改性壳聚糖制备胶粘剂及其胶合机理研究
摘要
为了制备无甲醛木材胶粘剂,解决壳聚糖资源大量浪费的问题,探索开发新型无毒、环保、绿色的胶粘剂,本文采用改性壳聚糖的方法,制备了可再生和环保的生物质壳聚糖胶粘剂,并对改性壳聚糖的胶合机理进行了研究。主要内容包括四个部分:第一部分:酸化壳聚糖制备胶粘剂的工艺研究,其中包括单因素试验和工艺优化试验。分析了酸化化工艺参数(壳聚糖浓度、冰醋酸浓度、存放时间等)对酸化壳聚糖胶粘剂粘度及胶合性能的影响,为直接利用壳聚糖资源制备人造板胶粘剂理论提供理论基础和技术参数;第二部分:魔芋葡甘聚糖/壳聚糖共混制备胶粘剂的工艺研究;第三部分:研究了胶合板热压工艺条件(温度、时间、压力、涂胶量等)对魔芋葡甘聚糖/壳聚糖共混胶粘剂性能的影响,探索魔芋葡甘聚糖/壳聚糖共混胶粘剂的合理适用的压板工艺;第四部分:应用傅立叶变换红外光谱(FT-IR)仪、流变仪等仪器检测了酸化壳聚糖和葡甘聚糖/壳聚糖共混后官能团的变化,初步探讨了改性壳聚糖制备胶粘剂的胶合机理。主要结论如下:
(1)通过对酸化壳聚糖制备胶粘剂的工艺参数的考察,得到胶合板的胶合强度随着壳聚糖浓度、存放时间的增加而增大,随着冰醋酸浓度的增加先增大后减小;其中壳聚糖浓度对胶合强的影响最大,其次为冰醋酸浓度和存放时间。酸化壳聚糖制备胶粘剂的工艺为:在壳聚糖浓度3%,冰醋酸溶液浓度2%,存放时间为48h时,板材干强最大;壳聚糖浓度3%,冰醋酸溶液浓度1%,存放时间为24h时,板材湿强最大;最经济的配比为壳聚糖浓度3%,冰醋酸溶液浓度2%,存放时间为24h,其胶合强度能达到国家二类胶合板标准。
(2)通过对魔芋葡甘聚糖/壳聚糖共混制备胶粘剂的工艺进行研究,得到:壳聚糖浓度对胶合板干、湿状胶合强度的影响最大,其次为葡甘聚糖和NaOH的浓度。魔芋葡甘聚糖/壳聚糖共混制备胶粘剂的较优工艺为:壳聚糖浓度1%,葡甘聚糖溶液浓度1.5%,NaOH浓度为1%时,板材干强最大;壳聚糖浓度1%,葡甘聚糖溶液浓度1%,NaOH浓度为2%时,板材湿状胶合强度最大。
(3)通过单因素实验对魔芋葡甘聚糖/壳聚糖共混胶粘剂压制胶合板的热压工艺参数进行研究,得出杨木胶合板的热压温度160℃左右,热压时间10min左右,热压压力1.5MPa;施胶量700～800g/m2。
(4)通过红外光谱分析得出,经不同浓度的冰醋酸处理后N-H伸缩振动(3400～3420cm-1)减弱,峰值减小,1020cm-1附近C-O伸缩振动减弱,可能是由于壳聚糖在稀酸中的缓慢水解有关。
(5)通过流变仪的流变分析得出,壳聚糖溶液表现出剪切变稀,为典型的假塑性流体。在固定应力为50,固定温度为120~150℃条件下,约在800秒左右,胶粘剂固化。在固定时间为10min,并固定应力为50条件下,壳聚糖溶液的固化温度约为120~150℃。
In order to prepare formaldehyde-free wood adhesive, solution to the waste chitosan resources problem,to explore new non-toxic, environmental protection, green adhesives, paper, used of modified chitosan, preparation renewable and environmental friendly biomass adhesive and the bonding principle of modified chitosan were studied. Paper includes four parts: Part I: Preparation of chitosan adhesive acidification process, including the single-factor test and trial process optimization. Analysis of the acidification process parameters (the amount of chitosan, acetic acid consumption, storage time, etc.) on acidification and viscosity of chitosan adhesive Preparation for the use of wood-based panel adhesive chitosan resources to provide the theoretical basis and technical parameters; Part II: konjac glucomannan / chitosan blend adhesive preparation process; Part III: plywood hot conditions (temperature, time, pressure, glue, etc.) on konjac glucomannan / chitosan blend adhesive properties, and explore konjac glucomannan / chitosan blend reasonable application of the adhesive plate technology; Part IV: Application of infrared spectroscopy (FT-IR) instrument, apparatus, etc. rheometer tested Acidification of chitosan and konjac glucomannan / chitosan blend of changes in functional groups after the initial modified chitosan Preparation of the bonding mechanism of adhesive. The main conclusion of the study are as follows:
(1) Preparation of chitosan adhesive acidification process parameters of the study, the bonding strength of plywood can be seen with the chitosan dosage, storage time increases, with the increase in glacial acetic acid to increase the amount of and then decreased; Drawn amount of the number of chitosan glue strong impact on the largest, followed by glacial acetic acid dosage and storage time. Preparation of chitosan adhesives come acidification level of the combination of 3% chitosan concentration, the concentration of 2% glacial acetic acid solution, storage time of 48h, the largest sheet dry strength; chitosan concentration of 3% glacial acetic acid 1% solution concentration, storage time of 24h, the plate's largest wetlands strong; the most economical ratio A3B2C2, the bonding strength at this time be able to meet the state standards for second-class strength of plywood.
(2) By studying the konjac glucomannan / chitosan blend adhesive preparation process, can be seen: the amount of chitosan on the plywood dry and wet bonding strength like the greatest impact, followed by glucomannan and NaOH usage. Be concluded that konjac glucomannan / chitosan blend adhesive preparation level of the combination of the factors of 1% chitosan concentration, the concentration of glucomannan solution 1.5%, NaOH concentration of 1%, the largest sheet dry strength; chitosan concentration of 1% konjac solution concentration 1%, NaOH concentration of 2%, the wet-plate-shaped maximum bonding strength.
(3) Through the single factor experiment on konjac glucomannan / chitosan blend adhesive to suppress the hot-pressing process parameters plywood study poplar plywood reached the temperature of the hot-pressing about 160℃, 10min about pressing time, pressing pressure of 1.5 MPa; sizing the volume of 700 ~ 800g/m2.
(4) Through the infrared spectrum obtained by the different concentrations of acetic acid treated NH stretching vibration (3400 ~ 3420cm-1) reduced the peak decreases, 1020cm-1 near the CO stretching vibration weakened crust may be due to poly of sugar in the acid hydrolysis of the slow.
(5) Through the rheometer Rheological analysis, chitosan solution showed shear-thinning, typical pseudoplastic fluid. At a fixed stress of 50, a fixed temperature of 120 ~ 150℃under the conditions of about 800 seconds or so, adhesive curing. At a fixed time was 10 minutes, and 50 fixed-stress conditions, the curing temperature of chitosan solution is about 120 ~ 150℃.
(1)通过对酸化壳聚糖制备胶粘剂的工艺参数的考察,得到胶合板的胶合强度随着壳聚糖浓度、存放时间的增加而增大,随着冰醋酸浓度的增加先增大后减小;其中壳聚糖浓度对胶合强的影响最大,其次为冰醋酸浓度和存放时间。酸化壳聚糖制备胶粘剂的工艺为:在壳聚糖浓度3%,冰醋酸溶液浓度2%,存放时间为48h时,板材干强最大;壳聚糖浓度3%,冰醋酸溶液浓度1%,存放时间为24h时,板材湿强最大;最经济的配比为壳聚糖浓度3%,冰醋酸溶液浓度2%,存放时间为24h,其胶合强度能达到国家二类胶合板标准。
(2)通过对魔芋葡甘聚糖/壳聚糖共混制备胶粘剂的工艺进行研究,得到:壳聚糖浓度对胶合板干、湿状胶合强度的影响最大,其次为葡甘聚糖和NaOH的浓度。魔芋葡甘聚糖/壳聚糖共混制备胶粘剂的较优工艺为:壳聚糖浓度1%,葡甘聚糖溶液浓度1.5%,NaOH浓度为1%时,板材干强最大;壳聚糖浓度1%,葡甘聚糖溶液浓度1%,NaOH浓度为2%时,板材湿状胶合强度最大。
(3)通过单因素实验对魔芋葡甘聚糖/壳聚糖共混胶粘剂压制胶合板的热压工艺参数进行研究,得出杨木胶合板的热压温度160℃左右,热压时间10min左右,热压压力1.5MPa;施胶量700～800g/m2。
(4)通过红外光谱分析得出,经不同浓度的冰醋酸处理后N-H伸缩振动(3400～3420cm-1)减弱,峰值减小,1020cm-1附近C-O伸缩振动减弱,可能是由于壳聚糖在稀酸中的缓慢水解有关。
(5)通过流变仪的流变分析得出,壳聚糖溶液表现出剪切变稀,为典型的假塑性流体。在固定应力为50,固定温度为120~150℃条件下,约在800秒左右,胶粘剂固化。在固定时间为10min,并固定应力为50条件下,壳聚糖溶液的固化温度约为120~150℃。
In order to prepare formaldehyde-free wood adhesive, solution to the waste chitosan resources problem,to explore new non-toxic, environmental protection, green adhesives, paper, used of modified chitosan, preparation renewable and environmental friendly biomass adhesive and the bonding principle of modified chitosan were studied. Paper includes four parts: Part I: Preparation of chitosan adhesive acidification process, including the single-factor test and trial process optimization. Analysis of the acidification process parameters (the amount of chitosan, acetic acid consumption, storage time, etc.) on acidification and viscosity of chitosan adhesive Preparation for the use of wood-based panel adhesive chitosan resources to provide the theoretical basis and technical parameters; Part II: konjac glucomannan / chitosan blend adhesive preparation process; Part III: plywood hot conditions (temperature, time, pressure, glue, etc.) on konjac glucomannan / chitosan blend adhesive properties, and explore konjac glucomannan / chitosan blend reasonable application of the adhesive plate technology; Part IV: Application of infrared spectroscopy (FT-IR) instrument, apparatus, etc. rheometer tested Acidification of chitosan and konjac glucomannan / chitosan blend of changes in functional groups after the initial modified chitosan Preparation of the bonding mechanism of adhesive. The main conclusion of the study are as follows:
(1) Preparation of chitosan adhesive acidification process parameters of the study, the bonding strength of plywood can be seen with the chitosan dosage, storage time increases, with the increase in glacial acetic acid to increase the amount of and then decreased; Drawn amount of the number of chitosan glue strong impact on the largest, followed by glacial acetic acid dosage and storage time. Preparation of chitosan adhesives come acidification level of the combination of 3% chitosan concentration, the concentration of 2% glacial acetic acid solution, storage time of 48h, the largest sheet dry strength; chitosan concentration of 3% glacial acetic acid 1% solution concentration, storage time of 24h, the plate's largest wetlands strong; the most economical ratio A3B2C2, the bonding strength at this time be able to meet the state standards for second-class strength of plywood.
(2) By studying the konjac glucomannan / chitosan blend adhesive preparation process, can be seen: the amount of chitosan on the plywood dry and wet bonding strength like the greatest impact, followed by glucomannan and NaOH usage. Be concluded that konjac glucomannan / chitosan blend adhesive preparation level of the combination of the factors of 1% chitosan concentration, the concentration of glucomannan solution 1.5%, NaOH concentration of 1%, the largest sheet dry strength; chitosan concentration of 1% konjac solution concentration 1%, NaOH concentration of 2%, the wet-plate-shaped maximum bonding strength.
(3) Through the single factor experiment on konjac glucomannan / chitosan blend adhesive to suppress the hot-pressing process parameters plywood study poplar plywood reached the temperature of the hot-pressing about 160℃, 10min about pressing time, pressing pressure of 1.5 MPa; sizing the volume of 700 ~ 800g/m2.
(4) Through the infrared spectrum obtained by the different concentrations of acetic acid treated NH stretching vibration (3400 ~ 3420cm-1) reduced the peak decreases, 1020cm-1 near the CO stretching vibration weakened crust may be due to poly of sugar in the acid hydrolysis of the slow.
(5) Through the rheometer Rheological analysis, chitosan solution showed shear-thinning, typical pseudoplastic fluid. At a fixed stress of 50, a fixed temperature of 120 ~ 150℃under the conditions of about 800 seconds or so, adhesive curing. At a fixed time was 10 minutes, and 50 fixed-stress conditions, the curing temperature of chitosan solution is about 120 ~ 150℃.
引文
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