Synthesis and characterization of waterborne polyurethane dispersion from glycolyzed products of waste polyethylene terephthalate used as soft and hard segment

Waste polyethylene terephthalate (PET) bottles were collected, cleaned and then depolymerized by glycolysis with neopentyl glycol (NPG) and dipropylene glycol (DPG), in the presence of N-butyl titanate catalyst. The product, named glycolyzed oligoesters, obtained through the depolymerization, were employed respectively in hard segment and soft segment in the synthesis of novel waterborne polyurethane dispersions (PUDs) via a simple and environmentally benign process. In addition, a polyurethane dispersion without glycolyzed oligoesters was synthesized as a comparison. The bulk structure of PET glycolyzed oligoesters and PUDs films were characterized by Fourier transform infrared spectroscopy (FT-IR), H-nuclear magnetic resonance (¹H NMR) and Gel permeation chromatography (GPC). The results illustrated that glycolyzed oligoesters were successfully introduced into the hard and soft segment of the polyurethanes. Furthermore, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to investigate the thermal properties of the PET glycolyzed oligoesters and PUDs films. The results showed that the thermal resistance of waterborne polyurethanes obtained with glycolyzed oligoesters increased due to lower degrees of phase separation. X-ray diffraction indicated that all synthesized polyurethanes exhibited reduced degrees of orientation. Due to the balance between hard-/soft-segment of the waterborne polyurethane dispersions, the formulations containing glycolyzed oligoesters within the hard segment sections of the polyurethanes provided the best performance.     

Waterborne polyurethane-silica nanocomposite adhesives based on castor oil-recycled polyols: Effects of (3-aminopropyl)triethoxysilane (APTES) content on properties

Waterborne castor oil-recycled polyol based polyurethane-silica nanocomposite adhesives (WPU) with polymer matrix and silica nanoparticles chemically bonded have been successfully prepared through a sol-gel process. A series of waterborne polyurethane adhesives with hard segment contents from 71.3 to 74.5 wt%, were synthesized using an isophorone diisocyanate, 2-bis(hydroxymethyl) propionic acid, recycled castor oil-based as soft segments and (3-aminopropyl)triethoxysilane (APTES) as chain extender. The depolymerized oligoester obtained from glycolysis of poly(ethylene terephthalate) (PET) waste using triethylene glycol (TEG), was transesterified with castor oil (CO) which resulted in the formation of hydroxyl-functional polyester polyol, with hydroxyl value of 414 mgKOH g⁻¹. The molecular structures and mass of glycolyzed PET oligoesters, castor oil-based polyol and castor oil-based polyurethane-silica nanocomposite adhesives were estimated by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The structure and properties of the resulting films were investigated by FTIR, wide angle X-ray diffraction measurement (XRD), thermogravimetry (TG) and differential scanning calorimetry (DSC). TG analysis indicated that APTES can improve the thermal stability of WPU. XRD showed that the crystallinity of WPU decreased with the increase alkoxysilane content. The extent of crosslinking was investigated to show a dependence on silica concentration, which increased the glass transition temperature and particle size of polyurethane nanocomposites with increasing alkoxysilane content due to the condensation of the alkoxysilane groups. The hardness, adhesion and gloss quality of the polyurethane films were also determined considering the effect of APTES content, so this paper confirmed the suitability of using these castor oil-based waterborne polyurethane-silica nanocomposites as new adhesive materials with high performance coatings materials. The experimental results reveal that the APTES and the hard segment content play a key role in controlling the structure and properties of the PU cast films based on castor oil-recycled polyols.     

The chain extender content and NCO/OH ratio flexibly tune the properties of natural rubber‐based waterborne polyurethanes

The effects of chain extender content (ethylene diamine, EDA) and NCO/OH ratio on the properties of natural rubber‐based waterborne polyurethanes (WPUs) were investigated experimentally. The particle size of WPU increased significantly with the NCO/OH ratio, in the presence of the EDA chain extender, while it was unaffected by the EDA content. The water uptake of WPU film increased with the EDA content, while the swelling in various solvents decreased. In a thermal analysis, the second decomposition stage of a WPU film increased with the EDA content and with the NCO/OH ratio that also positively affected the dynamic mechanical and mechanical properties. These factors in WPU films had no the effect on the T_g. The stress–strain curves clearly showed the change in WPU films from soft elastomeric materials to ductile and hard plastics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42505.     

Preparation and characterization of waterborne polyurethane/silica hybrid dispersions from castor oil polyols obtained by glycolysis poly(ethylene terephthalate) waste

Castor oil polyols (COLs) have been synthesized from glycolyzed oligoester polyol in order to produce waterborne polyurethane (WPU)/silica hybrid dispersions. Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of poly(ethylene glycol) ( PEG 400), in the presence of zinc acetate as catalyst. The obtained glycolyzed products were reacted with castor oil (CO) to attain castor oil polyols by the process of transesterification. Five castor oil polyols were used with hydroxyl values of 255, 275, 326, 366 and 426 mg KOH g⁻¹. Several castor oil-based, polyurethane/silica hybrid dispersions having soft segment content of 39.6% to 28.2% and two concentrations of SiO₂ nanoparticles (0.5 and 1.0) have been prepared.The incorporation effect of SiO₂ nanoparticles into the PU matrix and the hydroxyl functionality of the COLs on the thermal and mechanical properties of resulting polyurethane films has been examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TG) and measurement of the mechanical properties. The degree of phase separation (DPS) between oxide nanoparticles and hard segment, and particle size in the polyurethane, depends to some extent on nanosilica content and the hydroxyl functionality of the polyols employed in the polyurethane preparation process.Thermal stability of obtained hybrid materials depends on the hydroxyl functionality of the COLs and nanosilica content. The T_10% and T_50% (the temperature where 10 and 50% weight loss occurred) of WPU films decreased with the rise of OH functionality of castor oil polyols, caused by the increase of hard segment content. Glass transition temperature increased with increasing OH functionality and SiO₂ content. The hardness, adhesion and gloss quality of the polyurethane films were also determined with a view to assessing the effect of mole ratios of PET to glycol in glycolyzed products, the hydroxyl functionality and the SiO₂ content.     

Recycling of off‐grade pet via partial alcoholysis to synthesize functionalized pet oligomer nanocomposites

Off‐grade poly(ethylene terephthalate) (PET) of industrial manufacturers was partially depolymerized using excess ethylene glycol in the presence of manganese acetate as a transesterification catalyst to synthesize PET oligomers. Influences of reaction time, Ethylene Glycol (EG)/PET molar ratio, catalyst concentrations, and particle size of off‐grade PET on yield of partial glycolysis reaction were investigated based on Box–Behnken's design of experiment. Thermal analyses of glycolyzed products are examined by differential scanning calorimetry. The optimum samples were also well‐characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy (¹H‐NMR and ¹³C‐NMR). The optimal conditions to synthesize PET oligomer (melting point of about 180°C) for a 120‐min glycolysis reaction time were EG/PET molar ratio of 2 with no catalyst using granule‐shaped PET. The same results were obtained for a 60‐min glycolysis reaction time, including EG/PET molar ratio of 1 with the weight ratio (catalyst to PET) of 0.5% using average particle size of PET. Then, maleated PET as a compatibilizer for preparing PET nanocomposites was produced via reaction between maleic anhydride/phthalic anhydride composition and optimized PET oligomers based on central composite design of experiment. The combination of reaction time of 106 min and PhA/MA molar ratio of 0.85 gave the best results based on d‐spacing and peak shift of nanocomposite samples. Hence, melt mixing of maleated PET with organoclay produced a good intercalation of layered silicate and good dispersion of clay in maleated PET matrix. Analysis of variance (ANOVA) was studied for both glycolyzed products and functionalized PET oligomers. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

聚酯-聚醚混合型水性聚氨酯的合成工艺研究

以聚己二酸丁二醇酯二醇（PBAG）和聚乙二醇（PEG）为软链段,以异佛尔酮二异氰酸酯（IPDI）和二羟甲基丙酸（DMPA）为硬链段,采用预聚体法制备了水性聚氨酯（WPU）,研究了R值（NCO／OH摩尔比）、DMPA用量、聚酯与聚醚摩尔比等对乳液的粘度、粒径、稳定性和聚氨酯胶膜力学性能的影响。结果表明,选用尺值为2．0、DMPA质量分数为3．5％、聚酯与聚醚摩尔比为2．5,制备的聚酯-聚醚混合型WPU的粒径可以达到310nm,粘度达到65mPa·s,其离心稳定性和wPU膜力学性能良好。经WPU涂层整理织物的耐静水压达到6．08kPa,透湿量达4550g／（m2×24h）,符合服用性能的要求。     

Thermal and crystalline properties of water‐borne polyurethanes based on IPDI,DMPA, and PEBA/HNA

A series of water‐borne polyurethanes (WPUs) with different soft segments, various COOH contents, and various hard segment contents were prepared through a prepolymerization process. Thermal and crystalline properties of their films were studied by the measurement of differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and thermogravimetry (TG), respectively. Two T_g areas in DSC of WPUs with polyethylene‐butylene adipate glycol (PEBA) as the soft segment were found; an endothermic peak at ～ 33°C was also found with polyhexane neopentyl adipate glycol (HNA) as the soft segment. The DSC of WPUs with the mixture of PEBA/HNA as soft segment was investigated to show similarity to those from HNA, but with a relatively smaller endothermic peak at ～ 34°C. Three sharp diffraction peaks at 2θ = 20.50°, 21.72°, and 24.54° in XRD of water‐borne PUs from HNA were found to indicate the crystallization of soft segments, which was disrupted by the addition of polyacrylate (PA), as evidenced by the amorphous shoulder at ～ 2θ = 20°. TG analysis and differential thermogravimetric (DTG) analysis were measured to indicate that the films lost weight in two stages, and the decomposition temperatures of the films depended on the COOH content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1936–1941, 2007     

Effects of the reagent molar ratio on the phase separation and properties of waterborne polyurethane for application in a water‐based ink binder

Waterborne polyurethane (WPU) dispersions with a high solid content and low viscosity were prepared successfully by a two‐step polymerization with isophorone diisocyanate, poly(propylene glycol), and dimethylol propionic acid as the main raw materials. The molar ratio of hard segments to soft segments was controlled to investigate its influence on the particle size, particle morphology, stability of dispersions, and final properties of the WPU films. Measurements including attenuated total reflectance/Fourier transform infrared spectroscopy, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction, polarizing optical microscopy, and contact angle tests were used to characterize the bulk structures, phase separation, thermal stability, crystallinity, and wettability of the WPU dispersions. The results indicate that all of the WPU dispersions with a high solid content (ca. 40 wt %) and low viscosity (ca. 20–50 mPa s) displayed excellent stability. The prepared WPU dispersions with acetone contents of 5–7 wt % could be used directly as an ink binder without removing the acetone; this is beneficial to industrial applications of water‐based ink binders. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45406.     

水性聚氨酯/聚甲基丙烯酸甲酯杂化乳液的合成

用异佛尔酮二异氰酸酯(IPDI)、聚丙二醇(PPG)和二羟甲丙酸(DMPA)合成了水性聚氨酯分散体(WPU),讨论了PPG摩尔质量,NCO/OH及PPG/DMPA比例对WPU乳液和涂膜性能的影响。以WPU为种子与甲基丙烯酸甲酯进行乳液聚合制备杂化乳液,研究了不同PU/PMMA物质的量比例对杂化乳液及涂膜性能的影响,并采用TEM对WPU及杂化乳液粒子进行了表征。结果表明,在以PPG1000为原料,NCO与OH物质的量比为1.4∶1,PPG与DMPA物质的量比为1∶0.8条件下制备的WPU杂化乳液,随着PMMA比例增加,杂化乳液的稳定性和成膜性变差,聚合物膜断裂伸长率降低,但铅笔硬度、耐水性及耐乙醇性均得到了改善。     

丙烯酸六氟丁酯用量对改性水性聚氨酯性能的影响

采用聚氧化丙烯二醇(PPG2000)、异佛尔酮二异氰酸酯(IPDI)、二羟甲基丙酸(DMPA)、1,4-丁二醇(BDO)、丙烯酸羟乙酯(HEA)和丙烯酸六氟丁酯(FA)为主要原料合成了含氟水性聚氨酯(WPU)。讨论了FA用量对WPU乳液、胶膜及WPU处理后棉织物疏水性能的影响。结果表明,随着FA用量的增加,胶膜的热稳定性能提高,拉伸强度增大,耐水性能提高,棉织物的疏水性能也得到提高。     

Effect of novel aliphatic fluoro-diol content on synthesis and properties of waterborne polyurethanes

This study synthesized a waterborne polyurethane (WPU) prepolymer by using polytetramethylene glycol, isophorone diisocyanate, and 2,2,3,3,4,4,4-Heptafluoro-butynic acid 2,2-bis-hydroxymethyl-butyl ester (HFBA). Subsequently, a series of novel HFBA/WPUs were synthesized by adopting ethylenediamine as the chain extender. The results from Fourier transform infrared spectroscopy demonstrated that the CO groups of HFBA/WPUs shifted to lower wavenumbers as the HFBA content increased. Moreover, when the HFBA content of the synthesized HFBA/WPUs increased, the WPU initial decomposition temperature, glass transition temperature, tensile strength, and Young's modulus also increased. Furthermore, the results of atomic force microscopy identified a relatively high number of humpy protrusions and roughness levels in the HFBA/WPUs with a relatively high HFBA content, causing higher hydrophobicity of these HFBA/WPUs. Furthermore, in vitro platelet and erythrocyte adhesion experiments revealed that increasing the HFBA content lowered platelet and erythrocyte adhesion on the surface of the WPUs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47356.     

Effects of a soft segment component on the physical properties of synthesized waterborne polyurethanes by using triblock ester-ether copolydiol as the soft segment

This paper examines the effect of an ester-ether soft segment structure on the physical properties of synthesized WBPUs. The CET series, CPT series, and CMT series anionic waterborne polyurethane (WBPU) were prepared with PCL-PEG-PCL, PCL-PPG-PCL, and PCL-PTMG-PCL triblock copolydiol as the soft segment. These copolydiols were synthesized from polyethylene glycol (PEG), polypropylene glycol (PPG), or polytetramethylene glycol (PTMG), respectively, by end capping with caprolactone (CL). Particle size and its distribution, solvent absorption, thermal properties, and the mechanical properties of the WBPUs were studied. The particle size of WBPU dispersion was in the sequence of CET > CPT > CMT series. The CET series WBPU had better phase mixing between the soft and hard segment, whereas the CMT series WBPU had good phase separation and better mechanical properties. In addition, both the phase mixing and mechanical properties increased with PCL content, except for the CMT series WBPU.     

软硬段比对磺酸盐型水性聚氨酯性能的影响

以聚己二酸乙二醇酯二醇(PBA)、异佛尔酮二异氰酸酯(IPDI)和六亚甲基二异氰酸酯(HDI)为主要原料,以乙二胺基乙磺酸钠为亲水性扩链剂,合成了固含量为50%的磺酸盐型水性聚氨酯(WPU)乳液。考察了软硬段比对乳液黏度、粒径及其分布、聚合物重均相对分子质量(Mw)、胶膜结晶性以及力学性能等影响。结果表明:当软硬段比值为2.96时,可以制得固含量为50%的磺酸盐型WPU乳液,其平均粒径为146.0 nm、黏度为143 mPa.s,聚合物Mw为128 488,结晶熔融温度为50℃,结晶性相对最好;此时WPU胶膜的拉伸强度(31.6 MPa)和断裂伸长率(1 702%)相对较大;WPU胶粘剂的初始剥离强度(118.6 N/cm)和最终剥离强度(156.3 N/cm)相对最高。     

聚硅氧烷改性水性聚氨酯的合成及其表面性能

以聚氧化丙烯二醇(PPG)、双羟基亲水性聚硅氧烷多元醇(UC3667)为软段,异佛尔酮二异氰酸酯(IPDI)、1,4-丁二醇(BDO)、二羟甲基丙酸(DMPA)、乙二胺(EDA)为硬段,制备了一系列聚硅氧烷改性水性聚氨酯(WPUs)。用DLS和FTIR表征了水性聚氨酯乳液粒径和膜结构。通过热重分析、拉伸测试、接触角测试、XPS对水性聚氨酯胶膜的性能进了测定。结果表明:随着聚硅氧烷加入量的增多,水性聚氨酯膜拉伸强度先增大后减小;且聚硅氧烷的加入提高了水性聚氨酯膜的热稳定性、断裂伸长率、接触角,降低了水性聚氨酯膜的表面能。当聚硅氧烷质量分数为5.0%时,胶膜表面的硅迁移量达到饱和,表面能为27.27 mJ/m~2。     

Glycolyzed products from PET waste and their application in synthesis of polyurethane dispersions

Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of glycol, such as propylene glycol (PG), triethylene glycol (TEG) and poly(ethylene glycol) (PEG 400), in the presence of a zinc acetate catalyst. These glycolyzed products were characterized by hydroxyl value (HV) determinations. The obtained glycolyzed products were reacted with isophorone diisocyanate (IPDI), dimethylol propionic acid (DMPA), as potential ionic center for water dispersibility, and mixed with ethylene diamine (EDA) as extender chain to prepare polyurethane dispersions. The PET glycolyzed products and polyurethane formation were characterized using Fourier transform infrared spectroscopy (FTIR). The molecular masses distribution of oligoester polyol and polyurethane dispersions were determined by using gel permeation chromatography (GPC). The effect of different PET/glycol molar ratio, on the physico-mechanical properties, such as hardness, adhesion test and gloss of polyurethane films were investigated. Thermal properties were investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC).     

磺酸盐型水性聚氨酯胶粘剂的研究

以聚己二酸-1,4-丁二醇酯(PBA)和聚丙二醇醚(PPG)为软段、N-(2-氨乙基)-2-氨基乙磺酸钠(AAS-Na)为亲水基团、六亚甲基二异氰酸酯(HDI)和异佛尔酮二异氰酸酯(IPDI)为硬段,采用丙酮法合成了磺酸盐型水性聚氨酯(WPU)分散体(PUDs),并以此作为WPU胶粘剂的基体树脂。结果表明:不同配方的PUDs乳液均具有较低的黏度(1 000 mPa.s)、较小的粒径(200 nm)、较高的固含量(≥50%)和较好的储存稳定性(180 d无沉淀),不同配方的PUDs胶膜均具有良好的耐热性(250℃以下无降解)和耐水性(吸水率4%);当w(PPG)=4%、n(HDI)∶n(IPDI)=9∶1时,PUDs胶粘剂的成品剥离强度达到最大值(13.52 N/mm),此时初期剥离强度也相对较高(2.11 N/mm)。     

Study of the glycolysis of PET by oligoesters

A series of oligoesters was synthesized via the transesterification of dimethyl isophthalate with neopentyl glycol or tetraethylene glycol and the esterification of adipic acid with neopentyl glycol or tetraethylene glycol under diol/diester or diol/diacid molar ratios sufficient to limit molecular weight increasing.These oligoesters were used to depolymerize poly(ethylene terephthalate) (PET) in the presence of zinc acetate to yield new types of glycolysates. The oligoesters and the glycolysates are characterized by ¹H NMR, size exclusion chromatography (SEC), differential scanning calorimetry (DSC), thermogravimetric analyses and matrix assisted laser desorption/ionisation time of flight mass spectrometry (MALDI-TOF MS). These analyses revealed the structure of the different glycolysates.     

Synthesis of self‐matting waterborne polyurethane coatings with excellent transmittance

The effect of structural factors, including the type of diisocyanates and glycols, degree of crosslinking, hard‐segment content, crystallinity and hydrophilic group content, on optical properties of waterborne polyurethane (WPU) was investigated. Based on the relationship between structure and properties, a series of self‐matting WPUs with excellent transmittance were synthesized. Results demonstrated that refractive index of constituent groups was an important factor to influence the optical properties of coatings. For multiphase polyurethane, aromatic ring, ester bond, ? NH? COO? and urea groups with high refractive index could decrease the matting effect and transmittance. Higher hard‐segment content resulting in an increase of the number of ? NH? COO? or urea bonds also decreased the matting effect and transmittance. The aggregation structure of WPU was another factor to influence the optical properties of coatings. Crystalline soft and hard segment domains could decrease the transmittance and matting effect, whilst non‐crystalline segments, pendent groups and crosslinking destroyed the regularity or crystallinity of macromolecules, behaving as an auxiliary function to improve the transmittance. The particle size of WPU was of great importance for the matting effect. Smaller particle size (<5.0 µm) would endow the coating with a smoother surface and higher reflected light ratio, and thus the expected matting effect was hard to be achieved. A larger particle size could improve the matting effect but impart to the coating a coarse surface and hand‐feel. When the 2,2‐bis(hydroxymethyl)propionic acid content was 1.6 wt%, spherical particles with a size distribution of 7–8 µm were aggregated on the coating surface, giving the coating an excellent matting effect and hand‐feel. © 2017 Society of Chemical Industry     

HDI/IPDI对水性聚氨酯及胶膜性能的影响

采用预聚体分散法制备了一系列固含量为50%的水性聚氨酯(WPU),并通过傅里叶红外光谱(FT-IR)、粒径分析仪、X射线衍射(XRD)、差示扫描量热分析(DSC)、拉力试验机等仪器进行表征,研究了HDI/IPDI摩尔比对WPU的乳液性能和胶膜结晶性能、力学性能、耐水性能,以及基材EVA/PVC粘接性能的影响,分析了不同摩尔比的HDI/IPDI和粘接时间与WPU胶黏剂对EVA/PVC粘接性能的关系。研究发现,随着HDI/IPDI摩尔比增加,水性聚氨酯的乳液性能、软硬段的结晶性都得到提高,而胶膜拉伸强度呈先增大后减小的趋势,断裂伸长率则先减小后增大。所有WPU胶膜都有很好耐水性,胶膜吸水率都在5.0%（质量）以下。粘接实验结果表明,WPU胶黏剂对EVA/PVC具有优异的粘接性能,24 h后可对基材产生界面破坏,随着HDI/IPDI摩尔比增加,胶黏剂的粘接强度增大。当HDI/IPDI=7∶1时,水性聚氨酯的综合性能最好。     

The physical properties of nonionic waterborne polyurethane with a polyether as side chain

A series of nonionic waterborne polyurethanes (WPU) based on hydrogenated methylene diphenylene diisocyanate, polybutylene succinate diol, polybutylene adipate diol, polyethylene glycol, and diethylene glycol as chain extender were synthesized with a polyether, MPEG‐(OH)₂, as side chain. The physical properties such as tensile strength, elongation, hardness, molecular weight, kinetic viscosity, and so on were detected. The WPUs made with polyesters have the best tensile strength but the lowest elongation. Because of the hydrophilic property of MPEG‐(OH)₂ grafted on the WPUs, they have obvious increases of solid contents and water absorptions with the ratio of MPEG‐(OH)₂. The functional group ratio of NCO/OH is another reason affecting the hydrophilic properties of the WPUs. In addition, the water ratios of the dispersions dramatically affect the stability of WPU systems. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013