowest point of the formation of gaps or holes, resulting in the exposed part of the underlying cellulose. P (meo2ma-co-egma360) crosslinked film thickness at 30-35oc decreased significantly, and the surface of hydrophilic transition occurred. It lays a theoretical foundation for the application of temperature-sensitive polymer P (meo2ma-co-egma 360) in fabrics. (3) The temperature-sensitive copolymer P (meo2ma-co-egma 360) with a molar ratio of 17:3 was selected to cross-link with cotton fabrics, and the temperature-sensitive intelligent textiles were prepared. The equilibrium swelling ratio (esr), contact angle (ca) and wetting time (wt) of the cross-linked cotton fabrics obtained by the reaction of the cross-linking finishing solution with 8% complex concentration and the cotton fabrics baked at 130 OC for 2 minutes showed that the cross-linked cotton fabrics had better temperature-sensitive properties, because P (meo2ma-co-egma360) was below the transition temperature. Hydrophilicity, significantly enhance the cleanliness of cross-linked cotton fabrics; when the temperature exceeds the transition temperature, P (meo2ma-co-egma360) film surface from dense membrane structure into porous structure, so it can be achieved to adjust the permeability and moisture permeability, improve the wearing comfort of the fabric. (4) Considering the biocompatibility of poly (n-isopropylacrylamide) P NIPAM and the copolymerization with pegma 360, the glass transition temperature (tg) of poly (n-isopropylacrylamide) P NIPAM can be greatly reduced. The results showed that with the increase of the content of monomer EGMA360, the Tg of copolymer P (NIPAM-co-EGMA360) decreased, the thermal stability decreased, and the TT of copolymer P (18NIPA Mco-2EGMA360) increased. The Tg of P (18NIPA Mco-2EGMA360) was 0 oC, TT was 40 oC, and the thermal stability was excellent. Therefore, the introduction of P (18NIPAM-co-2EGMA360) would not affect the crosslinking. Flexibility of cotton fabrics. The transition range of P (18NIPAM-co-2EGMA360) cotton fabrics is 36-39oC. Based on the temperature sensitivity of PNIPAM, cross-linked cotton fabrics can adjust the air permeability and moisture permeability by changing the pore size of the surface polymer layer under the stimulation of temperature. Moreover, due to the hydrophilicity of EGMA360, it has the function of intelligent and comfortable control. A hydrophilic film was formed on the surface of the cross-linked cotton fabric to inhibit bacterial adsorption on the surface of the cross-linked fabric. At the same time, the P (NIPAM-co-EGMA360) cross-linked cotton fabric has good wash fastness and stable temperature response, which meets the requirements of functional stability in daily life of intelligent textiles.
【學位授予單位】：浙江理工大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：TS195.5
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