竹材液化制备墙体新材料的研究进展

分析我国竹材加工利用现状,介绍浙江省林业科学研究院与南京林业大学合作研发的"小径竹液化发泡制备轻质高强度墙体工程材料技术"的背景及主要技术内容。该技术利用小径竹及竹材加工剩余物,在催化液化及液化产物树脂化、液化树脂制备发泡材料,及液化树脂与其他材料复合等方面,具有突破性技术。     

竹材苯酚液化及胶黏剂制备工艺

采用单因素试验和正交试验研究了竹材加工剩余物的苯酚液化工艺,并进一步研究了竹材苯酚液化产物-甲醛树脂胶黏剂(BPF)的制备工艺和性能。试验结果表明:竹材苯酚液化过程中,液化温度对液化效果的影响最为显著,其次是液比和液化反应时间,催化剂用量2%~4%范围内对液化效果影响不大。竹材加工剩余物苯酚液化的优选工艺为:液固比值3.5、催化剂用量4%、液化温度145℃、液化时间60 min;在此工艺下竹材液化率为99.1%。胶黏剂制备过程中,竹材苯酚液化物与甲醛溶液(甲醛质量分数为37%)的合理质量比为100∶164.8~199.5,其中以100∶182.1较佳。BPF的固化温度低于普通酚醛树脂胶黏剂(PF),因而可在较低温度下固化良好,在130℃或140℃热压温度条件下,用其制备的胶合板的胶合强度均比较理想,热压温度为140℃时的试验结果更佳。     

竹材液化树脂发泡材料的性能与技术要求

根据生产性试验,对竹材液化树脂发泡材料及复合发泡材料的制备工艺进行修正和完善,并对其性能和技术要求进行探讨.分析结果表明:竹材液化树脂发泡材料及复合发泡材料的制备工艺成熟,可实现重复性生产；参考或借鉴相应的国家标准测试方法,可全面测试材料的性能；产品规格尺寸能够满足装配式建筑工程要求.     

竹材液化树脂发泡材料发泡工艺的研究

利用竹材液化产物树脂发泡,制备新型墙体材料。在已进行竹化液化和树脂化优化工艺试验的基础上,通过单因素试验,筛选出发泡剂为正戊烷;再通过正交试验,分析发泡剂、填料和固化剂等用量,对发泡材料表观密度和压缩强度的影响。在试验得出优化工艺的条件下,制得发泡材料的表观密度约0.14g/cm3,压缩强度达454.5kPa。     

竹材在溶剂中的催化液化技术研究进展

比较分析了不同种类液化介质条件下竹材的催化液化特性,包括液化产率、影响因素和液化产物的应用等。其中最常用的液化溶剂为苯酚和醇类,对竹材均具有很好的催化效果,而其他液化溶剂的催化液化工艺的实际应用技术还有待进一步优化。     

林产工业专业文摘

<正>竹材液化树脂发泡材料的性能与技术要求文章根据生产性试验,对竹材液化树脂发泡材料及复合发泡材料的制备工艺进行修正和完善,并对其性能和技术要求进行探讨。分析结果表明:竹材液化树脂发泡材料及复合发泡材料的制备工艺成熟,可实现重复性生产;参考或借鉴相应的国家标准测试方法,可全面测试材料的性能;产品规格尺寸能够满足装配式建筑工程要求。[刘乐群,钱华,王进,等.竹材液化树脂发泡材料的性能与技术要求.木材工业,2012,26(5):9-13.]     

竹材液化树脂发泡材料发泡工艺的研究北大核心

利用竹材液化产物树脂发泡,制备新型墙体材料。在已进行竹化液化和树脂化优化工艺试验的基础上,通过单因素试验,筛选出发泡剂为正戊烷;再通过正交试验,分析发泡剂、填料和固化剂等用量,对发泡材料表观密度和压缩强度的影响。在试验得出优化工艺的条件下,制得发泡材料的表观密度约0.14g/cm3,压缩强度达454.5kPa。     

杉木液化产物制备环保型PF树脂的研究

用硫酸和苯酚将杉木液化,采用傅立叶变换红外光谱和凝胶渗透色谱技术对液化产物进行了分析,并对用液化产物代替苯酚制备PF树脂的工艺进行了探讨。研究结果表明:杉木液化产物中含有大量的具有苯环结构的小分子活性物质,分子量主要分布在800～2 300之2;原料配比、树脂化温度、升温方式和残渣率等因素对PF树脂的质量有明显影响,采用优化工艺制备的PF树脂的游离酚和游离醛的含量分别为0.5%和0.3%,且胶合性能优良。     

竹材苯酚液化物及其甲醛树脂的FT-IR分析

采用傅立叶红外光谱和核磁共振法分析了竹粉在苯酚溶剂作用下酸催化液化产物的化学结构,以及液化物-甲醛树脂胶黏剂的结构特征.分析表明:竹材苯酚液化物的FT-IR图谱在1595.32～1512.70 cm-1处C=O伸缩振动、C=C伸缩振动、芳环骨架振动增强,在 1360.77 cm-1 处面内O-H弯曲振动、1028.62 cm-1 伯醇C-O伸缩振动及手纹区有强吸收峰;1512.70 cm-1处酚类C-O吸收及832.79～691.68 cm-1 处吸收带增强.竹材苯酚液化物-甲醛树脂和普通酚醛树脂的FT-IR图谱非常类似.     

沙柳苯酚液化产物制备酚醛树脂工艺研究

为了开辟沙生灌木利用的新途径,以沙柳苯酚液化产物为对象,进行液化产物树脂化试验,根据拉伸剪切强度的正交试验和单因素试验确定合适的工艺为甲醛与液化产物的摩尔比为1.5,合成温度75℃,氢氧化钠与液化产物的摩尔比为0.5;红外分析表明,液化产物树脂的官能团比酚醛树脂具有更高的反应活性.     

Rapid wood liquefaction by supercritical phenol

Wood was rapidly liquefied at the supercritical temperature of phenol. Under these conditions, wood was liquefied by over 90% for 0.5 min, and the combined phenol content of the obtained liquefied wood reached about 75%. The effects of various reaction conditions on liquefaction were investigated. With increases in reaction temperature, phenol/wood weight ratio, and the charged mass-to-reactor capacity (w/v) ratio, the amount of methanol-insoluble residue decreased and combined phenol content increased. The range of molecular weights and polydispersity of the products obtained after the time at which sufficient liquefaction was achieved were from 400 to 600 and from 1.5 to 2.5, respectively. Wood showed a marked decomposition to low molecular weight components early in the reaction, and then the molecular weight increased slightly with increasing reaction time. The properties of liquefied wood were investigated and compared with those obtained with conventional liquefaction methods. Combined phenol content was similar to that obtained by other liquefaction methods, except the sulfuric acid–catalyzed method, which resulted in flow properties comparable to those of other liquefaction methods. The flexural strength of moldings prepared using liquefied wood was also comparable to those prepared by other liquefaction methods.     

核桃壳苯酚液化及其产物树脂化制备木材胶黏剂的研究

采用硫酸催化剂,考察了苯酚与核桃壳质量比等条件对核桃壳液化的影响。结果表明相同液化条件下,随着苯酚与核桃壳质量比从2∶1升至5∶1,残渣率从26.49%降至6.60%;随着浓硫酸加入量从2%增至4%、反应时间从5 min延至120 min、反应温度从100℃增至150℃,残渣率则分别从20.79%降至10.48%、48.84%降至15.62%、28.86%降至9.39%,游离酚含量分别从17.32%降至12.67%、41.71%降至10.25%、21.94%降至14.33%。同时,液化产物重均相对分子质量(MW)可降至706~1 030、分散度可降至1.04~1.25;液化产物中高相对分子质量部分随着苯酚与核桃壳质量比的增加有所降低,但随着浓硫酸加入量、液化反应时间和温度的增加而有所增加;核桃壳液化产物/苯酚/甲醛共缩聚树脂胶黏剂(WPF)与传统酚醛树脂胶黏剂(PF)的对比表明,WPF的胶接强度可达1.33 MPa,可作为胶合板用胶黏剂。     

Effects of phosphoric acid on liquefaction of wood in phenol and optimum liquefaction processing parameters

To clarify the influencing factors of liquefaction of wood in phenol using phosphoric acid as a catalyst and get its liquefaction technology, a study on the liquefaction technology of Chinese fir (Cunninghamia lanceolata) and poplar (triploid Populus tomentosa Carr) under different conditions was conducted. The results indicate that the residue rate decreases with the increase of liquefaction temperature, liquefaction time, catalyst content or liquid ratio. It is also found that the optimum condition of liquefaction for poplar is estimated as: the reaction temperature of 180 ℃, the reaction time of 2.5 h, liquid ratio (phenol/wood ratio)of 4.5 and catalyst content of 8%, and 4.2% residue rate could be obtained. Under the processing parameters of temperature 180 ℃, the reaction time of 2.5 h, liquid ratio (phenol/wood ratio) of 4 and catalyst content of 10%, the residue rate of Chinese fir can reach 5.6%.     

Technologies of liquefaction of bamboo and preparation of adhesive

The technology of liquefying processed-waste bamboo with phenol is investigated by single factor trials and an orthogonal design. We studied the preparation technology and properties of adhesives from this phenol-liquefied bamboo with formaldehyde (BPF). The results show that temperature has a significant effect on liquefaction. The effect of the mass ratio of phenol to bamboo comes second and the catalyst dosage within the range of 2%–4% is the least effective. The optimum conditions of liquefaction are as follows: a mass ratio of phenol to bamboo 3.5, a catalyst dosage of 4%, liquefying temperature 145°C and liquefying time 60 min. The liquefaction rate of bamboo reached 99.1%. For the preparation of the adhesive, a mass ratio of liquefied bamboo products to formaldehyde (37%) is 100 to 164.8–199.5, while the ratio 100 to 108.2 is the best. This adhesive has a lower curing temperature than that of normal PF resin. At a hot-press temperature of 130 or 140°C, this new adhesive provides excellent bonding strength of plywood. The most favorable temperature for hot-pressing is 140°C. __________ Translated from Chemistry and Industry of Forest Products, 2007, 27(6): 65–70 [译自: 林产化学与工业]     

油茶饼粕的苯酚液化及产物的结构表征

为了综合利用油茶饼粕,分析了油茶饼粕的基本组成,采用苯酚为液化剂,硫酸为催化剂,对油茶饼粕进行了液化实验。结果显示油茶饼粕中糖类、粗纤维和粗蛋白质的总质量分数约为75%,能够有效进行液化。研究了反应温度、苯酚与油茶饼粕的质量比(液比)、催化剂的用量及液化时间对液化反应的影响,实验得出较佳的液化工艺条件为:硫酸用量4%,液化时间1.5 h,液化温度140℃,液比值4,此时液化残渣率16.25%。利用傅里叶红外光谱(FT-IR)分析了油茶饼粕及其液化残渣和产物的结构特征,结果显示苯酚与油茶饼粕组分发生了明显酚化反应和醚化反应,形成了更多的活性官能团。油茶饼粕中蛋白质结构遭到破坏,蛋白质也发生了液化反应。     

思茅松的苯酚液化及树脂化研究

研究了硫酸催化条件下,将恩茅松在苯酚中液化用于制备酚醛树脂的技术工艺,分析了各工艺参数对思茅松液化效率的影响,测定了由液化产物制备的液化木基酚醛树脂的物理化学性质和胶合强度。结论如下：1）．液比、反应温度、时间和木粉目数是影响液化反应效率的重要因素,液化产物的残渣率均随上述工艺参数值的升高而降低。2）．残渣含量对树脂物化性质和胶合强度均有影响,残渣含量降低,树脂粘度减小,聚合时间缩短,游离酚含量降低,胶合强度升高。3）．甲醛／苯酚摩尔比对树脂的物化性质和胶合强度也有影响,甲醛／苯酚摩尔比增加,树脂粘度增加,聚合时间减少,游离酚含量减低,胶合强度升高。     

Liquefaction of bamboo, preparation of liquefied bamboo adhesives, and properties of the adhesives

This study investigated the liquefaction of bamboo in phenol, which involved the effects of weight ratios of phenol to bamboo, amount of catalyst, temperature, etc. The study showed that liquefaction could be accomplished with a phenol to bamboo weight ratio of 2–1: 1, a 5% catalyst of HCl or BF₃, and a temperature of 115°C. Liquefied bamboo formaldehyde (BLF) resin adhesive for exterior use could be obtained with a phenol to formaldehyde molar ratio of 1:1.6–2.0. The curing behavior of BLF resin adhesive, studied by TG-DSC and IR analyses, showed that BLF resin adhesives had a lower curing temperature than PF adhesives but had the same characteristic trough in IR spectra as PF adhesives. __________ Translated from Chemistry and Industry of Forest Products, 2004, 24(3) [译自: 林产化学与工业, 2004, 24(3)]     

落叶松锯屑液化技术的研究

以兴安落叶松锯屑、苯酚为主要原料,以硫酸为主要催化剂,采用均匀设计试验方法和单因子试验法,研究液化温度、液化时间以及硫酸等催化剂的用量对落叶松锯屑液化率的影响。结果表明,酚木比为2.8∶1的前提下,硫酸用量为4%,TSA用量为硫酸的5%,液化温度为135℃,液化时间为120 min时,兴安落叶松锯屑的液化率为95.60%,且液化物中游离酚含量为39.88%,可被溴化物含量为49.33%。     

油茶饼粕苯酚液化物的树脂化研究

以油茶饼粕苯酚液化物为原料制备酚醛树脂,测定树脂的理化性能,评价树脂的胶合性能.考察了甲醛与苯酚的摩尔比(F/P)、氢氧化钠与苯酚的摩尔比(NaOH/P)和树脂化时间对树脂理化性能和胶合性能的影响.结果显示,在F/P 1.8、NaOH/P 0.6、树脂化时间70 min的条件下合成的酚醛树脂压制的胶合板能满足Ⅰ类胶合板强度要求.FTIR分析显示液化物树脂具有常规酚醛树脂典型的官能团特征,树脂中含有较多的羟甲基等活性官能团.     

杉木粉液化与液化产物树脂化的研究

以硫酸为催化剂、苯酚为液化剂采用溶剂热法对杉木粉进行液化,用杉木粉液化产物制备出酚醛树脂;考察了反应温度、反应时间、液比(苯酚-木粉的质量比)和催化剂用量对杉木粉液化效率的影响,并初步探讨了液化产物残渣率对所制酚醛树脂性能的影响。实验结果表明,杉木粉液化的最佳工艺条件是:反应温度160℃,液化时间12 h,液比值3,催化剂用量3%,在此条件下残渣率约为10%。液化产物残渣率的测定表明,升高反应温度、延长反应时间、增加液比和催化剂用量可以降低残渣率,提高液化效率;液比值为0.5~1.5时残渣率随液比增加而显著降低,催化剂用量为0.5%~2%时液化效率的变化明显。红外光谱结果表明,由液化产物所合成的酚醛树脂中羟甲基含量较高。液化产物残渣率低时制备的酚醛树脂残碳率较高。