本文選題：超支化聚氨酯 + 水溶性樹脂　； 參考：《太原理工大學(xué)》2015年碩士論文

【摘要】：日益嚴(yán)峻的環(huán)境問題催生對新型節(jié)能環(huán)保材料的需求，生產(chǎn)節(jié)能、無害、安全系數(shù)高、易處理降解的材料成為當(dāng)前熱點(diǎn)。水性材料因使用水代替?zhèn)鹘y(tǒng)有機(jī)物做溶劑，具有成本低廉，環(huán)境友好，，不易燃燒等特點(diǎn)，受到市場的親睞。水性聚氨酯結(jié)構(gòu)具有良好的拉伸性能、撓抓性能、黏度控制、毒性低等優(yōu)勢，在高分子、新型功能材料領(lǐng)域被廣泛研究和應(yīng)用。傳統(tǒng)的線性聚氨酯因缺少支鏈結(jié)構(gòu)及交聯(lián)度低，耐水性、耐熱性、機(jī)械性能等方面劣于有機(jī)溶劑型聚氨酯。提高交聯(lián)度是解決這一缺陷的有效途徑，通過引入超支化結(jié)構(gòu)，結(jié)合超支化三維球狀結(jié)構(gòu)黏度低、末端多官能團(tuán)容易接枝改性（易于提高交聯(lián)度）、溶解性好等優(yōu)勢，可大大提升水性聚氨酯的性能。 本文以超支化聚酯為核，通過核接枝法，合成了多種結(jié)構(gòu)類似但基團(tuán)比例不同的非離子水溶性超支化聚氨酯結(jié)構(gòu)，進(jìn)一步探討影響其性質(zhì)的結(jié)構(gòu)因素并研究了其作為涂層用樹脂的性能特征和原料配比。為超支化聚氨酯的固化成型應(yīng)用以及新功能的開發(fā)提供技術(shù)支持。 本論文的主要過程如下： ①以二代超支化聚酯（HBPs）為核，通過異佛爾酮二異氰酸酯（IPDI）中的一個(gè)異氰酸根（─NCO）與HBPs末端羥基反應(yīng)形成超支化聚氨酯結(jié)構(gòu)，另一份─NCO接枝水性鏈段基團(tuán)聚乙二醇單甲醚1000（MPEG-1000）及不飽和雙鍵基團(tuán)甲基丙烯酸羥乙酯（HEMA）。非離子親水鏈段MPEG的引入使分子具有了水溶性，而雙鍵則使其可實(shí)現(xiàn)自交聯(lián)或與其他不飽和基團(tuán)反應(yīng)形成交聯(lián)網(wǎng)狀結(jié)構(gòu)，合成的水性超支化聚氨酯（WHBPU）可作為水性聚合原料或是減水添加劑使用。使用(紅外表征)FT-IR、（核磁分析）1H-NMR和（凝膠色譜）GPC對產(chǎn)物WHBPU的合成過程，結(jié)構(gòu)特征，分子量大小進(jìn)行了表征分析。 ②對產(chǎn)物的基礎(chǔ)性質(zhì)進(jìn)行了研究測試，評價(jià)引入鏈段性質(zhì)對最終結(jié)構(gòu)的影響。通過紫外可見光譜分析(UV-vis)、激光粒度分析儀測試WHBPU的水溶性及分散體粒徑；WHBPU的流變行為、結(jié)晶性由旋轉(zhuǎn)流變儀、XRD等表征測得，顯示分子間作用力對鏈段結(jié)構(gòu)的影響進(jìn)而造成表觀性質(zhì)的差異；熱力學(xué)測試中示差掃描量熱DSC和熱重分析TG顯示聚合物隨著溫度的升高，在形態(tài)、分子結(jié)構(gòu)發(fā)生的變化，為評價(jià)其相結(jié)構(gòu)以及耐熱性提供依據(jù)。 ③UV-vis分析表明WHBPU水溶液在220nm處有最大吸光度，說明其末端不飽和基團(tuán)可吸收紫外光固化成型。在4%Wt光引發(fā)劑Api-180作用下，利用紫外光將四種WHBPU固化為薄膜涂層，對其乳液穩(wěn)定性、涂層硬度、平整性、吸水率、凝膠率、固化過程等研究，總結(jié)涂層性能與分子結(jié)構(gòu)以及鏈段比例間的關(guān)系。 ④最后根據(jù)WHBPU結(jié)構(gòu)具有倆親性的特性，設(shè)計(jì)包覆染料亞甲基藍(lán)小分子遷移到其不良溶劑氯仿相實(shí)驗(yàn)，利用UV-vis分析表征遷移亞甲基藍(lán)水相中最大吸收峰的吸光度變化，算出遷移的小分子量，驗(yàn)證WHBPU的包覆遷移能力。 通過以上的實(shí)驗(yàn)設(shè)計(jì)、結(jié)構(gòu)表征、性質(zhì)分析得出： WHBPU合成過程由IPDI中-NCO與HBPs的末端-OH反應(yīng)形成超支化聚氨酯結(jié)構(gòu)，測試分子量趨勢與設(shè)計(jì)相符但較理論值低，分子量分布良好。 WHBPU有良好的水溶性，溶解性隨著親水基團(tuán)增加而增加，在水中形成不同的形態(tài)，造成粒徑先增大后減小變化；結(jié)晶性與接枝的MPEG一致，為球晶結(jié)構(gòu)，旋轉(zhuǎn)剪切使晶體結(jié)構(gòu)和分子間作用被破壞，造成黏度急劇下降，表現(xiàn)出非牛頓流體的特征；溫度升高，聚合物熔融，硬軟段的受熱分解分別發(fā)生在310℃和370℃，呈倆段分解模式，耐熱性能較優(yōu)。 WHBPU作水性涂料樹脂，乳液穩(wěn)定性隨著親水基團(tuán)含量增加而增強(qiáng)，漆膜綜合性能與雙鍵密度、交聯(lián)度成正比；綜合評價(jià)，WHBPU-4:8為涂層用最佳原料配比。 WHBPU可負(fù)載遷移亞甲基藍(lán)分子進(jìn)入氯仿相，最大可達(dá)到90%移除，負(fù)載量由親疏段的比例決定。這一特性使其在涂膜染料保護(hù)、藥物負(fù)載、水處理等領(lǐng)域有應(yīng)用潛力和價(jià)值。
[Abstract]:The water - borne polyurethane has the advantages of low cost , environmental friendliness , low viscosity , low toxicity and the like , and has the advantages of low cost , environmental friendliness , difficult combustion and the like , and has the advantages of low cost , environmental friendliness , difficult combustion and the like , and is widely researched and applied in the fields of polymer and novel functional materials .

A variety of non - ionic water - soluble hyperbranched polyurethane structures with similar structure but different groups were synthesized by using hyperbranched polyester as the core . The structural factors affecting its properties were further discussed and the performance characteristics and raw material proportion of the resin were studied . The technical support was provided for the application of curing molding of hyperbranched polyurethanes and the development of new functions .

The main process of this paper is as follows :

The synthesis process , structural characteristics and molecular weight of the product WHBPU were characterized by FT - IR , 1H - NMR and ( gel chromatography ) GPC .

( 2 ) The basic properties of the products were studied and tested . The influence of the properties on the final structure was evaluated . The water solubility and dispersion particle size of WHBPU were measured by UV - vis and laser particle size analyzer .
The rheological behavior and crystallinity of WHBPU were measured by rotating rheometer , XRD and so on .
The differential scanning calorimetry ( DSC ) and TG ( TG ) analysis in thermodynamic tests show that the polymer increases with temperature , changes in morphology and molecular structure , and provides a basis for the evaluation of its phase structure and heat resistance .

( 3 ) UV - vis analysis shows that the WHBPU aqueous solution has the maximum absorbance at 220 nm , which shows that its terminal unsaturated group can absorb ultraviolet light curing . Under the action of 4 % Wt photoinitiator , four kinds of WHBPU are cured into thin film coating , the stability of emulsion , hardness , smoothness , water absorption , gel rate and curing process are studied , and the relationship between coating performance and molecular structure and segment ratio is summarized .

( 4 ) finally , according to the characteristics of the amphiphilic property of the WHBPU structure , the dye methylene blue small molecule is designed to be migrated to the chloroform phase experiment of the poor solvent , and the absorbance change of the maximum absorption peak in the migration methylene blue aqueous phase is characterized by UV - vis analysis , the small molecular weight of the migration is calculated , and the coating migration capability of the WHBPU is verified .

Through the above experimental design , structural characterization and property analysis ,

In the WHBPU synthesis process , the hyperbranched polyurethane structure was formed by the reaction of NCO with the terminal - OH of HBPs . The molecular weight trend of WHBPU was consistent with the design , but the molecular weight distribution was good .

WHBPU has good water solubility , and the solubility increases with the increase of hydrophilic group .
The crystallinity is consistent with the grafted MPEG , which is a spherulites structure , which causes the interaction between the crystal structure and the molecules to be destroyed , resulting in a sharp drop in viscosity and a characteristic of non - Newtonian fluid .
The temperature rise , the melting of the polymer , the thermal decomposition of the hard and soft segments occur at 310 鈩

本文編號：1955247