覆膜铁用功能聚酯的合成及其应用研究
发布时间：2018-10-19 10:12
【摘要】：覆膜铁是利用高温压合的方法将塑料薄膜贴合在金属板上的技术,可以代替金属板内涂和外涂技术应用在食品包装、家居建材、汽车等领域。其具有铁塑两重性,与传统的印涂铁相比具有更好的耐腐蚀性、耐深冲性、易装饰的特点。特别是其生产过程无有毒有害物质产生,无需烘干处理,满足工业生产绿色环保以及高效节能的需求。双向拉伸聚酯薄膜(BOPET)以其良好的韧性、力学性能、阻隔性、无毒等特性,在制备覆膜铁材料应用领域具有可行性。然而由于其本身分子链结构的规整性导致其易结晶表面活性低、熔点比较高难以与钢铁表面直接进行热覆合。本论文以降低聚酯熔点、提高BOPET薄膜的表面能,代替胶覆合工艺制备覆膜铁材料为主要目标,设计以表面改性和本体共聚改性两种方法制备覆膜铁用聚酯薄膜。首先以酸/醇同时改性PET合成覆膜铁用聚酯,对所合成的功能聚酯进行结构和性能的表征,并实施拉伸成膜实验,以电晕处理的方法提高薄膜表面能,评估了薄膜与无锡钢板(TFS)的热覆合强度。然后以上述功能聚酯合成工艺为基础,利用引入离子单体共聚改性PET合成两种离子聚酯。根据对离子聚酯结构和性能的分析,优化出一种兼具高表面能和优异加工性能的配方进行了工业合成和制膜,结合离子聚酯特殊的物理性质研究确定了与之匹配的工业化制膜生产工艺,考察了薄膜在无表面处理的条件下直接与TFS热压覆合,聚酯薄膜与TFS的热覆合强度以及界面结合机制。采用直接酯化的方法,利用不对称结构的间苯二甲酸(IPA)和新戊二醇(NPG)同时与乙二醇(EG)、对苯二甲酸(TPA)共聚合成不同单体配比的聚(对苯二甲酸乙二醇-co-对苯二甲酸新戊二醇-co-间苯二甲酸乙二醇-co-间苯二甲酸新戊二醇)酯(PENIT)。PENIT经双向拉伸工艺制备PENIT薄膜,利用电晕处理提高薄膜表面能用于覆膜铁制备。确定了合成聚酯的单体比例、催化剂用量、稳定剂用量、反应温度和缩聚终止搅拌功率等关键工艺条件。利用氢核磁(1H-NMR)、差示量热扫描仪(DSC)、热失重(TG)、偏光显微镜(POM)、特性粘度等测试手段研究了该聚酯的基本性能,同时考察了薄膜在不同层压温度下与TFS板的热覆合强度以及薄膜结晶性能的变化。结果表明不对称结构的单体IPA和NPG的嵌入降低了PET的结晶性和熔点,但对PET的热稳定性和特性粘度影响不大,可延续现有制膜工艺进行双向拉伸成膜。PENIT薄膜经电晕处理后表面能由37.2 m J/m2提高到51.4 mJ/m2,电晕后的PENIT薄膜在适当的层压温度下与TFS具有很好的结合强度。利用反射红外光谱(ATR-FTIR)、X光电子能谱(XPS)、扫描电子显微镜(SEM)、原子力学显微镜(AFM)和表面能等测试手段研究了电晕处理对聚酯薄膜表面性能的影响。利用静态接触角、XPS表征了聚酯薄膜表面衰减规律、分析了电晕聚酯薄膜表面衰减原因。结合电晕处理提高聚酯薄膜表面能的作用机制,分析了电晕聚酯薄膜与TFS的结合机理。首次提出了另一种覆膜铁用聚酯制备方法,即以直接引入离子单体共聚制备无需表面处理并具有持久表面能的离子聚酯。利用间苯二甲酸-5-磺酸钠(5-SSIPA)为第三单体,分别以1,4-丁二醇(BD)和聚乙二醇(PEG)为第四单体与EG、PTA共聚,借鉴PENIT合成工艺合成聚(对苯二甲酸乙二醇-co-对苯二甲酸-1.4-丁二醇-co-间苯二甲酸-5-磺酸钠乙二醇-co-间苯二甲酸-5-磺酸钠-1.4-丁二醇)酯(PEBST)和聚(对苯二甲酸乙二醇-co-间苯二甲酸-5-磺酸钠乙二醇-co-聚乙二醇)酯(PEPST)用于制备覆膜铁用薄膜。利用红外光谱(FT-IR)、1H-NMR、POM、热分析、特性粘度、流变和表面能等测试手段对两种功能聚酯的基本性能进行了表征。结果表明由于引入5-SSIPA,功能聚酯的表面能明显提高,第四单体的加入有效的改善了功能聚酯的流变性能。增加第四单体的含量,有助于提高功能聚酯的结晶性,通过调节第三单体和第四单体的含量可以得到表面能及熔点可调节的覆膜铁用聚酯。选用具有合适熔点的PEPST配方放大合成并进行工业化双向拉伸成膜试生产。鉴于PEPST特殊的物理性能,对PEPST进行了非等温冷结晶动力学研究,以求获得接近实际薄膜拉伸过程中结晶性的变化规律,确定了与PEPST匹配的双向拉伸制膜工艺,以热压直接热覆合工艺制备了覆膜铁层压材料,考察了离子聚酯薄膜与TFS的结合强度。结果表明PEBST薄膜无需表面处理并在适当的温度下即可与TFS进行永久覆合而达到本论文的目的。
[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.
【学位授予单位】：哈尔滨工业大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TQ323.4;TB383.4
[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.
【学位授予单位】：哈尔滨工业大学
【学位级别】：博士
【学位授予年份】：2015
【分类号】：TQ323.4;TB383.4
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