复合催化间苯二酚/膨润土改性酚醛树脂胶粘剂研究

以苯酚和甲醛为原料,选取氢氧化钡[Ba(OH)2]/氢氧化钠(NaOH)为复合催化剂,采用两步加入甲醛法合成了中温固化酚醛树脂(PF)胶粘剂;然后以间苯二酚、膨润土为改性剂,探讨了改性剂含量、反应时间等对改性PF胶粘剂性能的影响,并通过对改性PF胶粘剂的黏度、密度、固含量以及胶接强度等测试,比较了改性PF胶粘剂合成条件的影响。研究结果表明:间苯二酚作为改性剂可明显提高胶粘剂的耐水性能;合成的改性PF胶粘剂的储存期超过60 d,但延长反应时间会使PF胶粘剂的储存期缩短;膨润土对PF胶粘剂性能的影响较复杂;间苯二酚与膨润土同时加入时,前者对PF胶粘剂的性能改进起决定作用。     

水溶性中温快速固化酚醛树脂胶粘剂的工艺优化研究

以氢氧化钡[Ba(OH)2]和氢氧化钠(Na OH)作为复合催化剂,采用两步甲醛(F)加入法制备了高邻位羟甲基含量的PF(酚醛树脂)胶粘剂。以Na OH掺量、Ba(OH)2掺量和Ba(OH)2加入时间作为试验因素,PF胶粘剂的黏度、水溶倍数和固化时间作为考核指标,采用正交试验法优选出制备PF胶粘剂的最佳工艺条件。研究结果表明:同时采用Na OH和Ba(OH)2作为催化剂时,Na OH的催化效果优于Ba(OH)2;Na OH掺量是影响PF胶粘剂的黏度、水溶倍数和固化时间的最显著因素,Ba(OH)2加入时间是不显著因素;合成PF胶粘剂的最佳工艺条件是n(Na OH)=0.30 mol、n[Ba(OH)2]=0.03 mol和Ba(OH)2加入时间为40 min。     

耐高温硼改性酚醛树脂的合成及应用

以碳酸钠为催化剂,首先利用苯酚和甲醛水溶液合成水杨醇,水杨醇进一步与硼酸反应生成硼改性PF(酚醛树脂);然后以残炭率为考核指标,采用单因素试验法探讨了催化剂类型、醛酚比、硼酚比和合成水杨醇的反应时间等对硼改性PF性能的影响,并优选出制备硼改性PF的最佳工艺条件。研究结果表明:当合成水杨醇的反应时间为2.0 h、n(苯酚)∶n(甲醛)∶n(硼酸)=1∶(1.7~2.0)∶0.3和以碳酸钠作为催化剂时,硼改性PF的800℃残炭率(65.88%)相对最高,由其制成的异型Si3N4结合SiC材料和捣打料均具有良好的应用性能。     

橡胶籽壳/苯酚液化物酚醛树脂的合成及表征

采用液化技术和树脂化技术,制备了橡胶籽壳/苯酚液化物(简称液化物);然后以此为原料,制备了胶合板用液化物PF(酚醛树脂)胶粘剂,并采用单因素试验法和正交试验法优选出制备液化物PF的最佳工艺条件。研究结果表明:当反应温度为90℃、n(甲醛)∶n(液化物)=2.0∶1.0、反应时间为2.0 h和n(氢氧化钠):n(液化物)=0.7∶1.0时,由液化物PF胶粘剂压制而成的胶合板,其湿态胶接强度(为1.36 MPa)相对最大,并且达到GB/T 9846—2004标准中I类胶合板的指标要求;液化物PF与纯PF的结构基本相似,但前者的固化温度略高于后者、热稳定性低于后者。     

苯酚处理液体木质素改性酚醛树脂胶粘剂的制备及性能表征

在碱性条件下,液体木质素先经苯酚处理后替代部分苯酚对酚醛树脂进行改性,制备得到液体木质素改性酚醛树脂(LPF)胶粘剂。考察了催化剂用量(苯酚处理木质素时氢氧化钠用量)、苯酚与甲醛(P/F)的物质的量之比、聚合温度、聚合时间对LPF胶粘剂性能的影响。研究结果表明:当催化剂用量3%、n(苯酚)∶n(甲醛)=1∶1.975、聚合温度90℃、聚合时间50 min时,所制备的LPF胶粘剂的干湿胶合强度分别为3.15、1.46 MPa,较未经改性的PF胶粘剂分别提高了17.5%、8.1%,游离苯酚的含量降低至0.62%;LPF胶粘剂的游离甲醛含量为0.22%,固体含量为52.8%,黏度为125 mPa·s。红外分析结果表明,苯酚处理后的木质素可以代替苯酚与甲醛发生反应生成新的物质,该物质有可能与PF胶粘剂发生接枝共聚产生新的醚键桥接,由此也说明在制备LPF胶粘剂过程中木质素发生了化学反应。     

果糖三聚氰胺树脂胶粘剂的合成

以果糖代替甲醛,在酸性条件下合成了类似于脲醛树脂的绿色环保型果糖三聚氰胺树脂胶粘剂,通过正交实验获得了该树脂合成的最佳反应条件:n(果糖)∶n(三聚氰胺)=8∶1,催化剂用量2.0%,反应温度105℃,反应时间5 h。该树脂以邻苯二甲酸酐作固化剂的最佳固化条件为:固化剂用量8%,固化温度120℃,固化时间2 h。     

高替代率竹焦油酚醛树脂的合成工艺研究

竹焦油是竹炭产业的副产物之一,富含酚类物质,可部分替代昂贵苯酚合成竹焦油酚醛树脂(BPF)。以n(苯酚)/n(甲醛)、竹焦油替代率、n(NaOH)/n(苯酚)和反应时间为试验因素,以BPF的黏度和游离酚含量、相应胶合板的胶接强度和甲醛释放量为考核指标,采用正交试验法优选合成高替代率环保型BPF的最佳工艺条件。结果表明:当n(苯酚)/n(甲醛)=2.0、竹焦油替代率为50%、n(NaOH)/n(苯酚)=0.35和反应时间为60 min时,由BPF胶粘剂压制而成的胶合板,其胶接强度和甲醛释放量分别达到GB/T 9846.3—2004标准中Ⅰ类胶合板和E0级的指标要求。     

高温岩棉用水溶性钼酚醛树脂胶的研制

以Ba(OH)2为催化剂,合成了水溶性钼酚醛树脂Mo PF,研究了原料(苯酚、甲醛、钼酸铵和Ba(OH)2)配比、反应温度和时间对合成的影响,并用红外光谱、热重分析和差热分析对所粘接岩棉的结构和耐热性进行考察。结果表明,当m甲醛∶m苯酚∶m钼酸铵=3∶1∶0.54,60℃恒温反应1 h后升温至70℃,并于70℃恒温反应2 h,Mo PF所粘接岩棉的耐热性与纯酚醛树脂(PF)相比有明显提高。初始分解温度为450℃,比PF-岩棉提高190℃;885℃时失重8%,比PF-岩棉减少22%;红外光谱表明,钼元素以钼氧键的形式引入到PF结构中。     

高温岩棉用水溶性钼酚醛树脂胶的研制

以Ba(OH)2为催化剂,合成了水溶性钼酚醛树脂Mo PF,研究了原料(苯酚、甲醛、钼酸铵和Ba(OH)2)配比、反应温度和时间对合成的影响,并用红外光谱、热重分析和差热分析对所粘接岩棉的结构和耐热性进行考察。结果表明,当m甲醛∶m苯酚∶m钼酸铵=3∶1∶0.54,60℃恒温反应1 h后升温至70℃,并于70℃恒温反应2 h,Mo PF所粘接岩棉的耐热性与纯酚醛树脂(PF)相比有明显提高。初始分解温度为450℃,比PF-岩棉提高190℃;885℃时失重8%,比PF-岩棉减少22%;红外光谱表明,钼元素以钼氧键的形式引入到PF结构中。     

间苯二酚氨解法合成间氨基苯酚工艺研究

利用间苯二酚在高温、高压下,以四水合七钼酸铵为催化剂,氨水(25%)作为氨解剂,一步氨解法合成间氨基苯酚。使用HPLC进行产率测定,工艺条件优化实验表明,在2MPa压力下,反应物配比n(间苯二酚)∶n(氨气)=1∶5,催化剂用量n(四水合七钼酸铵)∶n(间苯二酚)=1∶2.5、温度220℃、反应时间6小时,此时间氨基苯酚产率91.12%,并对催化剂套用次数进行研究,表明该催化剂可以循环使用。     

氯丁橡胶与金属热硫化型胶膜的研究

采用机械共混法和胶料成膜技术制备出一种酚醛树脂(PF)-橡胶型膜状胶粘剂(胶膜)。结果表明:当n(37%甲醛)∶n(苯酚)∶n(氢氧化钠)=1.8∶1∶0.1、反应温度为70℃和反应时间为2.5 h时,合成的甲阶PF具有较高的羟甲基含量(28.3%),满足PF-橡胶型胶膜的制备要求;当m(氯丁橡胶)∶m(氯化天然橡胶)∶m(PF)∶m(炭黑)=100∶(5～10)∶(70～80)∶40、m(PF)∶m(硼酚醛树脂)=4∶1时,胶膜的剪切强度超过5.0 MPa、180°剥离强度超过4.0 kN/m且胶接件的破坏形式多为橡胶内聚破坏;该胶膜具有较好的热稳定性(热失重温度为300℃左右),满足氯化橡胶生胶片与金属之间的热硫化胶接要求;该胶膜与适宜底胶配合而成的双涂型胶接体系,可实现氯化橡胶生胶片与树脂基复合材料之间的热硫化胶接。     

The curing behavior of resol. III. Effect of alkali metal hydroxides and alkaline earth metal hydroxides as catalyst for the cure of resol

The effect of the addition of cure catalysts on the cure acceleration of ammonia free resol was investigated by means of Curelastometer. The resol which was prepared by the reaction between phenol and formaldehyde with molar ratio 1:1.2 in the presence of NaOH (0.02 mol to phenol) was neutralized with HCI. Catalyst selected from LiOH, NaOH, KOH, Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, and Ba(OH)₂ was added to the resol, and curing behavior of the resol was examined. Both alkali metal hydroxides and alkaline earth metal hydroxides accelerate the curing of resol. The cure acceleration effect of barium hydroxide is the largest. In the relation between the kinds of catalysts and the cure acceleration effect, the larger the ion radius of catalyst the faster the cure of resol. Cure speed of the resol containing either sodium hydroxide or barium hydroxide as a curing catalyst increases with an increase in the amount of catalyst. Apparent activation energies of curing behavior of the resols containing the cure catalysts were in the range 17.0–21.3 kcal/mol.     

Phenol–formaldehyde wood adhesive characterization by proton magnetic resonance spectroscopy

Acetylation of phenol–formaldehyde (PF) wood adhesives afforded derivatives which could be characterized by proton magnetic resonance (PMR) spectroscopy. Through use of the chemical shift and integral parameters, relative comparisons were made for the degree of polymerization of resins prepared with different molar ratios. Additionally, PMR studies of these acetylated derivatives provided a means of determining methylol content and number of aromatic protons remaining, and to some extent gave an estimate of molar formaldehyde-to-phenol ratio. Experiments conducted with Ca(OH)₂ and NaOH as catalysts showed the latter to be the more effective catalyst for PF systems.     

Eucalyptus bark lignin substituted phenol formaldehyde adhesives: A study on optimization of reaction parameters and characterization

The major adhesive resin worldwide used in the manufacture of plywood is phenol formaldehyde resole (PF) resin. The raw material for this kind of adhesive is derived from petroleum oil. Because of rising prices of crude oil and the scarcity of petroleum products, their replacement by natural resource–based raw material has become a necessity. In the present work, the possibility of replacing phenol in PF resin with lignin was explored. The parameters for preparation of bark lignin substituted PF (LPF) adhesive, such as lignin concentration, formaldehyde to phenol molar ratio, catalyst concentration, reaction time, and reaction temperature, were optimized. It was found that up to 50 wt % of phenol can be substituted by lignin to give an LPF adhesive with better bonding strength compared to that of control PF resin. Prepared resins were characterized using IR, DSC, and TGA. IR spectra of LPF adhesive showed structural similarity with that of PF adhesives. Thermal stability of LPF adhesive was found to be lower compared to that of control PF (CPF) adhesive. DSC studies revealed a lower curing temperature for LPF resin than that for CPF resin. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3514–3523, 2004     

甲醛/苯酚配比对可发性甲阶酚醛树脂性能的影响研究

以苯酚、多聚甲醛、甲醛溶液为原料,NaOH为催化剂,采用逐步共聚的聚合工艺,制备可发性甲阶酚醛树脂,采用环保型发泡剂、匀泡剂、实验室自制复合酸固化剂制备阻燃保温酚醛泡沫材料。研究了甲醛/苯酚配比(物质的量之比即F/P)进行单因素分析,对可发性甲阶酚醛树脂的物理性能、有毒物质残余量、分子结构和活性的影响以及与树脂可发性的关系。结果表明,当F/P=2.0时,可发性甲阶酚醛树脂的粘度为2 680 mPa.s,游离甲醛含量为0.75%,游离苯酚含量为2.3%,羟甲基含量为34.83%,泡沫表观密度为0.050 7 g/cm3。     

低醛三聚氰胺树脂的制备与工艺研究

以三聚氰胺(M)、甲醛(F)和乙二醇(EG)为主要原料,三乙醇胺为催化剂,己内酰胺、H2O2为甲醛吸收剂,采用低n(F)∶n(M)比例、乙二醇醚化MF(三聚氰胺-甲醛)树脂、三聚氰胺分次加料和添加甲醛吸收剂等手段,制备MF树脂。研究结果表明:当n(F)∶n(M)=2.5∶1、n(EG)∶n(M)=2.0∶1、pH值为8～9、反应温度为80℃、三聚氰胺分次加料量为50∶40∶10(质量比)和n(己内酰胺)∶n(H2O2)∶n(甲醛)=10∶5∶100时,制成的MF树脂具有相对较低的游离甲醛含量(0.13%)和相对较长的储存稳定期(>120 d)。     

Development and characterization of a wood adhesive using bagasse lignin

Bagasse is spent fiber left after extraction of sugar. It is mainly used as a fuel to concentrate sugarcane juice. In the present work, the possibility of preparing wood adhesives from bagasse has been explored. The parameters for the preparation of a lignin phenol formaldehyde (LPF) adhesive, (lignin concentration, formaldehyde to phenol molar ratio, catalyst concentration, reaction time and reaction temperature) have been optimized. It was found that up to 50% of phenol can be substituted by bagasse lignin to give LPF wood adhesive having better bonding strength in comparison to a control phenol formaldehyde (CPF) wood adhesive. Prepared resins were characterized using IR, DSC and TGA. IR spectra of LPF resin showed structural similarity with CPF resin. Thermal stability of LPF resin was found to be lower as compared to CPF resin. DSC studies reveal a lower curing temperature for LPF adhesive in comparison to CPF adhesive. A shelf-life study reveals that LPF exhibits consistent behavior as compared to CPF in respect to adhesive strength.     

豆渣苯酚液化物合成热固性酚醛树脂的研究

为了提高大豆豆渣的附加值,利用豆渣苯酚液化物与甲醛在碱性环境中进行反应,制取热固性酚醛树脂(PF)。考察了n(甲醛)/n(液化物)[即n(F)/n(L)]比值、n(氢氧化钠)/n(液化物)[即n(NaOH)/n(L)]比值、树脂化温度和树脂化时间对PF理化性能的影响;通过正交实验法,确定了树脂化合成的最佳工艺。研究结果表明,最佳树脂化合成的工艺条件为:n(F)/n(L)=1.8,n(NaOH)/n(L)=0.5,树脂化温度为72.5℃,树脂化时间为3h;将最佳工艺条件下制取的PF用于胶合板的压制,则所得胶合板的胶合强度符合GB/T9846-2004中Ⅱ类胶合板的标准要求。     

丙二酸二乙酯改性酚醛树脂胶粘剂的制备与性能研究

以甲醛和苯酚为主要原料、丙二酸二乙酯为改性剂,制备碱催化水溶性酚醛树脂(PF)胶粘剂;采用DMA(动态力学分析)法、DSC(差示扫描量热)法、FT-IR(红外光谱)法和TGA(热失重分析)法等对改性PF的性能进行了表征。结果表明:适量改性剂的引入,能有效提高改性PF胶粘剂的韧性,但其固化温度和胶合板的胶接强度下降;当w(改性剂)=0.015%(相对于苯酚质量而言)时,改性体系的固化温度下降了4℃,相应胶合板的胶接强度(>0.80 MPa)仍满足GB/T 9846—2004标准中I类胶合板的指标要求。