脱脂豆粉制木材胶粘剂的改性研究
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摘要
随着世界各国对木材加工产品甲醛释放量限制的日益严格,寻求无醛胶粘剂已成为木材工业的重要研究课题。大豆是可再生资源,易于种植,来源广,成本低,环保性能好,是理想的胶粘剂原料。但传统豆胶不具耐水性,需要进行改性。因此围绕豆胶的改性研究成了国内外木材工业研究的热点。
本论文以脱脂豆粉(DSF)为原料,研究了酸法(酸H)、碱法(碱N)、酸碱联合法(酸H和碱N)、酸盐碱联合法(酸H、盐F和碱N)分别改性豆胶的效果,并研究改性剂加入的反应时间对豆胶耐水胶合强度的影响,用试验得出的最佳改性豆胶探讨压板工艺;以傅里叶红外光谱(FTIR)和X射线光电子能谱(XPS)分析豆胶改性过程中各阶段样品的变化,再用活性物质(三聚氰胺、双氰胺、尿素、丙烯酰胺和三乙醇胺)进一步改性豆胶,研究活性物质对豆胶的改性效果;再用FTIR、XPS、热重(TG)分析活性物质改性豆胶各阶段样品的变化,探索改性豆胶耐水胶合强度增加的机理。
按传统方法制备的豆胶干状胶合强度为1.70MPa。若用GB9846.3-2004“胶合板”中规定的Ⅱ类胶的标准检测,全部开胶,不具有耐水性,为Ⅲ类胶。
用浓度为38%的酸H(38%H)为改性因素,研究了三个水平(5.9%、11.9%、17.8%,相对于DSF质量,下同)的添加量对豆胶耐水胶合强度的影响。结果表明,38%H可以提高改性豆胶的耐水胶合强度,改性效果呈现先上升后下降趋势;当添加量为11.9%时,有最好的耐水胶合强度,为0.48MPa。
浓度为30%的碱N(30%N)作为豆胶的改性剂,研究结果表明,随着30%N用量的提高,改性豆胶耐水胶合强度下降;30%N用量为26.6%时,改性后的豆胶有最好耐水胶合强度,为0.43MPa,略低于38%H改性的效果。不同配比的酸H与碱N联合改性豆胶的结果表明,适当比例的38%H与30%N对改性豆胶的耐水胶合强度起正效应;当38%H和30%N的添加量分别为11.9%和39.9%时,改性后的豆胶耐水胶合强度提高到0.61MPa。
采用L9(34)正交试验对酸盐碱联合改性豆胶(H-F-N-DSF)的效果作研究,结果表明,盐F和碱N对改性后的豆胶耐水胶合强度影响显著;1%和3%用量的盐F改性的豆胶均有较好的耐水胶合强度,但盐F用量为3%时,改性的豆胶成泡沫状,操作性能差;配方中各组份质量比分别为DSF: H2O: 38%H: F: 30%N=100: 400: 11.9: 1: 39.9时,改性豆胶的耐水胶合强度为0.64MPa;当此配方中盐F用量降低为0.01时,改性豆胶的耐水胶合强度提高至0.85MPa,达到GB9846.3-2004“胶合板”中规定的Ⅱ类胶合板的要求,但试件合格率仅为70%。因此,选用各组份质量比为DSF: H2O: 38%H: F: 30%N=100: 400: 11.9: 0.01: 39.9的配方继续作研究。
采用L9(34)正交试验对改性豆胶H-F-N-DSF制作过程中加入改性剂的反应时间进行研究,结果表明,三个阶段的反应时间对改性豆胶H-F-N-DSF耐水胶合强度影响大小为DSF与水混合搅拌时间(A)>盐F与38%H的混合液加入后的反应时间(B)>30%N加入后的反应时间(C),其中B阶段的影响显著;当A、B、C三阶段的反应时间分别为60min、30min、10min时,改性豆胶有最好的耐水胶合强度,为0.89MPa,试件合格率为80%。
采用L9(34)正交试验对改性豆胶H-F-N-DSF进行压板工艺研究,结果表明,压板因素对改性豆胶H-F-N-DSF耐水胶合强度影响大小依次为热压温度>单位压力>热压时间,其中热压温度的影响显著;当热压温度、单位压力、热压时间分别为140℃、1.0MPa、1.25 min·mm-1时,改性豆胶H-F-N-DSF最好的耐水胶合强度为0.91MPa,试件合格率为70%。
对改性豆胶H-F-N-DSF制备过程的各产物进行FTIR分析发现,各样品都存在酰胺I、Ⅱ、Ⅲ谱带特征吸收;酸与金属盐改性会使豆胶中形成大量的-COOH和-NH3+,并在1725 cm-1处出现-COOH的C=O特征吸收峰,1570 cm-1处酰胺谱带Ⅱ吸收峰下降为1537 cm-1;再加入30%N改性,则与基团-COOH产生中和反应,1725 cm-1处的吸收峰消失,与1650.75 cm-1处的吸收峰合并成宽强峰;固化的改性豆胶H-F-N-DSF不存在-NH3+,红外光谱中1570 cm-1酰胺谱带Ⅱ的吸收峰重新出现。
对改性豆胶H-F-N-DSF制备过程的各产物进行XPS分析,显示各样品中C元素的C1s结合能共有五种状态,分别为284.6eV、286.1eV、287.7eV、289.1eV和289.2eV ;N元素的N1s结合能有两种状态,分别为399.8eV、401.11eV ;O元素的O1s结合能有三种状态,分别为532.00eV、532.98eV和533.77eV;从中可以分析出,DSF经酸与金属盐改性后,发生了蛋白质高级结构的破坏及少量酰胺键酸水解和部分羧基的脱羧反应,表面的C、O元素含量与DSF相比有所下降;碱液的加入在终止酰胺键酸水解的同时会导致碱水解的发生,肽链上部分氨基脱除生成氨气逸出,N元素含量下降,O元素含量上升;固化后的改性豆胶有新的酰胺键生成,表面O元素含量迅速下降。
在上述分析的基础上,选用活性物质进一步改性H-F-N-DSF豆胶,旨在提高其稳定性及耐水性。活性物质改性后的结果表明,在试验范围内,采用三聚氰胺、尿素、三乙醇胺改性豆胶,性能不稳定,压制的胶合板耐水胶合强度变化大;采用双氰胺改性豆胶效果好,添加DSF质量4.5%的双氰胺制备的改性豆胶压制的胶合板耐水胶合强度均大于0.8MPa,试件合格率大于80%;最佳双氰胺改性豆胶(H-F-N-S-DSF)的各组份质量比为:DSF: H2O: 38%H: F:双氰胺: 30%N=100: 400: 11.9: 0.01: 4.5: 39.9。
对改性豆胶H-F-N-S-DSF进行红外光谱分析表明,添加双氰胺反应1h后,样品仍存在双氰胺-CN及-C=N特征吸收峰;而固化后的改性豆胶H-F-N-S-DSF在1596.84 cm-1处-NH3+的特征吸收峰消失,说明改性豆胶H-F-N-S-DSF固化过程以新生成的酰胺键发生交联。
对改性豆胶H-F-N-S-DSF进行XPS分析,发现双氰胺加入后N、O的表面含量提高;碱加入后使N元素含量下降,说明碱在终止酸水解的同时会使酰胺键发生碱水解,有氨气生成并逸出。当双氰胺与豆胶中的物质发生反应制成H-F-N-S-DSF改性豆胶后,O的含量降低了,说明双氰胺酸水解生成的伯氨基与亲水性基团-COO-结合形成-COONH3-结构,部分疏水基团转而向外,提高了H-F-N-S-DSF改性豆胶的稳定性;H-F-N-S-DSF固化后O元素的表面含量继续下降,说明在固化过程中,改性豆胶中的活性基团进一步以-COONH3-结构发生缩聚交联。
用热重分析仪TG对DSF、H-F-N-DSF、H-F-N-S-DSF进行分析,发现DSF在76.2℃时失重速率最大,达到1.85%/min,H-N-S-DSF的最大失重速率出现在67.0℃,为2.48%/min,H-F-N-S-DSF的最大失重速率对应的温度最小,为51.7℃,失重速率为3.61%/min;说明改性后的豆胶对水分形成的束缚力(范德华力)减小,蛋白质分子部分疏水基团朝外,耐水性更好;当温度达到130℃时,三个样品具有相同的失重速率,从侧面反应了新生成酰胺键数量H-F-N-S-DSF>H-F-N-DSF,因而H-F-N-S-DSF形成的交联结构更稳定。
经成本估算,改性豆胶H-F-N-S-DSF为1666元/吨,每吨比UF树脂胶高308元,但改性豆胶H-F-N-S-DSF不含游离醛,环保性能好。
本研究最终确定的改性豆胶配方各组份质量比为DSF: H2O: 38%H: F:双氰胺: 30%N=100: 400: 11.9: 0.01: 4.5: 39.9;该胶用于压制胶合板,热压工艺为:热压温度140℃、单位压力1.0MPa、热压时间1.25 min·mm-1;胶合板耐水胶合强度达到GB9846.3-2004“胶合板”中规定的Ⅱ类胶合板的要求(≥0.80MPa),试件合格率≥80%,稳定性好;改性豆胶成本略高于UF树脂胶,但环保性能好,生态效益显著。
With the restrictions of formaldehyde emission in wood processing product more and more stringency on the worldwide, searching for a non-formaldehyde wood adhesive has become an important research topic of timber industry. Soy as an ideal adhesive material has many advantages, such as renewable, easy cultivation, low cost, environmental performance. But traditional soy based adhesives have not water-resistance, need for modification. Therefore, focus on the modification of soy based adhesive has become a research hotspot of timber industry on the worldwide.
In this paper, defatted soy flour (DSF) was used for raw materials, and the effects of the acid (acid H), base (base N), acid-base (H acid and base N) and acid-salt-base (acid H, salt F and base N) on soy based adhesive were investigated at first; secondly, the influences of reagents’reaction time on water-resistant bonding strength of soy based adhesive were researched; third, the optimum formula was used for studied the hot-pressing technology of plywood; then Fourier Infrared Spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used for analysis the products which from preparation of the modified soy based adhesive, and then the effects of active substance (melamine, dicyandiamide, urea, acrylamide and triethanolamine) on water-resistant bonding strength of modified soy based adhesive were studied further; final, the FTIR, XPS and thermal gravimetric (TG) were used for analysis the products which from process of soy based adhesive modified by active substances to researched the mechanism of increasing water-resistant bonding strength .
The dried bonding strength of the plywood which bond with traditional soy based adhesive was 1.70MPa. But all the samples will be delaminated and water-resistant bonding strength was 0MPa, when the plywood test with the request of China National Standard (GB9846.3-2004, plywood typeⅡ). So, the traditional soy based adhesive is the adhesive typeⅢ.
The acid H with 38% concentration (38%H) for the modification factor, the effects of 38%H usage (5.9%, 11.9%, 17.8% relative the mass of DSF, the same below) on water-resistant bonding strength of modified soy based adhesive was studied. The results showed that, 38%H can improve the water-resistant bonding strength of modified soy based adhesive, the results were decrease after rise; the best water-resistant bonding strength was 0.48MPa when the usage of 38%H was 11.9%.
The base N with concentration 30% (30%N) as a modifier of the soy based adhesive, the study showed that the water-resistant bonding strength of soy based adhesive decrease with the usage of 30%N increase; the best water-resistant bonding strength was 0.43MPa, when the usage of 30%N was 26.6%, but the modified effect of 30%N less than 38%H.
The soy based adhesive modified with different ratio acid H and base N, the results show that moderate proportion of 38%H and 30%N have positive correlation on water-resistant bonding strength of modified soy based adhesive; when the usage of 38%H and 30%N were 11.9% and 39.9%, the water-resistant bonding strength of modified soy based adhesive increased to 0.61MPa.
The L9 (34) orthogonal test was used on research soy based adhesive which modified by acid, salt and base (H-F-N-DSF). Results show that the salt F and base N have significant impact on water-resistant bonding strength of modified soy based adhesive; when the usage of salt F was 1% or 3%, the water-resistant bonding strength of modified soy based adhesive were better, but 3% salt F results to modified soy based adhesive form lots of bubble and difficult to operation; the water-resistant bonding strength of modified soy based adhesive reached 0.64MPa, when quality of ingredients were DSF: H2O: 38%H: F: 30%N=100: 400: 11.9: 1: 39.9; when the usage of salt F was 0.01 in this formula, the water-resistant bonding strength of modified soy based adhesive enhanced to 0.85MPa, reached the request of China National Standard (GB9846.3-2004,plywood typeⅡ), but the qualified sample only 70%. Therefore, continue to study the formula (DSF: H2O: 38%H: F: 30%N=100: 400: 11.9: 0.01: 39.9) was need.
The L9 (34) orthogonal test was used for research reaction time of reagents on the production of H-F-N-DSF. Results showed that reagents reaction time on the production of H-F-N-DSF have an affect on the water-resistance bonding strength, and effects as follow: stirring time of DSF mixed with water (stage A)> the reaction time of the mixture salt F and 38%H was added (stage B)> the reaction time after 30%N was added (stage C), among the three-stage, stage B have significant impact; when the reaction time of stage A, stage B and stage C were 60min, 30min and 10min, the best water-resistance bonding strength of H-F-N-DSF was 0.89MPa, and the qualified sample was 80%.
The L9 (34) orthogonal test was used on research hot-pressing technology of H-F-N-DSF. Results showed that hot-pressing technology of H-F-N-DSF have an affect on the water-resistance bonding strength, and effects as follow: hot-pressing temperature> unit pressure> hot-pressing time, among the hot-pressing technology, hot-pressing temperature have significant impact; when hot-pressing temperature, unit pressure and hot-pressing time were 140℃, 1.0MPa and 1.25 min ? mm-1, the best water-resistance bonding strength of H-F-N-DSF was 0.91MPa, and the qualified sample was 70%.
FTIR was used for analysis the products which from preparation of H-F-N-DSF, the analysis showed that amide identity absorption bands I,ⅡandⅢwere existence in all samples; when soy based adhesive was modified by acid and salt will form lots of–COOH and -NH3+, and identity absorption peaks of C=O in -COOH appeared on 1537cm-1, the amide absorption bandsⅡdecreased from 1570cm-1 to 1537cm-1; further modified by adding 30% N, that neutralized with -COOH, the 1725cm-1 absorption peak disappeared, and form width strong peak with 1650.75cm-1 absorption; curing H-F-N-DSF does not exist-NH3+, the amide absorption bandsⅡ(1570 cm-1) reappear.
XPS was used for analysis the products which from preparation of H-F-N-DSF, the analysis showed that the C1s binding energy of elements C have five states, that was 284.6eV, 286.1eV, 287.7eV, 289.1eV and 289.2eV; the N1s binding energy of elements N have two states, that was 399.8eV and 401.11eV; the O1s binding energy of elements O have three states, that was 532.00eV, 532.98eV and 533.77eV; from this, we can analyze, after DSF was modified by the acid and salt, the high-level structure of protein was damaged and a small amount of amido link was hydrolyzed by acid and some decarboxylation happened on the carboxyl, elements C and O of surface decrease compared with the DSF; after adding base, amido bond acid hydrolysis was terminated and the basic hydrolysis occurrence, and part of amino on peptide linkage was removed and escaped as ammonia, and the content of element N decreased, element O increased; after modified soy based adhesive curing, new amido bond formation, the content of surface element O decreased rapidly.
In the above analysis, active substances were used for modified H-F-N-DSF to enhance its stability and water resistance. The results showed that, in the range of the experiment, the water-resistant bonding strength of modified soy based adhesive were instability when melamine, urea and triethanolamine as modifiers; dicyandiamide was a good modifier, the water-resistant bonding strength of H-F-N-DSF which modified by 4.5% dicyandiamide reached 0.80MPa, and the qualified sample was 80%; the optimum formula of H-F-N-DSF modified by dicyandiamide (H-F-N-S-DSF) as follow: DSF: H2O: 38%H: F: Dicyandiamide: 30%N=100: 400: 11.9: 0.01: 4.5: 39.9.
FTIR was used for analysis H-F-N-S-DSF, the analysis showed that characteristic absorption peaks of–C≡N and -C=N in Dicyandiamide still existence, after Dicyandiamide reaction 1 hour; after the H-F-N-S-DSF curing the characteristic absorption peaks of -NH3 + (1596.84 cm-1) disappeared, new amido bond of H-F-N-S-DSF was formed during cure and cross-linking each other.
XPS was used for analysis H-F-N-S-DSF, the analysis found that after the Dicyandiamide was added the surface content of elements N and O improved; the surface content of element N decreased when base was added, which indicated that amido bond acid hydrolysis was terminated and the basic hydrolysis occurrence, and part of amino on peptide linkage was removed and escaped as ammonia. In H-F-N-S-DSF, the surface content of element O reduced, which illustrated that the primary amino groups generated by acid hydrolysis of Dicyandiamide were combined with -COO- and formed of -COONH3- structure, and part of the hydrophobic groups turn out, the stability of raise; after H-F-N-S-DSF curing, the surface content of element O continued to decline, which indicated that the active groups of H-F-N-S-DSF further polycondensation and cross-linking as -COONH3- structure in the curing process.
TG was used for analysis on the DSF, H-F-N-DSF and H-F-N-S-DSF, the analysis found that the maximum weight loss rate of DSF was 1.85%/min at 76.2℃, the largest weight loss rate of H-N-S-DSF was 2.48%/min at 67.0℃, and the largest weight loss rate of H-F-N-S-DSF corresponding to the minimum temperature for the 51.7℃, weight loss rate was 3.61%/min; which indicated that its water binding (van der Waals force) decreases after the soy based adhesives were modified, some hydrophobic group of protein molecules outward, a better water-resistance structure was formed; when the temperature reached 130℃, the three samples have the same weight loss rate, in other side, the number of new generate amide H-F-N-S-DSF> H-F-N-DSF, so, the cross-linked structure of H-F-N-S-DSF was more stable.
By the cost estimates, H-F-N-S-DSF for 1666 yuan/ton, high than UF resin adhesive 308 yuan/ton, but H-F-N-S-DSF did not contain free formaldehyde, have good environmental performance.
The final formula of modified soy based adhesive (mass ratio of ingredients) as follows: DSF: H2O: 38%H: F: Dicyandiamide: 30%N=100: 400: 11.9: 0.01: 4.5: 39.9, and hot-pressing technology are pressing temperature 140℃, unit pressure 1.0MPa, hot-pressing time 1.25min?mm-1; the water-resistant bonding strength of plywood reached the request of China National Standard (GB9846.3-2004,plywood typeⅡ,≥0.80MPa), the qualified samples≥80%, good stability; the cost of modified soy based adhesive is slightly higher than the UF resin adhesive, but it has good environmental performance and ecological benefit significantly.
本论文以脱脂豆粉(DSF)为原料,研究了酸法(酸H)、碱法(碱N)、酸碱联合法(酸H和碱N)、酸盐碱联合法(酸H、盐F和碱N)分别改性豆胶的效果,并研究改性剂加入的反应时间对豆胶耐水胶合强度的影响,用试验得出的最佳改性豆胶探讨压板工艺;以傅里叶红外光谱(FTIR)和X射线光电子能谱(XPS)分析豆胶改性过程中各阶段样品的变化,再用活性物质(三聚氰胺、双氰胺、尿素、丙烯酰胺和三乙醇胺)进一步改性豆胶,研究活性物质对豆胶的改性效果;再用FTIR、XPS、热重(TG)分析活性物质改性豆胶各阶段样品的变化,探索改性豆胶耐水胶合强度增加的机理。
按传统方法制备的豆胶干状胶合强度为1.70MPa。若用GB9846.3-2004“胶合板”中规定的Ⅱ类胶的标准检测,全部开胶,不具有耐水性,为Ⅲ类胶。
用浓度为38%的酸H(38%H)为改性因素,研究了三个水平(5.9%、11.9%、17.8%,相对于DSF质量,下同)的添加量对豆胶耐水胶合强度的影响。结果表明,38%H可以提高改性豆胶的耐水胶合强度,改性效果呈现先上升后下降趋势;当添加量为11.9%时,有最好的耐水胶合强度,为0.48MPa。
浓度为30%的碱N(30%N)作为豆胶的改性剂,研究结果表明,随着30%N用量的提高,改性豆胶耐水胶合强度下降;30%N用量为26.6%时,改性后的豆胶有最好耐水胶合强度,为0.43MPa,略低于38%H改性的效果。不同配比的酸H与碱N联合改性豆胶的结果表明,适当比例的38%H与30%N对改性豆胶的耐水胶合强度起正效应;当38%H和30%N的添加量分别为11.9%和39.9%时,改性后的豆胶耐水胶合强度提高到0.61MPa。
采用L9(34)正交试验对酸盐碱联合改性豆胶(H-F-N-DSF)的效果作研究,结果表明,盐F和碱N对改性后的豆胶耐水胶合强度影响显著;1%和3%用量的盐F改性的豆胶均有较好的耐水胶合强度,但盐F用量为3%时,改性的豆胶成泡沫状,操作性能差;配方中各组份质量比分别为DSF: H2O: 38%H: F: 30%N=100: 400: 11.9: 1: 39.9时,改性豆胶的耐水胶合强度为0.64MPa;当此配方中盐F用量降低为0.01时,改性豆胶的耐水胶合强度提高至0.85MPa,达到GB9846.3-2004“胶合板”中规定的Ⅱ类胶合板的要求,但试件合格率仅为70%。因此,选用各组份质量比为DSF: H2O: 38%H: F: 30%N=100: 400: 11.9: 0.01: 39.9的配方继续作研究。
采用L9(34)正交试验对改性豆胶H-F-N-DSF制作过程中加入改性剂的反应时间进行研究,结果表明,三个阶段的反应时间对改性豆胶H-F-N-DSF耐水胶合强度影响大小为DSF与水混合搅拌时间(A)>盐F与38%H的混合液加入后的反应时间(B)>30%N加入后的反应时间(C),其中B阶段的影响显著;当A、B、C三阶段的反应时间分别为60min、30min、10min时,改性豆胶有最好的耐水胶合强度,为0.89MPa,试件合格率为80%。
采用L9(34)正交试验对改性豆胶H-F-N-DSF进行压板工艺研究,结果表明,压板因素对改性豆胶H-F-N-DSF耐水胶合强度影响大小依次为热压温度>单位压力>热压时间,其中热压温度的影响显著;当热压温度、单位压力、热压时间分别为140℃、1.0MPa、1.25 min·mm-1时,改性豆胶H-F-N-DSF最好的耐水胶合强度为0.91MPa,试件合格率为70%。
对改性豆胶H-F-N-DSF制备过程的各产物进行FTIR分析发现,各样品都存在酰胺I、Ⅱ、Ⅲ谱带特征吸收;酸与金属盐改性会使豆胶中形成大量的-COOH和-NH3+,并在1725 cm-1处出现-COOH的C=O特征吸收峰,1570 cm-1处酰胺谱带Ⅱ吸收峰下降为1537 cm-1;再加入30%N改性,则与基团-COOH产生中和反应,1725 cm-1处的吸收峰消失,与1650.75 cm-1处的吸收峰合并成宽强峰;固化的改性豆胶H-F-N-DSF不存在-NH3+,红外光谱中1570 cm-1酰胺谱带Ⅱ的吸收峰重新出现。
对改性豆胶H-F-N-DSF制备过程的各产物进行XPS分析,显示各样品中C元素的C1s结合能共有五种状态,分别为284.6eV、286.1eV、287.7eV、289.1eV和289.2eV ;N元素的N1s结合能有两种状态,分别为399.8eV、401.11eV ;O元素的O1s结合能有三种状态,分别为532.00eV、532.98eV和533.77eV;从中可以分析出,DSF经酸与金属盐改性后,发生了蛋白质高级结构的破坏及少量酰胺键酸水解和部分羧基的脱羧反应,表面的C、O元素含量与DSF相比有所下降;碱液的加入在终止酰胺键酸水解的同时会导致碱水解的发生,肽链上部分氨基脱除生成氨气逸出,N元素含量下降,O元素含量上升;固化后的改性豆胶有新的酰胺键生成,表面O元素含量迅速下降。
在上述分析的基础上,选用活性物质进一步改性H-F-N-DSF豆胶,旨在提高其稳定性及耐水性。活性物质改性后的结果表明,在试验范围内,采用三聚氰胺、尿素、三乙醇胺改性豆胶,性能不稳定,压制的胶合板耐水胶合强度变化大;采用双氰胺改性豆胶效果好,添加DSF质量4.5%的双氰胺制备的改性豆胶压制的胶合板耐水胶合强度均大于0.8MPa,试件合格率大于80%;最佳双氰胺改性豆胶(H-F-N-S-DSF)的各组份质量比为:DSF: H2O: 38%H: F:双氰胺: 30%N=100: 400: 11.9: 0.01: 4.5: 39.9。
对改性豆胶H-F-N-S-DSF进行红外光谱分析表明,添加双氰胺反应1h后,样品仍存在双氰胺-CN及-C=N特征吸收峰;而固化后的改性豆胶H-F-N-S-DSF在1596.84 cm-1处-NH3+的特征吸收峰消失,说明改性豆胶H-F-N-S-DSF固化过程以新生成的酰胺键发生交联。
对改性豆胶H-F-N-S-DSF进行XPS分析,发现双氰胺加入后N、O的表面含量提高;碱加入后使N元素含量下降,说明碱在终止酸水解的同时会使酰胺键发生碱水解,有氨气生成并逸出。当双氰胺与豆胶中的物质发生反应制成H-F-N-S-DSF改性豆胶后,O的含量降低了,说明双氰胺酸水解生成的伯氨基与亲水性基团-COO-结合形成-COONH3-结构,部分疏水基团转而向外,提高了H-F-N-S-DSF改性豆胶的稳定性;H-F-N-S-DSF固化后O元素的表面含量继续下降,说明在固化过程中,改性豆胶中的活性基团进一步以-COONH3-结构发生缩聚交联。
用热重分析仪TG对DSF、H-F-N-DSF、H-F-N-S-DSF进行分析,发现DSF在76.2℃时失重速率最大,达到1.85%/min,H-N-S-DSF的最大失重速率出现在67.0℃,为2.48%/min,H-F-N-S-DSF的最大失重速率对应的温度最小,为51.7℃,失重速率为3.61%/min;说明改性后的豆胶对水分形成的束缚力(范德华力)减小,蛋白质分子部分疏水基团朝外,耐水性更好;当温度达到130℃时,三个样品具有相同的失重速率,从侧面反应了新生成酰胺键数量H-F-N-S-DSF>H-F-N-DSF,因而H-F-N-S-DSF形成的交联结构更稳定。
经成本估算,改性豆胶H-F-N-S-DSF为1666元/吨,每吨比UF树脂胶高308元,但改性豆胶H-F-N-S-DSF不含游离醛,环保性能好。
本研究最终确定的改性豆胶配方各组份质量比为DSF: H2O: 38%H: F:双氰胺: 30%N=100: 400: 11.9: 0.01: 4.5: 39.9;该胶用于压制胶合板,热压工艺为:热压温度140℃、单位压力1.0MPa、热压时间1.25 min·mm-1;胶合板耐水胶合强度达到GB9846.3-2004“胶合板”中规定的Ⅱ类胶合板的要求(≥0.80MPa),试件合格率≥80%,稳定性好;改性豆胶成本略高于UF树脂胶,但环保性能好,生态效益显著。
With the restrictions of formaldehyde emission in wood processing product more and more stringency on the worldwide, searching for a non-formaldehyde wood adhesive has become an important research topic of timber industry. Soy as an ideal adhesive material has many advantages, such as renewable, easy cultivation, low cost, environmental performance. But traditional soy based adhesives have not water-resistance, need for modification. Therefore, focus on the modification of soy based adhesive has become a research hotspot of timber industry on the worldwide.
In this paper, defatted soy flour (DSF) was used for raw materials, and the effects of the acid (acid H), base (base N), acid-base (H acid and base N) and acid-salt-base (acid H, salt F and base N) on soy based adhesive were investigated at first; secondly, the influences of reagents’reaction time on water-resistant bonding strength of soy based adhesive were researched; third, the optimum formula was used for studied the hot-pressing technology of plywood; then Fourier Infrared Spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were used for analysis the products which from preparation of the modified soy based adhesive, and then the effects of active substance (melamine, dicyandiamide, urea, acrylamide and triethanolamine) on water-resistant bonding strength of modified soy based adhesive were studied further; final, the FTIR, XPS and thermal gravimetric (TG) were used for analysis the products which from process of soy based adhesive modified by active substances to researched the mechanism of increasing water-resistant bonding strength .
The dried bonding strength of the plywood which bond with traditional soy based adhesive was 1.70MPa. But all the samples will be delaminated and water-resistant bonding strength was 0MPa, when the plywood test with the request of China National Standard (GB9846.3-2004, plywood typeⅡ). So, the traditional soy based adhesive is the adhesive typeⅢ.
The acid H with 38% concentration (38%H) for the modification factor, the effects of 38%H usage (5.9%, 11.9%, 17.8% relative the mass of DSF, the same below) on water-resistant bonding strength of modified soy based adhesive was studied. The results showed that, 38%H can improve the water-resistant bonding strength of modified soy based adhesive, the results were decrease after rise; the best water-resistant bonding strength was 0.48MPa when the usage of 38%H was 11.9%.
The base N with concentration 30% (30%N) as a modifier of the soy based adhesive, the study showed that the water-resistant bonding strength of soy based adhesive decrease with the usage of 30%N increase; the best water-resistant bonding strength was 0.43MPa, when the usage of 30%N was 26.6%, but the modified effect of 30%N less than 38%H.
The soy based adhesive modified with different ratio acid H and base N, the results show that moderate proportion of 38%H and 30%N have positive correlation on water-resistant bonding strength of modified soy based adhesive; when the usage of 38%H and 30%N were 11.9% and 39.9%, the water-resistant bonding strength of modified soy based adhesive increased to 0.61MPa.
The L9 (34) orthogonal test was used on research soy based adhesive which modified by acid, salt and base (H-F-N-DSF). Results show that the salt F and base N have significant impact on water-resistant bonding strength of modified soy based adhesive; when the usage of salt F was 1% or 3%, the water-resistant bonding strength of modified soy based adhesive were better, but 3% salt F results to modified soy based adhesive form lots of bubble and difficult to operation; the water-resistant bonding strength of modified soy based adhesive reached 0.64MPa, when quality of ingredients were DSF: H2O: 38%H: F: 30%N=100: 400: 11.9: 1: 39.9; when the usage of salt F was 0.01 in this formula, the water-resistant bonding strength of modified soy based adhesive enhanced to 0.85MPa, reached the request of China National Standard (GB9846.3-2004,plywood typeⅡ), but the qualified sample only 70%. Therefore, continue to study the formula (DSF: H2O: 38%H: F: 30%N=100: 400: 11.9: 0.01: 39.9) was need.
The L9 (34) orthogonal test was used for research reaction time of reagents on the production of H-F-N-DSF. Results showed that reagents reaction time on the production of H-F-N-DSF have an affect on the water-resistance bonding strength, and effects as follow: stirring time of DSF mixed with water (stage A)> the reaction time of the mixture salt F and 38%H was added (stage B)> the reaction time after 30%N was added (stage C), among the three-stage, stage B have significant impact; when the reaction time of stage A, stage B and stage C were 60min, 30min and 10min, the best water-resistance bonding strength of H-F-N-DSF was 0.89MPa, and the qualified sample was 80%.
The L9 (34) orthogonal test was used on research hot-pressing technology of H-F-N-DSF. Results showed that hot-pressing technology of H-F-N-DSF have an affect on the water-resistance bonding strength, and effects as follow: hot-pressing temperature> unit pressure> hot-pressing time, among the hot-pressing technology, hot-pressing temperature have significant impact; when hot-pressing temperature, unit pressure and hot-pressing time were 140℃, 1.0MPa and 1.25 min ? mm-1, the best water-resistance bonding strength of H-F-N-DSF was 0.91MPa, and the qualified sample was 70%.
FTIR was used for analysis the products which from preparation of H-F-N-DSF, the analysis showed that amide identity absorption bands I,ⅡandⅢwere existence in all samples; when soy based adhesive was modified by acid and salt will form lots of–COOH and -NH3+, and identity absorption peaks of C=O in -COOH appeared on 1537cm-1, the amide absorption bandsⅡdecreased from 1570cm-1 to 1537cm-1; further modified by adding 30% N, that neutralized with -COOH, the 1725cm-1 absorption peak disappeared, and form width strong peak with 1650.75cm-1 absorption; curing H-F-N-DSF does not exist-NH3+, the amide absorption bandsⅡ(1570 cm-1) reappear.
XPS was used for analysis the products which from preparation of H-F-N-DSF, the analysis showed that the C1s binding energy of elements C have five states, that was 284.6eV, 286.1eV, 287.7eV, 289.1eV and 289.2eV; the N1s binding energy of elements N have two states, that was 399.8eV and 401.11eV; the O1s binding energy of elements O have three states, that was 532.00eV, 532.98eV and 533.77eV; from this, we can analyze, after DSF was modified by the acid and salt, the high-level structure of protein was damaged and a small amount of amido link was hydrolyzed by acid and some decarboxylation happened on the carboxyl, elements C and O of surface decrease compared with the DSF; after adding base, amido bond acid hydrolysis was terminated and the basic hydrolysis occurrence, and part of amino on peptide linkage was removed and escaped as ammonia, and the content of element N decreased, element O increased; after modified soy based adhesive curing, new amido bond formation, the content of surface element O decreased rapidly.
In the above analysis, active substances were used for modified H-F-N-DSF to enhance its stability and water resistance. The results showed that, in the range of the experiment, the water-resistant bonding strength of modified soy based adhesive were instability when melamine, urea and triethanolamine as modifiers; dicyandiamide was a good modifier, the water-resistant bonding strength of H-F-N-DSF which modified by 4.5% dicyandiamide reached 0.80MPa, and the qualified sample was 80%; the optimum formula of H-F-N-DSF modified by dicyandiamide (H-F-N-S-DSF) as follow: DSF: H2O: 38%H: F: Dicyandiamide: 30%N=100: 400: 11.9: 0.01: 4.5: 39.9.
FTIR was used for analysis H-F-N-S-DSF, the analysis showed that characteristic absorption peaks of–C≡N and -C=N in Dicyandiamide still existence, after Dicyandiamide reaction 1 hour; after the H-F-N-S-DSF curing the characteristic absorption peaks of -NH3 + (1596.84 cm-1) disappeared, new amido bond of H-F-N-S-DSF was formed during cure and cross-linking each other.
XPS was used for analysis H-F-N-S-DSF, the analysis found that after the Dicyandiamide was added the surface content of elements N and O improved; the surface content of element N decreased when base was added, which indicated that amido bond acid hydrolysis was terminated and the basic hydrolysis occurrence, and part of amino on peptide linkage was removed and escaped as ammonia. In H-F-N-S-DSF, the surface content of element O reduced, which illustrated that the primary amino groups generated by acid hydrolysis of Dicyandiamide were combined with -COO- and formed of -COONH3- structure, and part of the hydrophobic groups turn out, the stability of raise; after H-F-N-S-DSF curing, the surface content of element O continued to decline, which indicated that the active groups of H-F-N-S-DSF further polycondensation and cross-linking as -COONH3- structure in the curing process.
TG was used for analysis on the DSF, H-F-N-DSF and H-F-N-S-DSF, the analysis found that the maximum weight loss rate of DSF was 1.85%/min at 76.2℃, the largest weight loss rate of H-N-S-DSF was 2.48%/min at 67.0℃, and the largest weight loss rate of H-F-N-S-DSF corresponding to the minimum temperature for the 51.7℃, weight loss rate was 3.61%/min; which indicated that its water binding (van der Waals force) decreases after the soy based adhesives were modified, some hydrophobic group of protein molecules outward, a better water-resistance structure was formed; when the temperature reached 130℃, the three samples have the same weight loss rate, in other side, the number of new generate amide H-F-N-S-DSF> H-F-N-DSF, so, the cross-linked structure of H-F-N-S-DSF was more stable.
By the cost estimates, H-F-N-S-DSF for 1666 yuan/ton, high than UF resin adhesive 308 yuan/ton, but H-F-N-S-DSF did not contain free formaldehyde, have good environmental performance.
The final formula of modified soy based adhesive (mass ratio of ingredients) as follows: DSF: H2O: 38%H: F: Dicyandiamide: 30%N=100: 400: 11.9: 0.01: 4.5: 39.9, and hot-pressing technology are pressing temperature 140℃, unit pressure 1.0MPa, hot-pressing time 1.25min?mm-1; the water-resistant bonding strength of plywood reached the request of China National Standard (GB9846.3-2004,plywood typeⅡ,≥0.80MPa), the qualified samples≥80%, good stability; the cost of modified soy based adhesive is slightly higher than the UF resin adhesive, but it has good environmental performance and ecological benefit significantly.
引文
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