本文選題：陽(yáng)離子丙烯酸樹(shù)脂 + 乳液聚合�。� 參考：《陜西科技大學(xué)》2017年碩士論文

【摘要】：在皮革制品涂飾領(lǐng)域,陽(yáng)離子型的丙烯酸樹(shù)脂涂飾產(chǎn)品占有極大的比重,其主要用在皮革加工工序的底涂和頂涂中。因其凸顯的陽(yáng)離子性能可以實(shí)現(xiàn)“三明治”涂飾,市場(chǎng)前景廣闊。但傳統(tǒng)的陽(yáng)離子丙烯酸樹(shù)脂存在熱黏冷脆、機(jī)械性能及耐溶劑性較差等缺陷。因此,為了提高陽(yáng)離子丙烯酸樹(shù)脂的耐熱性、機(jī)械性能及耐溶劑性等,本研究主要通過(guò)交聯(lián)改性思路來(lái)設(shè)計(jì)膠膜分子結(jié)構(gòu),將不同的乙烯基單體進(jìn)行共聚,制備陽(yáng)離子丙烯酸樹(shù)脂乳液(CPA),添加交聯(lián)劑對(duì)其進(jìn)行改性,形成具有室溫自交聯(lián)功能的復(fù)合乳液(CPA-ATPE),并分別對(duì)各乳液及其膠膜性能進(jìn)行測(cè)試,具體研究?jī)?nèi)容如下:首先,固定單體總量及各單體比例,分別采用偶氮二異丁腈(AIBN)和2,2-偶氮二異丙基咪唑啉鹽酸鹽(AIBI)為引發(fā)劑,以單體轉(zhuǎn)化率、凝膠率、預(yù)乳化液穩(wěn)定性、乳液氣味、聚合物分子量為指標(biāo),考察引發(fā)劑的類(lèi)別、用量及加料方式對(duì)聚合工藝過(guò)程的影響。研究結(jié)果表明:AIBI具有更高的引發(fā)效能,最佳質(zhì)量分?jǐn)?shù)為1.2%。隨后,以乳液Zeta電位及乳液的貯存穩(wěn)定性為指標(biāo),考察了DMAEMA的用量對(duì)聚合物乳液的影響。研究表明:隨著DMAEMA用量的逐漸增加,乳液電位持續(xù)增高,當(dāng)DMAEMA的質(zhì)量分?jǐn)?shù)達(dá)到3%時(shí),聚合物乳液的穩(wěn)定性良好,Zeta電位為14.5mV,當(dāng)W(DMAEMA)超過(guò)3%時(shí),CPA乳液的穩(wěn)定性基本不變,因此W(DMAEMA)=3%。在此基礎(chǔ)上,固定DMAEMA和AIBI用量,探討1631/OS-15與1227/OS-15兩種復(fù)合乳化體系的乳化能力、配比及其用量對(duì)CPA乳液粒徑及PDI、凝膠率、穩(wěn)定性及外觀的基影響。研究結(jié)果表明:復(fù)合乳化劑1227/OS-15的綜合乳化性能較佳,其最佳應(yīng)用參數(shù):總用量為W(1227/OS-15)=3%,m(1227):m(OS-15)=1:2。其次,通過(guò)控制AAEM功能交聯(lián)單體用量以及相應(yīng)ATPE的添加量,制備CPA-ATPE復(fù)合乳液。采用FT-IR、XRD、AFM等對(duì)CPA及CPA-ATPE膠膜的結(jié)構(gòu)和形貌進(jìn)行表征;測(cè)定乳液粒徑及PDI、最低成膜溫度、Zeta電位及穩(wěn)定性和膠膜的親水性、吸水率、機(jī)械強(qiáng)度、耐溶劑性及玻璃化轉(zhuǎn)變溫度(Tg),考察AAEM的用量對(duì)CPA-ATPE復(fù)合乳液及其膠膜性能影響。研究表明:CPA-ATPE復(fù)合膠膜中AAEM的活性酮羰基與ATPE的端氨基已成功進(jìn)行了交聯(lián),AFM顯示膠膜表面凸起均勻;與CPA乳液相比,CPA-ATPE復(fù)合乳液平均粒徑減小,分散系數(shù)減小且其分布趨于均勻,電位呈現(xiàn)正電性,膠膜耐溶劑性、親水性、吸水率,抗張能力和斷裂伸長(zhǎng)率均提高,玻璃化溫度(Tg)提高了2.5℃,耐熱性能增強(qiáng);隨著AAEM用量的增加,CPA-ATPE復(fù)合乳液的最低成膜溫度從15.8℃降到13℃,表現(xiàn)為更易成膜,膠膜的機(jī)械性能增強(qiáng),吸水率降低,膠膜吸水率從67.2%降至17.8%,耐溶劑性增強(qiáng),當(dāng)W(AAEM)=3%時(shí),CPA-ATPE復(fù)合乳液及膠膜的綜合性能優(yōu)異。最后,將不同結(jié)構(gòu)的ATPE添加至CPA乳液中,制得系列CAP-ATPE復(fù)合乳液�？疾炷z膜的親水性、吸水率、機(jī)械強(qiáng)度、耐溶劑性,探討ATPE的結(jié)構(gòu)對(duì)CPA-ATPE復(fù)合乳液及膠膜基本性能的影響。采用FT-IR及AFM對(duì)系列膠膜的結(jié)構(gòu)及表面構(gòu)造進(jìn)行表征。結(jié)果發(fā)現(xiàn):系列膠膜中AAEM的酮羰與不同結(jié)構(gòu)的ATPE均已交聯(lián);隨著ATPE分子鏈的增長(zhǎng),AFM圖中白點(diǎn)增多,交聯(lián)程度下降,膠膜吸水率增強(qiáng),斷裂伸長(zhǎng)率稍微增加,抗張強(qiáng)度減小,接觸角減小,耐溶劑性緩慢降低,因此使用ATPE作為交聯(lián)劑時(shí),其分子鏈不宜過(guò)長(zhǎng)。
[Abstract]:In the field of leather finishing, cationic acrylic resin finishing products occupy a great proportion, which is mainly used in leather processing base coating and top coating. Because of its prominent cationic properties can achieve the "sandwich" finishing, the market prospect is broad. But the traditional cationic acrylic resin adhesive of thermal cold brittle the mechanical properties and solvent resistance and other defects. Therefore, in order to improve the heat resistance of cationic acrylic resin, the mechanical properties and solvent resistance, this study mainly through the cross linking modification ideas to the design film molecular structure, different vinyl monomers were copolymerized to prepare cationic acrylic resin emulsion (CPA). Adding a crosslinking agent to modify it, forming a self crosslinkable functional composite emulsion (CPA-ATPE), and were tested on the properties of the emulsion and film. The specific contents are as follows: firstly, fixed The amount of monomer and monomer ratio, respectively using two azo isobutyronitrile (AIBN) and 2,2- azo two isopropyl imidazoline hydrochloride (AIBI) as the initiator, the monomer conversion rate, gel rate, pre emulsion stability, emulsion odor, polymer molecular weight as index, effects of initiator dosage categories, influence and the feeding mode on the polymerization process. The results show that AIBI has led to higher efficiency, the best concentration was 1.2%. then to Zeta potential and storage stability of emulsion emulsion as the index, the effects of DMAEMA content on the properties of polymer emulsion. The results show that: with the gradual increase of the amount of DMAEMA increased continuously emulsion potential, when the mass fraction of DMAEMA reached 3%, the stability of polymer emulsion is good, Zeta potential is 14.5mV, when the W (DMAEMA) more than 3%, the stability of CPA emulsion is basically unchanged, so W (DMAEMA) =3%. on the basis of solid DMAEMA and AIBI investigate the dosage, emulsifying capacity of 1631/OS-15 and 1227/OS-15 two composite emulsion system, gel ratio and dosage of rate on the particle size of CPA emulsion and PDI, influence the appearance and stability of the base. The results show that the comprehensive performance of emulsion compound emulsifier 1227/OS-15 were the best, the best application parameters: the total amount of W (1227/OS-15) =3%, m (1227): m (OS-15) =1:2. second, by controlling the AAEM function of the amount of crosslinking monomer and the amount of the corresponding ATPE CPA-ATPE composite emulsion prepared by FT-IR, XRD, AFM etc. the structure and morphology of CPA and CPA-ATPE film were characterized; determination of particle size and PDI. The minimum film forming temperature, hydrophilicity, Zeta potential and stability and film water absorption, mechanical strength, solvent resistance and glass transition temperature (Tg), to investigate the effect of AAEM dosage on CPA-ATPE composite emulsion and film performance. The study shows that CPA-ATPE compound The activity of amino ketone carbonyl and ATPE membrane in AAEM has been successfully carried out crosslinking, AFM display surface projection film evenly; compared with CPA emulsion, CPA-ATPE emulsion mean particle size decreases, the dispersion coefficient decreases and the distribution becomes uniform, showing the potential positive film, solvent resistant, hydrophilic, water absorption rate, tensile strength and elongation were increased, the glass transition temperature (Tg) increased by 2.5 DEG C, heat resistance increased; with the increase of AAEM content, the minimum film forming temperature from 15.8 degrees down to 13 degrees of CPA-ATPE composite emulsion, performance is more likely to film, enhance the mechanical properties of the film, water absorption rate reduced film water absorption rate decreased from 67.2% to 17.8%, solvent resistance increased, when W (AAEM) =3%, the comprehensive performance of CPA-ATPE composite emulsion and film excellent. Finally, the different structure of ATPE added to CPA emulsion, CAP-ATPE emulsion prepared series of hydrophilic film on, Water absorption, mechanical strength, solvent resistance, to investigate the effect of ATPE structure on the basic properties of CPA-ATPE composite emulsion and film. The FT-IR and AFM structure and surface structure of the series of glue film were characterized. The results showed that the AAEM film in the series with different structure ATPE ketone carbonyl was crosslinked with ATPE; the molecular chain growth, increase the white AFM diagram, the crosslinking degree decreased, film absorption rate increased slightly increase the elongation, tensile strength decreases, the contact angle decreased, solvent resistance decreased slowly, so the use of ATPE as a crosslinking agent, its molecular chain should not be too long.

【學(xué)位授予單位】：陜西科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：TQ325.7;TS529.5

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