CN108165204A - 一种人造板用淀粉粘合剂的制备方法 - Google Patents
一种人造板用淀粉粘合剂的制备方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C09J103/04—Starch derivatives
- C09J103/10—Oxidised starch
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
本发明属于粘合剂制备技术领域,具体说是一种人造板用淀粉粘合剂的制备方法。制备方法步骤包括:(1)木薯淀粉变性:取木薯淀粉加入NaOH充分润湿后采用60Coγ‑射线进行辐照处理后即得到变性淀粉;(2)机械化学法制备变性淀粉复合材料:取经过辐照后的变性淀粉加入到螺杆研磨机,然后加入氧化剂、苯乙烯化醇酸树脂、聚烯烃树脂、乙烯‑醋酸乙烯共聚物、三偏磷酸钠、过硫酸钾、硅藻土、聚乙烯醇、阻燃剂、仲烷基磺酸钠、十六烷基三甲基氯化铵、聚六亚甲基胍、甘草酸二甲、调节研磨参数进行研磨后即得到变性淀粉复合材料;再将制备得到的变性淀粉复合材料加水洗涤,烘干,粉碎,过筛后即得产品。
Description
技术领域
本发明属于粘合剂制备技术领域,具体说是一种人造板用淀粉粘合剂的制备方法。
背景技术
粘合剂是一种能够把同类或者异类的物质粘合在一起的物质。粘合剂具有重量轻、粘结强度高、应力分布均匀等优点,广泛应用于工业、交通、医疗、农业、日常生活等领域。人造板是以木材或其他非木材植物为原料,经一定机械加工分离而成的各种单元材料,施加或不施加胶黏剂和其他添加剂胶合而成的板材或模压制品。人造板能够高效利用枝梗材、小径级材以及木材加工过程中剩余物等,解决木材边角料资源的浪费,减少对林业树木的砍伐,对环境保护有一定的作用。
随着合成高分子材料科学的发展,在木材加工业中出现了以合成高分子材料为基础物质的合成高分子粘合剂。其中种类包括“三醛胶”类:脲醛树脂、酚醛树脂和三聚氰胺甲醛树脂粘合剂。此外,在人造板粘合剂中还包括以淀粉粘合剂、木质素粘合剂、单宁粘合剂等为代表的天然高分子粘合剂。三醛胶类粘合剂在使用过程中会散发出刺激的甲醛气体,长期吸入甲醛气体会对人体健康造成危害,严重的甚至会造成恶性肿瘤。随着人们对健康的重视,人们越来越注重高品质、高质量、功能化、绿色环保的产品。面对激烈的竞争压力,赢得市场,“低毒、环保、安全、健康”的粘合剂才是未来发展的方向。
淀粉粘合剂是一种天然高分子粘合剂,具有使用方便,原料易得、来源广泛、价格低廉、无毒环保、环境友好的优点,将淀粉粘合剂应用到人造板中,能够有效利用资源,降低有害物质对人体健康造成的危害。在淀粉粘合剂应用过程中发现单独使用或者以改性淀粉作为粘合剂制造人造板,会存在着粘合剂粘结性能差,初粘性差,易吸潮霉变等为题,这些因素极大地限制了淀粉粘合剂在人造板中的应用。
发明内容
本发明提供一种人造板用淀粉粘合剂的制备方法,制备得到的淀粉粘合剂粘结性能强、初粘性强、耐水性好、稳定性好,方便运输和储存。
本发明的方案是通过这样实现的:
一种人造板用淀粉粘合剂的制备方法,制备方法步骤包括:
(1)木薯淀粉变性:取木薯淀粉100~150份,加入5%NaOH充分润湿后采用60Coγ-射线进行辐照处理后即得到变性淀粉,设定辐照剂量为12~18KGY,辐照温度为30~50℃,辐照时间为30~60min;
(2)机械化学法制备变性淀粉复合材料:取经过辐照后的变性淀粉加入到螺杆研磨机,然后加入氧化剂20~40份、苯乙烯化醇酸树脂20~30份、聚烯烃树脂60~80份、乙烯-醋酸乙烯共聚物60~80份、三偏磷酸钠15~20份、过硫酸钾18~20份、硅藻土20~30份、聚乙烯醇8~10份、阻燃剂8~10份、仲烷基磺酸钠5~6份、十六烷基三甲基氯化铵6~8份、聚六亚甲基胍8~10份、甘草酸二甲8~12份、调节研磨的功率为1.8~2.4KW,研磨时间为30~90min,即得到变性淀粉复合材料;
(3)将制备得到的变性淀粉复合材料加水洗涤,烘干,粉碎,过筛后即得产品。
作为本发明的进一步改进,所述的氧化剂为次氯酸钠、过氧化氢、高锰酸钾中的一种或者一种以上的组合物。
作为本发明的进一步改进,所述的阻燃剂为甲基磷酸二甲酯、镁铝水滑石、磷酸酯中的一种或一种以上的组合。
本发明实现的技术原理是:首先利用氢氧化钠和60Coγ-射线对木薯淀粉进行变性处理,氢氧化钠可以破坏淀粉分子的氢键作用,减弱淀粉分子间作用,能够使淀粉更容易溶胀糊化,,增强淀粉分子与其他试剂的相互作用,从而使淀粉粘合剂有粘合性能。60Coγ-射线辐照会使淀粉大分子裂解,聚合度下降,粘度降低,糊化时使淀粉颗粒容易溶胀破裂,在氢氧化钠和60Coγ-射线辐协同作用下,能够有效促进淀粉分子的糊化,降低淀粉分子的粘度和初始糊化温度。采用机械化学法对变性淀粉进行复合,采用的机器为螺杆研磨机。螺杆研磨机与球磨机相比,螺杆研磨机对物料产生物料产生轴向分力、径向分力以及研磨腔内壁对物料产生的摩擦阻力,能够使物料与物料以及物料与机器内壁充分产生碰撞、挤压、剪切、摩擦,能够使物料充分接触反应,反应充分。螺杆研磨机直接将机械力通过挤压、剪切作用传递到原料粉体上,大大提高了机械能转换的效率,同时螺杆研磨机的机械力作用较长,粉体处于高能活化的时间大大被延长,有利于反应的进行。
在研磨过程中可以同时发生多种反应。氧化剂可以使变性淀粉中的羟甲基氧化成醛基、羧基,增大变性淀粉的亲和性,从而增强了变性淀粉渗透性和粘结能力以及使变性淀粉性质更稳定,有利于变性淀粉与物料进行反应。加入的三聚磷酸钠可以促进乙烯-醋酸乙烯共聚物与变性淀粉发生酯化反应,能够使粉粘合剂具有较高的抗老化性,有利于淀粉粘合剂的保存。乙烯-醋酸乙烯共聚物能够增强淀粉粘合剂与纸制品的粘结性,在纸层间形成良好成膜以此来提高提高纸层间的粘结强度,提高纸制品的抗冲击性、防水性能,提高纸制品的韧性还能够有效防止纸制品开裂、变型。过硫酸钾可以引发变性淀粉产生更多的自由基活性位点,有利于聚丙烯树脂与变性淀粉发生接枝反应,接枝后直链淀粉含量降低,可以降低淀粉糊化的温度,接枝后聚合物乳液颗粒粒径变小,使用时能够使淀粉粘合剂在纸层间更容易形成膜,增强淀粉粘合剂的强度,减少纸制品掉毛掉粉脱落的现象。乙烯-醋酸乙烯共聚物能够有效提高聚合物在成膜后的柔韧性和延展性,从而增强纸制品的的韧性和强度,使纸制品不易掉毛掉粉。加入的硅藻土可以进入淀粉复合材料的孔隙中,缩短可以使纸制品的强度达到最大值。聚乙烯醇可以促进淀粉粘合剂原料之间的粘合强度。苯乙烯化醇酸树脂与淀粉粘合剂中的原料相互交联可以提高淀粉粘合剂的耐水性。仲烷基磺酸钠、十六烷基三甲基氯化铵可以快速促进淀粉粘合剂渗透进入纸制品中,提高粘合速度;此外十六烷基三甲基氯化铵可以提高纸制品的抗静电能力、抗菌防霉能力。聚六亚甲基胍具有杀菌广谱,使用量少,杀菌效果好,作用速度快的优点,与十六烷基三甲基氯化铵协同作用能够有效提高淀粉粘合剂的贮存稳定性。甘草酸二甲也具有抑菌作用,还能够除去纸制品产生的臭味物质,减少臭味物质给环境和人带来的不良影响。
本发明实现的技术效果:
1.本发明制备得到的淀粉粘合剂粘合强度高,易上胶、稳定性强、不易吸湿返潮,耐贮存;用在人造板中能够提高人造板的性能,不易使人造板变型、能够防霉菌,防水性能好,有效提高人造板的使用寿命,不含游离甲醛,对人体健康好。
2.在制备变性淀粉复合材料的过程中采用一次投料可以发生多种反应使变性淀粉的氧化、酯化和复配等反应一起发生,能够简化工艺步骤,采用螺杆研磨机能够使反应物料充分接触,反应达到充分,有效提高生产效率。
3.本发明的淀粉粘合剂粘度为917.6~943.8mPa.s,pH值为8.5~9.0,游离甲醛含量为0,胶合强度为14.8~16.1MPa,固含量为50.2~52.4%,固化时间为20~25s,耐水时间为85~87h,贮存期为230~241天,本发明制备得到的淀粉粘合剂与同类的产品相比各项性能较优。
具体实施方式
以下结合实施例描述本发明一种人造板用淀粉粘合剂的制备方法,这些描述并不是对本发明内容作进一步的限定。
实施例1
木薯淀粉变性:取木薯淀粉140份,加入5%NaOH充分润湿后采用60Coγ-射线进行辐照处理后即得到变性淀粉,设定辐照剂量为16KGY,辐照温度为35℃,辐照时间为60min;
机械化学法制备变性淀粉复合材料:取经过辐照后的变性淀粉加入到螺杆研磨机,然后加入氧化剂40份、苯乙烯化醇酸树脂30份、聚烯烃树脂75份、乙烯-醋酸乙烯共聚物70份、三偏磷酸钠18份、过硫酸钾20份、硅藻土28份、聚乙烯醇9份、阻燃剂10份、仲烷基磺酸钠6份、十六烷基三甲基氯化铵6.5份、聚六亚甲基胍9.5份、甘草酸二甲10份、调节研磨的功率为2.0KW,研磨时间为45min,即得到变性淀粉复合材料;
将制备得到的变性淀粉复合材料加水洗涤,烘干,粉碎,过筛后即得产品。
实施例2
木薯淀粉变性:取木薯淀粉110份,加入5%NaOH充分润湿后采用60Coγ-射线进行辐照处理后即得到变性淀粉,设定辐照剂量为15KGY,辐照温度为30℃,辐照时间为45min;
机械化学法制备变性淀粉复合材料:取经过辐照后的变性淀粉加入到螺杆研磨机,然后加入氧化剂20份、苯乙烯化醇酸树脂20份、聚烯烃树脂80份、乙烯-醋酸乙烯共聚物65份、三偏磷酸钠15份、过硫酸钾19份、硅藻土30份、聚乙烯醇8~10份、阻燃剂8~10份、仲烷基磺酸钠5份、十六烷基三甲基氯化铵7份、聚六亚甲基胍8份、甘草酸二甲11份、调节研磨的功率为2.4KW,研磨时间为75min,即得到变性淀粉复合材料;
将制备得到的变性淀粉复合材料加水洗涤,烘干,粉碎,过筛后即得产品。
实施例3
木薯淀粉变性:取木薯淀粉100份,加入5%NaOH充分润湿后采用60Coγ-射线进行辐照处理后即得到变性淀粉,设定辐照剂量为12KGY,辐照温度为45℃,辐照时间为52min;
机械化学法制备变性淀粉复合材料:取经过辐照后的变性淀粉加入到螺杆研磨机,然后加入氧化剂35份、苯乙烯化醇酸树脂23份、聚烯烃树脂60份、乙烯-醋酸乙烯共聚物75份、三偏磷酸钠20份、过硫酸钾18份、硅藻土25份、聚乙烯醇8份、阻燃剂9份、仲烷基磺酸钠5份、十六烷基三甲基氯化铵8份、聚六亚甲基胍9份、甘草酸二甲8份、调节研磨的功率为2.1KW,研磨时间为30min,即得到变性淀粉复合材料;
将制备得到的变性淀粉复合材料加水洗涤,烘干,粉碎,过筛后即得产品。
实施例4
木薯淀粉变性:取木薯淀粉130份,加入5%NaOH充分润湿后采用60Coγ-射线进行辐照处理后即得到变性淀粉,设定辐照剂量为13KGY,辐照温度为50℃,辐照时间为30min;
机械化学法制备变性淀粉复合材料:取经过辐照后的变性淀粉加入到螺杆研磨机,然后加入氧化剂25份、苯乙烯化醇酸树脂25份、聚烯烃树脂70份、乙烯-醋酸乙烯共聚物80份、三偏磷酸钠17份、过硫酸钾18.5份、硅藻土20份、聚乙烯醇10份、阻燃剂8.5份、仲烷基磺酸钠5.5份、十六烷基三甲基氯化铵6份、聚六亚甲基胍10份、甘草酸二甲9份、调节研磨的功率为1.8KW,研磨时间为90min,即得到变性淀粉复合材料;
将制备得到的变性淀粉复合材料加水洗涤,烘干,粉碎,过筛后即得产品。
实施例5
木薯淀粉变性:取木薯淀粉150份,加入5%NaOH充分润湿后采用60Coγ-射线进行辐照处理后即得到变性淀粉,设定辐照剂量为18KGY,辐照温度为40℃,辐照时间为37min;
机械化学法制备变性淀粉复合材料:取经过辐照后的变性淀粉加入到螺杆研磨机,然后加入氧化剂30份、苯乙烯化醇酸树脂28份、聚烯烃树脂65份、乙烯-醋酸乙烯共聚物60份、三偏磷酸钠16份、过硫酸钾19.5份、硅藻土23份、聚乙烯醇8份、阻燃剂9.5份、仲烷基磺酸钠6份、十六烷基三甲基氯化铵7.5份、聚六亚甲基胍8.5份、甘草酸二甲12份、调节研磨的功率为2.2KW,研磨时间为60min,即得到变性淀粉复合材料;
将制备得到的变性淀粉复合材料加水洗涤,烘干,粉碎,过筛后即得产品。
为了验证本发明制备得到的淀粉粘合剂的性能,将本发明实施例制备得到的淀粉粘合剂用于人造板胶合,同时以市售的淀粉粘合剂作为对照样品。按照GB/T 17657所规定方法进行测试,将试件放入63±3℃的热水中浸渍3h,然后将试件平放在63±3℃的空气对流干燥箱中干燥1h,取出后在室温下降温10min,再进行胶合强度测试。产品胶合强度、耐水性均内满足国家Ⅱ类胶合板相关标准。
表1 人造板粘合剂性能
本发明上述实施例方案仅是对本发明的说明而不能限制本发明,权利要求中指出了本发明产品组成成分、成分比例、制备方法参数的范围,而上述的说明并未指出本发明参数的范围,因此,在与本发明的权利要求书相当的含义和范围内的任何改变,都应当认为是包括在权利要求书的范围内。
本发明是经过多位淀粉粘合剂加工人员长期工作经验积累,并通过创造性劳动创作而出,本发明制备得到的淀粉粘合剂粘合强度高,环保,耐水性好、稳定性好,方便运输和储存,具有广阔的应用前景。
Claims (3)
1.一种人造板用淀粉粘合剂的制备方法,其特征在于,制备方法步骤包括:
步骤1)木薯淀粉变性:取木薯淀粉100~150份,加入5%NaOH充分润湿后采用60Coγ-射线进行辐照处理后即得到变性淀粉,设定辐照剂量为12~18KGY,辐照温度为30~50℃,辐照时间为30~60min;
步骤2)机械化学法制备变性淀粉复合材料:取经过辐照后的变性淀粉加入到螺杆研磨机,然后加入氧化剂20~40份、苯乙烯化醇酸树脂20~30份、聚烯烃树脂60~80份、乙烯-醋酸乙烯共聚物60~80份、三偏磷酸钠15~20份、过硫酸钾18~20份、硅藻土20~30份、聚乙烯醇8~10份、阻燃剂8~10份、仲烷基磺酸钠5~6份、十六烷基三甲基氯化铵6~8份、聚六亚甲基胍8~10份、甘草酸二甲8~12份、调节研磨的功率为1.8~2.4KW,研磨时间为30~90min,即得到变性淀粉复合材料;
步骤3)将制备得到的变性淀粉复合材料加水洗涤,烘干,粉碎,过筛后即得产品。
2.根据权利要求1所述的一种人造板用淀粉粘合剂的制备方法,其特征在于,所述的氧化剂为次氯酸钠、过氧化氢、高锰酸钾中的一种或者一种以上的组合物。
3.根据权利要求1所述的一种人造板用淀粉粘合剂的制备方法,其特征在于,所述的阻燃剂为甲基磷酸二甲酯、镁铝水滑石、磷酸酯中的一种或一种以上的组合。
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