【摘要】：覆膜鐵是利用高溫壓合的方法將塑料薄膜貼合在金屬板上的技術(shù),可以代替金屬板內(nèi)涂和外涂技術(shù)應(yīng)用在食品包裝、家居建材、汽車(chē)等領(lǐng)域。其具有鐵塑兩重性,與傳統(tǒng)的印涂鐵相比具有更好的耐腐蝕性、耐深沖性、易裝飾的特點(diǎn)。特別是其生產(chǎn)過(guò)程無(wú)有毒有害物質(zhì)產(chǎn)生,無(wú)需烘干處理,滿足工業(yè)生產(chǎn)綠色環(huán)保以及高效節(jié)能的需求。雙向拉伸聚酯薄膜(BOPET)以其良好的韌性、力學(xué)性能、阻隔性、無(wú)毒等特性,在制備覆膜鐵材料應(yīng)用領(lǐng)域具有可行性。然而由于其本身分子鏈結(jié)構(gòu)的規(guī)整性導(dǎo)致其易結(jié)晶表面活性低、熔點(diǎn)比較高難以與鋼鐵表面直接進(jìn)行熱覆合。本論文以降低聚酯熔點(diǎn)、提高BOPET薄膜的表面能,代替膠覆合工藝制備覆膜鐵材料為主要目標(biāo),設(shè)計(jì)以表面改性和本體共聚改性?xún)煞N方法制備覆膜鐵用聚酯薄膜。首先以酸/醇同時(shí)改性PET合成覆膜鐵用聚酯,對(duì)所合成的功能聚酯進(jìn)行結(jié)構(gòu)和性能的表征,并實(shí)施拉伸成膜實(shí)驗(yàn),以電暈處理的方法提高薄膜表面能,評(píng)估了薄膜與無(wú)錫鋼板(TFS)的熱覆合強(qiáng)度。然后以上述功能聚酯合成工藝為基礎(chǔ),利用引入離子單體共聚改性PET合成兩種離子聚酯。根據(jù)對(duì)離子聚酯結(jié)構(gòu)和性能的分析,優(yōu)化出一種兼具高表面能和優(yōu)異加工性能的配方進(jìn)行了工業(yè)合成和制膜,結(jié)合離子聚酯特殊的物理性質(zhì)研究確定了與之匹配的工業(yè)化制膜生產(chǎn)工藝,考察了薄膜在無(wú)表面處理的條件下直接與TFS熱壓覆合,聚酯薄膜與TFS的熱覆合強(qiáng)度以及界面結(jié)合機(jī)制。采用直接酯化的方法,利用不對(duì)稱(chēng)結(jié)構(gòu)的間苯二甲酸(IPA)和新戊二醇(NPG)同時(shí)與乙二醇(EG)、對(duì)苯二甲酸(TPA)共聚合成不同單體配比的聚(對(duì)苯二甲酸乙二醇-co-對(duì)苯二甲酸新戊二醇-co-間苯二甲酸乙二醇-co-間苯二甲酸新戊二醇)酯(PENIT)。PENIT經(jīng)雙向拉伸工藝制備PENIT薄膜,利用電暈處理提高薄膜表面能用于覆膜鐵制備。確定了合成聚酯的單體比例、催化劑用量、穩(wěn)定劑用量、反應(yīng)溫度和縮聚終止攪拌功率等關(guān)鍵工藝條件。利用氫核磁(1H-NMR)、差示量熱掃描儀(DSC)、熱失重(TG)、偏光顯微鏡(POM)、特性粘度等測(cè)試手段研究了該聚酯的基本性能,同時(shí)考察了薄膜在不同層壓溫度下與TFS板的熱覆合強(qiáng)度以及薄膜結(jié)晶性能的變化。結(jié)果表明不對(duì)稱(chēng)結(jié)構(gòu)的單體IPA和NPG的嵌入降低了PET的結(jié)晶性和熔點(diǎn),但對(duì)PET的熱穩(wěn)定性和特性粘度影響不大,可延續(xù)現(xiàn)有制膜工藝進(jìn)行雙向拉伸成膜。PENIT薄膜經(jīng)電暈處理后表面能由37.2 m J/m2提高到51.4 mJ/m2,電暈后的PENIT薄膜在適當(dāng)?shù)膶訅簻囟认屡cTFS具有很好的結(jié)合強(qiáng)度。利用反射紅外光譜(ATR-FTIR)、X光電子能譜(XPS)、掃描電子顯微鏡(SEM)、原子力學(xué)顯微鏡(AFM)和表面能等測(cè)試手段研究了電暈處理對(duì)聚酯薄膜表面性能的影響。利用靜態(tài)接觸角、XPS表征了聚酯薄膜表面衰減規(guī)律、分析了電暈聚酯薄膜表面衰減原因。結(jié)合電暈處理提高聚酯薄膜表面能的作用機(jī)制,分析了電暈聚酯薄膜與TFS的結(jié)合機(jī)理。首次提出了另一種覆膜鐵用聚酯制備方法,即以直接引入離子單體共聚制備無(wú)需表面處理并具有持久表面能的離子聚酯。利用間苯二甲酸-5-磺酸鈉(5-SSIPA)為第三單體,分別以1,4-丁二醇(BD)和聚乙二醇(PEG)為第四單體與EG、PTA共聚,借鑒PENIT合成工藝合成聚(對(duì)苯二甲酸乙二醇-co-對(duì)苯二甲酸-1.4-丁二醇-co-間苯二甲酸-5-磺酸鈉乙二醇-co-間苯二甲酸-5-磺酸鈉-1.4-丁二醇)酯(PEBST)和聚(對(duì)苯二甲酸乙二醇-co-間苯二甲酸-5-磺酸鈉乙二醇-co-聚乙二醇)酯(PEPST)用于制備覆膜鐵用薄膜。利用紅外光譜(FT-IR)、1H-NMR、POM、熱分析、特性粘度、流變和表面能等測(cè)試手段對(duì)兩種功能聚酯的基本性能進(jìn)行了表征。結(jié)果表明由于引入5-SSIPA,功能聚酯的表面能明顯提高,第四單體的加入有效的改善了功能聚酯的流變性能。增加第四單體的含量,有助于提高功能聚酯的結(jié)晶性,通過(guò)調(diào)節(jié)第三單體和第四單體的含量可以得到表面能及熔點(diǎn)可調(diào)節(jié)的覆膜鐵用聚酯。選用具有合適熔點(diǎn)的PEPST配方放大合成并進(jìn)行工業(yè)化雙向拉伸成膜試生產(chǎn)。鑒于PEPST特殊的物理性能,對(duì)PEPST進(jìn)行了非等溫冷結(jié)晶動(dòng)力學(xué)研究,以求獲得接近實(shí)際薄膜拉伸過(guò)程中結(jié)晶性的變化規(guī)律,確定了與PEPST匹配的雙向拉伸制膜工藝,以熱壓直接熱覆合工藝制備了覆膜鐵層壓材料,考察了離子聚酯薄膜與TFS的結(jié)合強(qiáng)度。結(jié)果表明PEBST薄膜無(wú)需表面處理并在適當(dāng)?shù)臏囟认录纯膳cTFS進(jìn)行永久覆合而達(dá)到本論文的目的。
[Abstract]:The coated iron is a technology for adhering a plastic film to a metal plate by a high-temperature pressing method, and can be applied to the fields of food packaging, household building materials, automobiles and the like instead of metal plate inner coating and external coating technology. Compared with the traditional printed-coated iron, the invention has the characteristics of better corrosion resistance, deep drawability and easy decoration. In particular, the production process of the invention has no toxic and harmful substance generation, does not need drying treatment, meets the requirements of green environmental protection of industrial production and high-efficiency energy-saving. The biaxially oriented polyester film (BOPET) has the characteristics of good toughness, mechanical property, barrier property, non-toxicity and the like, and is feasible in preparing the application field of the coated iron material. However, due to the regularity of its molecular chain structure, its easy crystallization surface activity is low, the melting point is high and it is difficult to directly heat-cover the steel surface. In order to reduce the melting point of polyester and improve the surface energy of BOPET film, the film-coated iron material was prepared by surface modification and bulk copolymerization. The structure and properties of the synthesized functional polyester were characterized by acid/ alcohol simultaneous modified PET, and tensile film-forming experiment was carried out. The film surface energy was improved by corona treatment, and the heat-clad strength of thin film and Wuxi steel plate (TFS) was evaluated. Then, based on the above functional polyester synthesis technology, two kinds of ionic polyester were synthesized by introducing ionic monomer copolymerization modified PET. According to the analysis of the structure and properties of the ionic polyester, a formula with high surface energy and excellent processing property is optimized, and industrial synthesis and membrane preparation are carried out, and an industrialized membrane production process matched with it is determined according to the special physical properties of the ionic polyester. The heat-clad strength and interfacial bonding mechanism of thin films with TFS were investigated under the condition of no surface treatment. A direct esterification process is employed, with the use of an asymmetric structure of m-acid (IPA) and neopentyl glycol (NPG) at the same time as ethylene glycol (EG), Polyethylene terephthalate (PENIT) is prepared by copolymerizing terephthalic acid (TPA) into polyethylene glycol-co-terephthalic acid (PENIT) with different monomer ratios. PENIT prepares PENIT film through a two-way stretching process, improve that surface energy of the film by using corona treatment can be used for the preparation of coating iron. The key technological conditions such as the monomer ratio of synthetic polyester, the amount of catalyst, the amount of stabilizer, the reaction temperature and the termination of stirring power are determined. The basic properties of the polyester were studied by means of hydrogen-nuclear magnetic (1H-NMR), differential thermal scanner (DSC), thermogravimetry (TG), polarization microscope (POM), intrinsic viscosity, etc. The heat-clad strength of thin film and TFS plate under different laminating temperatures and the change of film crystallization properties were also investigated. The results show that the intercalation of monomer IPA and NPG with asymmetric structure reduces the crystallinity and melting point of PET. However, the thermal stability and intrinsic viscosity of PET are not affected greatly, and the two-way stretching film forming can be carried out on the existing membrane process. The surface energy of PENIT film after corona treatment can be raised from 37.2m J/ m2 to 51.4 mJ/ m2, and the PENIT film after corona has good bonding strength with TFS under suitable laminating temperature. The effect of corona treatment on the surface properties of polyester film was studied by means of reflection infrared spectroscopy (ATR-FTIR), Xray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), atomic mechanical microscope (AFM) and surface energy. The surface attenuation law of polyester film was characterized by means of static contact angle and XPS, and the cause of surface attenuation of corona polyester film was analyzed. Combined with corona treatment, the mechanism of surface energy of polyester film was improved, and the bonding mechanism between corona polyester film and TFS was analyzed. Another kind of polyester preparation method is proposed for the first time, that is, the ionic polyester which does not need surface treatment and has long-lasting surface energy is prepared by direct introduction of ionic monomer copolymerization. performing copolymerization of 1,4-butanediol (BD) and polyethylene glycol (PEG) as the fourth monomer with EG and PTA, Synthesis of poly (ethylene terephthalate-co-terephthalic acid-1,4-butanediol-co-phthalic acid-5-sodium ethanediol-co-phthalic acid-5-sulfonate-1,4-butanediol) ester (PEBST) and poly (ethylene terephthalate-co-room) using PENIT synthetic process phthalic acid-5-sulfonate glycol-co-polyethylene glycol) ester (PEPST) is used for preparing film for coating iron. The basic properties of two functional polyesters were characterized by FT-IR, 1H-NMR, POM, thermal analysis, intrinsic viscosity, rheology and surface energy. The results show that the surface energy of the functional polyester can be obviously improved due to the introduction of 5-SSIPA, and the addition of the fourth monomer effectively improves the rheological property of the functional polyester. the content of the fourth monomer is increased, the crystallinity of the functional polyester is improved, and the polyester for coating iron with adjustable surface energy and melting point can be obtained by adjusting the content of the third monomer and the fourth monomer. A PEPST formula with proper melting point is selected to amplify and synthesize and carry out industrialized two-way stretching film-forming trial production. In view of the special physical properties of PEPST, the non-isothermal cold crystallization kinetics of PEPST is studied in order to obtain the change law of crystallinity in the process of drawing close to the actual film, and a two-way stretching film process matched with PEPST is determined. The bonding strength between ionic polyester film and TFS was investigated. The results show that PEBST thin films do not need surface treatment and can be permanently coated with TFS at appropriate temperature for the purpose of this paper.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TQ323.4;TB383.4

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