Amine-terminated nylon 6/66/1010 (AM-6/66/1010) used for hot melt adhesives: synthesis and properties

A new amine-terminated nylon 6/66/1010 (AM-6/66/1010) copolyamide hot melt adhesive with the molecular weight of 21,000–96,000 Da was synthesized and blocked with 1-hexadecylamine. The AM-6/66/1010 samples were characterized by ¹H-NMR spectroscopy, differential scanning calorimetry (DSC), thermal gravimetric analysis, and gel permeation chromatography. The ¹H-NMR spectroscopy demonstrated that 1-hexadecylamine functions as blocking agent in this polymerization. The DSC thermograms showed that the extra peak (peak (II)) and the melting peak (peak (I)) of AM-6/66/1010 are moving left and the glass transition temperature of AM-6/66/1010 decreases as the mole ratio α_H/C (1-hexadecylamine/total carboxyl) increases. The thermal gravimetric analysis indicated that AM-6/66/1010 hot melt adhesive has a high thermal stability. The peel strength of the test specimen obtained by hot melt glutinous lining of AM-6/66/1010 or AC-6/66/1010 and fabric 6535 (65% PET, 35% cotton) was studied using T-peel tests, and the results showed that the washable and dry-cleaning resistant of AM-6/66/1010 copolyamide hot melt adhesive is better than that of carboxyl-terminated nylon 6/66/1010 (AC-6/66/1010) copolyamide hot melt adhesive.     

MRP管道镀锌钢带与热熔胶之间粘接性能研究

钢带增强聚乙烯螺旋波纹管(MRP)中钢带与热熔胶之间的粘接对管道质量有很大的影响。本文主要从原材料选择、制样工艺条件和钢带表面处理3个方面对热熔胶与镀锌钢带之间的粘接性能进行了研究。不同型号的热熔胶和镀锌钢带对粘接性能有很大的影响;压力升高到5 MPa时热熔胶与钢带之间的粘接性有一定的提高,一定范围内升高温度对材料的粘接性有一定的提高;对镀锌钢带表面进行Zn系磷化能很好地提高界面粘接效果。     

Polyesteramides used for hot melt adhesives: Synthesis and effect of inherent viscosity on properties

Polyesteramides, with different inherent viscosities, were synthesized from dimer acid, sebacic acid, ethylenediamine, and diethylene glycolamine. The effect of inherent viscosity of the polyesteramides on their thermal properties, such as melt viscosity, softening point, heat of fusion, glass‐transition temperature, and low‐temperature flexibility, was studied. The effect of the inherent viscosity on mechanical properties, such as tensile strength, elongation at break, and hardness, and on adhesion properties, such as lap shear strength and T‐peel strength, was also investigated. The results show that melt viscosity, tensile strength, and elongation at break increase as the inherent viscosity increases, and that lap shear strength of the polyesteramides also increases with increasing inherent viscosity, whereas softening point, glass‐transition temperature, and shore D hardness of the polyesteramides essentially do not change as the inherent viscosity increases within a certain range. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2696–2701, 2001     

Synthesis and properties of polyamide/LLDPE composites with compatibilizer used as hot melt adhesive

In this work, a new polyamide (PA155) was synthesized from higher purity dimer acid, sebacic acid, ethylenediamine, and piperazine, and the ternary blends were prepared by blending PA155 with LLDPE in the presence of the compatibilizer, maleic anhydride grafted linear low-density polyethylene (LLDPE-g-MAH). The weight ratio of PA155 to LLDPE of the samples was kept constant at 80/20 and the amount of LLDPE-g-MAH was varied at 0, 3, 6, 9, and 12 wt% over the total weight of the blend respectively. The scanning electron microscope and mechanical properties tests showed that the compatibility and the mechanical properties were improved with the increase in LLDPE-g-MAH content, and the blend containing 9.0 wt% LLDPE-g-MAH exhibits an optimal miscibility behavior and mechanical properties. The hot melt adhesives which were prepared from the ternary blends were assessed by 180°peel tests of Al/adhesive/polypropylene stack. The peeling strength for the sample containing 9.0 wt% compatibilizer (82.5 N/2.5 cm) is much more than that of the samples without compatibilizer (<20 N/2.5 cm).     

Reactive hot melt polyurethane adhesives modified with pentaerythritol diacrylate: synthesis and properties

Pentaerythritol diacrylate (PEDA) was synthesized by direct esterification from acrylic acid and pentaerythritol, and the reactive hot melt polyurethane adhesives (PURs) with high green strength were prepared from Poly(1,6-hexamethyleneadipate), PHA-3000, two kinds of Poly(propylene glycol) (PPG-1000 and PPG-4000) and PEDA as well as terpene-phenolic resin. Five samples of PURs with different weight percent (α) of PEDA (α = 0, 3, 5, 7, and 10 wt%), were obtained. The rheological properties, thermal stability, and mechanical properties of the samples were investigated. The results showed that the melt viscosity (η) and the storage shear modulus of the samples increase with the increase in α, while the thermal stability changes little. The bonding strength of the samples after 10 min, 30 min, and 48 h was assessed by 180° peel tests of Fabric 6535/adhesives/Fabric 6535 stacks. The results showed that the green strength after 30 min increases with the increase in α when α is not higher than 7 wt%.     

聚酰亚胺热熔胶粘剂的合成与性能研究

制备了挠性印制电路中铜箔与聚酰亚胺基材间的聚酰亚胺粘接材料,由醚酐、脂肪族二胺和4,4’-二氨基二苯醚(ODA)或杂环芳香二胺共聚得到的聚酰亚胺薄膜的成膜性很好。通过红外分析,含ODA聚酰亚胺和含杂环聚酰亚胺薄膜已酰亚胺化完全。其力学性能较好。通过DSC分析,含ODA聚酰亚胺的玻璃化转变温度为141℃,结晶熔融温度为212℃;含杂环聚酰亚胺的玻璃化转变温度为136℃,并在225℃出现了一个吸热峰。采用含ODA或杂环聚酰亚胺胶粘剂制备的双面挠性印制电路基板的平均剥离强度为828．66N／m及710．98N／m。     

热塑性聚氨酯热熔胶的合成与性能研究

以己二酸系聚酯二醇为软段,二异氰酸酯与扩链剂生成的链段为硬段,制备了聚氨酯热熔胶;研究了软硬段组成、结构、相对分子质量、扩链剂、异氰酸酯指数等对聚氨酯热熔胶的力学性能、结晶性能、粘接性能及耐热性能的影响。     

新型聚酰胺热熔胶的研制与开发

采用尼龙1010代替尼龙66,从配方上改进了聚酰胺热熔胶的耐水洗性能,同时,采用环氧改性技术,提高了热熔胶的粘接强度和耐水洗性能。     

氯化钙对尼龙6/66结晶态结构的影响

本文采用示差扫描量热法(DSC)、傅立叶变换红外光谱法(FTIR)研究了CaCl2对尼龙6/66结晶态结构的影响.DSC测试结果表明,随着尼龙6/66中CaCl2含量的增加,尼龙6/66的结晶温度、熔融温度降低,结晶度逐渐减小直至变为无定型态.红外光谱研究结果证实了钙离子能够插入尼龙6/66分子链,与尼龙6/66分子链上的羰基发生络合作用,破坏尼龙6/66原有的氢键,阻碍尼龙6/66分子链的自由运动,从而使其无法结晶.     

热熔胶用马来酸酐接枝聚乙烯研究进展

通过双螺杆挤出机将马来酸酐熔融接枝聚乙烯,制备的聚乙烯热熔胶具有粘接性能强、价格低等优点,广泛地应用于钢塑复合管。本文根据近年来聚乙烯热熔胶的研究方向,综述了新型引发剂及引发方式对接枝反应的影响;比较了不同种类聚乙烯接枝效果的差异;总结了改性单体对热熔胶性能的改善以及温度、挤出机螺杆结构和转速等工艺条件对聚乙烯热熔胶的影响。分别总结了化学滴定法和红外光谱法对接枝率的表征;简述了材料表面处理和涂胶工艺对剥离强度的影响。分析了热熔胶剥离强度传统制样方法的不足,并总结了能得到稳定真实剥离强度的制样方案。展望了低马来酸酐含量、高粘接强度的绿色环保型聚乙烯热熔胶的研究前景。     

Lower purity dimer acid based polyamides used as hot melt adhesives: synthesis and properties

Hot melt polyamides exhibit high adhesive strength. The polyamides synthesized from dimer fatty acids and diamines can present low crystallinity and a broad range of melting temperatures. In this work, polyamides with different compositions of dimer fatty acids, piperazine, ethylenediamine, sebacic acid and stearic acid and different content of secondary diamine (piperazine) and primary diamine (ethylenediamine) were synthesized. Polyamides with higher purity of dimer acids showed greater molecular weight, adhesion performance and a better mechanical resistance evaluated in stress/strain test. Softening point increased with increase in monomers content. By differential scanning calorimetry analysis, it was observed that polyamides with low percentage of monomer content show only one narrow melting peak in 100 °C. The increase in the acids monomer content leads to a larger temperature range of melting peak. The use of dimer fatty acid with a low content of monomers (up to 6%) in the polyamides synthesis promotes the formation of hot melt adhesives with good adhesion performances. The lowest monomer content leads to an increase in molecular weight, viscosity and mechanical properties of polyamide. Increase in the content of primary amines in polyamides increases crystallinity, viscosity and mechanical properties due to the higher number of hydrogen bonds formed by amide groups.     

Synthesis and properties of flame-retardant reactive hot melt polyurethane adhesive

Abstract

A novel liquid polyphosphonate polyol (DMDP) was synthesized from dimethyl methylphosphonate and 1,6-hexanediol. Reactive hot melt polyurethane adhesives with high flame retardancy (HMPURs) were prepared from poly(tetramethylene ether glycol) (PTMG-2000), two kinds of poly(1,4-butylene adipate) (PBA-2000 and PBA-3000) and DMDP or dimethyl methylphosphonate as well as tetrahydrofuran acrylate. Five specimens of flame-retardant HMPURs with different weight percent of DMDP (0, 2, 4 and 6?wt%) and dimethyl methylphosphonate (4?wt%) were obtained. The mechanical properties, thermal stability, flammability, and bonding strength of the specimens were investigated. The results show that with the increase of DMDP content, the elongation at break and tensile strength decrease slightly, and the flame retardancy of HMPURs is significantly improved with the limiting oxygen index (LOI) value increasing from 17.2 to 28.2. The incorporation of DMDP leads to a higher thermal stability of HMPURs at high temperature and more char yield at 650?°C. With the increase of DMDP content, the final bond strength of HMPURs on the same substrate changes little, but the green strength of HMPUR-6 on the same substrate is observably less than other samples. The performance of HMPUR with the reactive flame retardant is superior to that of HMPUR with the additive flame retardant. In addition, the corresponding flame-retardant mechanism of DMDP-containing HMPURs was investigated by pyrolysis-gas chromatography coupled to mass spectrometry (Py-GC/MS). The results indicate that the pyrolysis of the HMPURs releases phosphorus-containing fragments to play a flame retardant role.     

热熔压敏胶粘剂的市场和技术动向

综述热熔压敏胶粘剂在美国、欧洲、日本和中国的市场动向 ,和热熔压敏胶 (热塑弹性体 ,丙烯酸系、UV/EB固化系 )的发展     

钢/塑复合管用热熔胶的制备与性能研究

以PE(聚乙烯)接枝母料、线性低密度聚乙烯(LLDPE)为主要原料,石油树脂为增黏树脂,苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物(SEBS)为改性剂,采用单因素试验法优选出制备钢/塑复合管用HMA(热熔胶)的最佳配方。结果表明:增黏树脂的引入能明显提高HMA的剥离强度和熔体指数,并且胶接层的破坏形式为内聚破坏;SEBS类弹性体的引入能显著提高HMA的剥离强度,但熔体指数明显降低,而且胶接层的破坏形式是黏附破坏;当m(PE接枝母料)∶m(LLDPE)∶m(石油树脂)∶m(SEBS)=30∶45∶15∶10时,HMA的综合性能相对最好,其剥离强度为397 N/cm、熔体指数为2.3 g/10 min且胶接层的破坏形式是内聚破坏。     

复合金属板用高强度耐腐蚀聚酯型热熔胶的研制

按照m[氯乙烯醋酸乙烯酯(VC-VAc)]∶m[二月桂酸二丁基锡(DBTDL)]∶m[邻苯二甲酸二丁酯(DBP)]∶m(硬脂酸钙)=50∶3∶4∶1比例配制复合氯醋树脂,然后以此作为聚酯热熔胶的改性剂。结果表明:当w(复合氯醋树脂)=30%(相对于热熔胶而言)时,改性热熔胶的粘接强度为7.6 MPa,Tg提高到91.2℃;改性热熔胶在10%醋酸或40%NaOH溶液中浸泡48 h后未发生剥离现象,其最大粘接强度分别为6.68 MPa和6.39 MPa;经5%NaCl喷雾24 h或10%Na2CO3溶液浸泡48 h后,其性能最接近未浸泡试样;该高性能热熔胶适用于双金属板的热复合。     

光/湿双固化聚氨酯热熔胶的制备与性能研究

以多元醇、异氰酸酯、含羟基丙烯酸酯和光引发剂等为原料,制备了PET(聚酯)基材粘接用光/湿双固化PU(聚氨酯)-PUA(聚氨酯丙烯酸酯)型反应性HMA(热熔胶)。研究结果表明:该HMA中同时含有可光固化基团(C=C)和可湿固化基团(-NCO);当n(C=C)∶n(-NCO)=20∶80、w(复合光引发剂)=1.5%~2.0%和引入甲基丙烯酸羟乙酯(HEMA)时,相应HMA具有较高的初始强度和最终强度;光/湿双固化HMA的透明度高于湿固化HMA,说明UV固化是增加光/湿双固化HMA透明度的主要原因。     

铝塑复合管用接枝型聚乙烯类热熔胶的制备及性能研究

以高密度聚乙烯(HDPE)和线型低密度聚乙烯(LLDPE)为主体树脂,过氧化二异丙苯(DCP)为引发剂,顺丁烯二酸酐(MAH)为主要单体进行接枝反应挤出制取PE-g-MAH接枝物;然后将该接枝物、增黏剂及其它助剂等进行共混挤出,制备出粘接强度高、流动性能好的铝塑复合管用热熔胶。讨论了原料配比、接枝单体、DCP、增黏树脂和乙烯类弹性体等对该热熔胶性能的影响,并采用红外光谱(FT-IR)技术对该接枝物的结构进行了表征。结果表明:以m(HDPE)∶m(LLDPE)=1∶5,适量控制DCP和不饱和单体的用量,并采用MAH/AA混合单体进行接枝改性,在保证热熔胶流动性能较好的前提下,可得到接枝率及剥离强度均较高的热熔胶;另外,加入适量的乙烯类弹性体,热熔胶的剥离强度明显提高。     

铝塑复合板用热熔胶的制备及性能研究

以过氧化二异丙苯(DCP)为引发剂、马来酸酐(MAH)为接枝改性单体和聚乙烯(PE)为主要原料,采用熔融挤出法制备了铝塑复合板用PE-g-MAH(聚乙烯接枝马来酸酐)基HMA(热熔胶),并着重探讨了DCP和MAH含量对PE-g-MAH的接枝效率和粘接性能等影响。结果表明:在试验范围内,PE-g-MAH的接枝效率(y)与DCP含量(x1)或MAH含量(x2)之间的关系符合y=28.03x1+1.49或y=0.73x2+10.65的线性关系;当w(DCP)=0.44%、w(MAH)=2%时,PE-g-MAH基HMA的粘接性能相对最好,其剪切强度(6.10 MPa)高于杜邦HMA(4.26 MPa),并且其接枝效率为12.91%。     

粘合衬用热熔胶全细粉的制备及性能研究

采用“溶涨”粉化法对聚酰胺热熔胶进行制粉 ,通过优化粉化条件 ,制得细粉 (通过 2 0 0目 )达 90 %以上。同深冷粉碎法相比 ,细粉收率高 ,胶粉的应用性能与其相当     

Miscibility and adhesive properties of ethylene vinyl acetate copolymer (EVA)‐based hot‐melt adhesives. I. Adhesive tensile strength

A series of ethylene vinyl acetate copolymers (EVA) were blended with some tackifier resins that are made from wood extracts, and possible relations between their miscibility and properties as hot‐melt adhesives (HMA) were investigated. From our previous report on miscibility of various EVA‐based HMAs, we chose some blends that represent some of typical miscibility types and measured their adhesive tensile strengths. When the blends were miscible at testing temperatures, the temperature at which the maximum value of adhesive tensile strength was recorded tended to move toward higher temperature as tackifier content of blends increased. This result corresponds to the glass transition temperature (T_g) of the blends that became higher as tackifier content of blends increased when blend components were miscible. In terms of HMA performances, we suggest that factors other than miscibility affect absolute values of adhesive tensile strength more directly than miscibility; this idea has to be investigated further in a future study. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 719–725, 2002