DSC法研究乙二醛-尿素树脂的固化性能

为从源头上降低UF树脂及其胶合板材的甲醛释放对环境和人体健康所造成的危害,选用乙二醛(G)取代甲醛(F)与尿素(U)反应,制备乙二醛-尿素(GU)树脂。用差示扫描量热分析(DSC)方法研究了原料物质的量比、反应pH、反应时间、反应温度、pH调节剂对所合成GU树脂固化性能的影响规律;并用不同原料物质的量比的GU树脂制备刨花板并测定了其各项性能。结果表明,GU树脂的较优合成条件为:在弱酸性条件下,乙二醛与尿素物质的量比(G/U)=1.2∶0～1.4∶1.0,反应温度70～80℃,反应时间3h;此条件下合成的GU树脂胶合的刨花板内结合强度IB达到0.44MPa、弹性模量MOE达2298MPa、静曲强度MOR为10.5 MPa,且无甲醛释放。     

二羟甲基脲制备的GUF树脂胶黏剂的结构与性能

为从源头上降低木材胶黏剂中的甲醛含量,减小胶合板释放的甲醛对环境和人体造成的危害,采用无毒的乙二醛(G)取代甲醛,与二羟甲基脲(DMU)反应,合成乙二醛-尿素-甲醛(GUF)共缩聚树脂。通过红外光谱(FT-IR)对树脂的结构机理进行了表征,并测定树脂的理化性能,以探讨一种优化GUF胶黏剂的合成工艺。结果表明,原料物质的量比对树脂的固含量和黏度均有较大影响,高n(DMU)/n(G)会导致树脂的黏度大幅提高;树脂对杨木单板具有良好的润湿性,不同GUF树脂胶合板的干状胶合强度和冷水浸泡24 h后的强度均大于0.70 MPa,但胶合板会释放一定量的甲醛,且甲醛释放量会随着n(DMU)/n(G)的增加而增加。综合考虑,n(DMU)/n(G)在1～1.2的范围比较合适。     

乙二醛-尿素树脂的合成、结构与性能研究

选用无毒、低挥发的乙二醛替代甲醛与尿素合成了乙二醛-尿素(GU)树脂,并对GU树脂的结构进行了表征;在此基础上,对GU树脂应用于刨花板的性能进行了研究。结果表明:GU树脂中含有共轭结构、大量胺基(—NH)和羟基(—OH)活性基团、不同取代结构的—CHOH和羰基(C=O),并不存在亚甲基(—CH2—)结构;GU树脂的相对分子质量分布较宽,并且主要以加成产物和低聚物为主;GU树脂与聚二苯基甲烷二异氰酸酯(PMDI)混合且当m(PMDI)∶m(GU)=5∶95时,制备的刨花板满足GB/T 4897.2—2003标准要求。     

有机硅改性苯酚-尿素-甲醛共缩聚树脂及其机理

采用有机硅对苯酚-尿素-甲醛共缩聚树脂进行改性,研究了有机硅的加入方式对树脂改性效果的影响,通过FT-IR对有机硅和有机硅改性PUF共聚树脂的结构进行了分析,结果表明:有机硅的加入,引起苯环的邻位、对位的亚甲基相对含量变化,形成更多的羟甲基、醚键(C—O—C和C—O—Si)。胶合强度实验表明:缩聚阶段加入树脂总质量0.3%的有机硅,可以大幅度提高树脂胶合强度。     

苯酚-尿素-甲醛三元共缩聚树脂合成工艺的研究

针对脲醛树脂在制板过程以及人造板材在使用过程中不断释放甲醛。危害人体健康的环保问题,以及耐水、耐老化性能差的缺点。以苯酚、尿素和甲醛为原料,采用高温（90℃）缩聚反应合成苯酚-尿素-甲醛共缩聚树脂（PUF胶黏剂）,缩短了反应时间,提高了耐水、耐老化性能,且游离甲醛含量〈O．3％,游离苯酚含量〈0．5％。对树脂的结构和性能进行全面的分析,得出当甲醛、尿素、苯酚摩尔比为10：8：1时树脂性能最佳,压制的胶合板力学性能好,板材甲醛释放量达到GB18580—2001中E2级水平。     

乙二醛-尿素-甲醛共缩聚树脂的结构与性能研究

以G(乙二醛)取代部分F(甲醛),合成了GUF[乙二醛-U(尿素)-甲醛共缩聚树脂];然后以此作为胶粘剂基体,制备了相应的GUF胶合板。着重探讨了原料配比对GUF黏度和固含量的影响,并对GUF的结构、相对分子质量及其分布进行了表征,同时对GUF胶合板的热压过程、固化性能、力学性能和F释放量等进行了测定。研究结果表明:合成GUF的最佳原料配比是n(G)∶n(U)∶n(F)=0.7∶1.0∶0.7,此时相应GUF胶合板的F释放量和力学性能均满足GB/T 9846.3—2004标准中的指标要求,并且该胶合板可在干燥状态下直接用于室内装修。     

三聚氰胺-尿素-甲醛共缩聚树脂的性能研究

合成了三聚氰胺-尿素-甲醛(MUF)共缩聚树脂,考察了不同施胶量、固化剂用量及木材种类对胶合木性能的影响。结果表明,MUF共缩聚树脂用量为300g/m2,双面施胶,固化剂用量在1~2%时,生产的胶合木性能最优。     

花生壳苯酚液化产物-尿素-甲醛树脂胶黏剂的研究

以花生壳苯酚液化产物为原料,制备花生壳苯酚液化产物-尿素-甲醛（PLPUF）树脂胶黏剂。采用正交试验探讨了制备PLPUF树脂胶黏剂的最优配比,以提高其综合性能,结果表明：第一批尿素（U₁）/第二批尿素（U₂）物质的量比、液化产物（PL）/尿素（U_总）物质的量比以及液化产物和尿素总用量（PL+U_总）与甲醛（F）物质的量比为3：1、1：1.5和1：1是PLPUF树脂胶黏剂制备的最佳配比;此配比下胶合强度达到了0.83 MPa,含固体量为47.11%,游离甲醛的量为0.05%,以酚醛树脂胶黏剂为标准,PLPUF树脂胶黏剂能满足木材工业树脂的使用要求。PLPUF树脂在贮存过程中黏度逐渐上升,贮存5~15 d胶合强度为0.87~1.15 MPa,22 d后胶合强度降低至0.74 MPa,仍可满足使用条件。PLPUF树脂的FT-IR图中出现酰胺C=O和C—N等伸缩振动峰,表明尿素参与反应、改性树脂,而加入固化剂前后树脂的FT-IR吸收峰相同,结合DSC曲线表明固化剂的加入不改变树脂结构,但可以改善PLPUF树脂的固化过程,降低固化温度和固化反应热。     

三聚氰胺改性树脂的研究进展

三聚氰胺改性树脂是 类逐步发展起来的新型胶粘剂，用三聚氰胺改性脲醛树脂和酚醛树脂，可以提高它们的耐水性和其他性能。三聚氰胺改性树脂包括三聚氰胺-尿素-甲醛树脂(MUF)、苯酚-三聚氰胺-甲醛树脂(PMF)、苯酚-尿素-三聚氰胺-甲醛树脂(PUMF)、尿素苯酚-三聚氰胺-甲醛树脂(UPMF)等，主要介绍了以上各种树脂的合成机理、制备工艺及其应用的研究进展情况。     

三聚氰胺-乙二醛-甲醛共缩聚树脂合成研究

以三聚氰胺、甲醛和乙二醛为原料,在碱性条件下成功合成了均一透明的三聚氰胺-乙二醛-甲醛共缩聚树脂(MGF),并将MGF胶粘剂用于刨花板的制备。以红外光谱(FT-IR)法、差示扫描量热(DSC)法和核磁共振(13C-NMR)法等为测试手段对MGF的结构和性能进行了表征和测定,并采用正交试验法优选出合成MGF的最佳工艺条件。结果表明:当n(甲醛)∶n(三聚氰胺)∶n(乙二醛)=2.2∶1∶0.4、反应温度为75℃和pH=9.0时,MGF的综合性能相对最好,并且其室温储存期超过30 d。     

Reduction of Formaldehyde Emission from Particleboard by Phenolated Kraft Lignin

The aim of this study was the reduction of formaldehyde emission from particleboard by phenolated Kraft lignin. For this purpose, the lignin was extracted from black liquor and then modified by phenolation. During the urea formaldehyde (UF) resin synthesis different proportions of unmodified and phenolated Kraft lignins (10%, 15%, and 20%) were added at pH = 7 instead of the second urea. Physicochemical properties and structural changes of resins so prepared, as well as the internal bond (IB) strength and formaldehyde emission associated with the panels bonded with them were measured according to standard methods. The Fourier transform infrared (FTIR) analysis of lignin indicated that the content of O–H bonds increased in phenolated lignin while the aliphatic ethers C–O bonds decreased markedly in the modified lignin. Since both synthesis of UF resins and lignin phenolation are carried out under acid conditions, phenolation is an interesting way of modifying lignin for use in wood adhesive. The panels bonded with these resins showed significantly lower formaldehyde emission compared to commercial UF adhesives. The UF resin with 20% phenolated lignin exhibited less formaldehyde release without significant differences in internal bond strength and physicochemical properties compared to an unmodified UF resin. XRD analysis results indicated that addition of phenolated lignin decreased the crystallinity of the hardened UF resins.     

Phenol–formaldehyde‐type resins made from phenol‐liquefied wood for the bonding of particleboard

Liquefaction of southern pine wood in phenol in 30–40 : 70–60 weight ratios resulted in homogeneous liquefied materials, which were directly used to synthesize phenol–formaldehyde (PF)‐type resins. The synthesized resins showed good physical and handling properties: low viscosity, stability for storage and transportation, and resin applicable by a common sprayer. Particleboard panels bonded with the synthesized resins showed promising physical properties and significantly lower formaldehyde emission values than those bonded with the urea–formaldehyde resin control. One deficiency observed for the synthesized resins was lower internal bond values, which might be overcome the use of a hot‐stacking procedure. Overall, the process of wood liquefaction with limited amounts of phenol as a solvent was shown to have the potential of providing practical, low‐cost PF‐type resins with very low formaldehyde emission potentials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Evaluation of block shear properties of selected extreme‐pH structural adhesives by short‐term exposure test

Nine structural adhesives with varying pH were selected to examine the effect of adhesive pH on wood–adhesive bond quality. The adhesives evaluated included four highly alkaline phenol–formaldehyde, one intermediate pH phenol–resorcinol–formaldehyde, two acidic melamine–urea–formaldehyde, and two acidic melamine–formaldehyde resins. Block shear specimens were prepared using Douglas‐fir and black spruce wood. The adhesive performance was evaluated by measuring the shear properties (strength and wood failure) of the specimens tested at the dry and vacuum–pressure–redry (VPD) conditions. Adhesive pH, test condition, and wood species showed significant effects on shear properties. The different adhesives performed differently at the dry and VPD conditions. The high‐pH adhesives (phenol–formaldehyde and phenol–resorcinol–formaldehyde) showed similar high wood failures at both test conditions and performed better than the low‐pH adhesives (melamine–formaldehyde and melamine–urea–formaldehyde), especially after the VPD conditioning. The low‐pH adhesives showed high wood failure at the dry condition, but wood failure decreased significantly after VPD conditioning for both species, indicating that the low‐pH adhesives were less durable than the high‐pH adhesives. High‐pH adhesives did not have a negative impact on the strength of the bonded specimens. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

杉木液化产物用于胶粘剂制备的研究

研究用少量的苯酚液化木材及其产物用于胶粘剂制备的方法,在硫酸催化剂作用下,用苯酚液化杉木木粉,得到木材液化产物.在液化产物中加入适量的甲醛和氢氧化钠溶液制备热固性酚醛树脂.压板测试结果表明,由木材液化产物所得树脂的干状胶合强度令人满意,但经蒸汽循环试验后,湿状胶合强度尚达不到JAS标准的要求,在下阶段工作中,需进一步研究木材液化产物胶粘剂的改性以提高其胶合耐久性.     

无甲醛聚合物胶粘剂的合成与应用研究

将尿素与两种活性化合物在一定条件下进行共缩聚反应,合成了尿素-化合物L-化合物R共缩聚(ULR)初期树脂。通过胶合板制造实验、力学性能测试以及甲醛释放量测试,初步探讨了ULR树脂作为胶粘剂应用于胶合板制造的可能性。结果表明:一定反应条件下,反应时间对ULR树脂的粘度影响不大;面粉添加量对ULR树脂胶接胶合板的胶合强度影响较大;当反应时间为120min、面粉添加量为15%时,ULR树脂胶接胶合板的胶合强度能够满足国家标准(≥0．7MPa),甲醛释放量接近0。因此,ULR树脂作为胶粘剂应用于胶合板制造是可行的。     

淀粉标签胶耐水性的改性研究

木薯淀粉经H2O2氧化后,在糊化过程中以H3PO4为酸催化剂,通过添加甲醛和尿素进行复合改性,由此制备出一种改性氧化淀粉粘合剂;然后将其分别与苯丙乳液(SAE)、脲醛树脂(UF)、改性脲醛树脂(M-UF)和SAE/M-UF进行交联复配制取标签用复合粘合剂,并利用傅里叶红外光谱(FT-IR)技术分析了交联复配过程中基团的变化情况。结果表明:改性氧化淀粉粘合剂的脱标时间为2h;相应的复合粘合剂的脱标时间分别为6、24、48、73h,即均能满足现代标签胶的使用要求;-OH伸缩振动吸收峰在复配过程中有变窄的趋势;反应过程中生成的UF在1550～1650cm-1附近出现了2～3个新的吸收峰,分别对应C-N和-NH-的伸缩振动吸收峰;复配过程中引入的SAE会在1750cm-1附近出现酯基的吸收峰。     

The effect of soda bagasse lignin modified by ionic liquids on properties of the urea–formaldehyde resin as a wood adhesive

The aim of this research was to investigate the influence of lignin modified by ionic liquids on physical and mechanical properties of plywood panels bonded with the urea–formaldehyde (UF) resin. For this purpose, soda bagasse lignin was modified by the 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) ionic liquid and then the various contents of unmodified and modified lignins (10, 15, and 20%) were added at pH=7 instead of second urea during the UF resin synthesis. The physicochemical properties of the prepared resins as well as the water absorption, shear strength, and formaldehyde emission of the plywood panels made with these adhesives were measured according to standard methods. According to Fourier Transform Infrared (FTIR) Spectrometry, by treatment of lignin, the C=O, C–C, and C–H bonds decrease while the content of the C–N bond dramatically increases. Based on the finding of this research, the performance of soda bagasse lignin in UF resins dramatically improves by modification by ILs; as the resins with modified lignin yielded lower formaldehyde emission and water absorption when compared to those made from unmodified lignin and commercial UF adhesives, respectively. The shear strength as well as wood failure percentages are lower for the panels produced with modified lignin than for the panels produced with UF resins alone.     

木焦油改性生物油-酚醛树脂胶粘剂的工艺条件研究

以木焦油作为BOPF(生物油-酚醛树脂)的改性剂,制备BTPF(木焦油改性生物油-酚醛树脂)胶粘剂,并用于胶合板的制备。以木焦油加入量、催化剂(NaOH)含量和反应时间作为试验因素,以胶接强度、黏度和凝胶时间作为评价指标,采用正交试验法优选出制备BTPF胶粘剂的最佳工艺条件。结果表明:当w(木焦油)=15%、w(NaOH)=4%和反应时间为40 min时,BTPF胶粘剂的综合性能相对最好,并且完全满足GB/T 14732-2006标准中的指标要求,相应胶合板的胶接强度(1.54 MPa)和甲醛释放量(0.25 mg/L)达到了GB/T 18580—2001标准中的Eo级指标要求。     

杉木苯酚液化物合成热固型酚醛树脂的研究

以杉木为研究树种,对比不同料液比(木材与苯酚质量比)液化物与甲醛在碱性环境中反应,进行热固酚醛树脂制备试验。考察不同甲醛与苯酚物质的量之比值(r_F/P)、氢氧化钠与苯酚物质的量之比值(r_NaOH/P)和树脂化温度对树脂理化性能的影响。结果表明,采用料液比为1:2的液化物,r_F/P1.8,r_NaOH/P0.7,树脂化温度 80℃ 条件下合成的杉木液化物树脂压制的杨木三层胶合板满足I类胶合板强度要求,各项物理力学性能与常规PF树脂压制的板材相当,板材的甲醛释放量为 0.1 mg/L,远低于GB/T 9846-2004《胶合板》中的E₀级要求。     

新型铸造用酚醛树脂粘结剂的生产工艺

苯酚、苯基苯酚、尿素与甲醛的反应产物进一步与糖醇缩聚生成新型铸造用改性酚醛树脂粘结剂。该粘结剂具有粘结强度高、低氨、低粘度等优点。其工艺技术已应用于工业生产。