CN106476367A - 木质素酚醛树脂环保板材 - Google Patents

木质素酚醛树脂环保板材 Download PDF

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CN106476367A
CN106476367A CN201610899289.4A CN201610899289A CN106476367A CN 106476367 A CN106476367 A CN 106476367A CN 201610899289 A CN201610899289 A CN 201610899289A CN 106476367 A CN106476367 A CN 106476367A
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phenol formaldehyde
formaldehyde resin
lignin
lignin phenol
liquid
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CN106476367B (zh
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邹海平
宗武
周磊
王涛
李刚
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Lattice Justice Circular Economy Industrial Garden Anhui Co Ltd
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Abstract

本发明涉及一种木质素酚醛树脂环保板材,属于建筑材料技术领域。所述的环保板材包括由上到下依次设置的上涂层、上板材、中间涂层、下板材和下涂层五层结构。本发明的木质素酚醛树脂环保板材的表层密度高、强度大、不易变形,生产工艺简单,不必在密封容器中对人工林软质木材进行处理,生产效率较高,工艺参数明确,可操作性强,能够直接作为家具、室内装饰装修用材料,具有高强抗震、阻燃、低烟无毒、耐水耐潮、耐腐蚀、耐高温绝缘、轻质、安装快捷、防老化以及耐磨损等特点,无污染安全又环保,同时使用寿命长。

Description

木质素酚醛树脂环保板材
技术领域
本发明涉及一种木质素酚醛树脂环保板材,属于建筑材料技术领域。
背景技术
目前在木材加工行业,大量生产的板材材质疏松、密度较低、力学强度差,不能直接作为家具、室内装饰装修等的材料使用。现有板材吸水易膨胀,导致板材变形起泡,同时存在耐水耐潮、耐腐蚀和防火性能均较差等问题。另外刨花板在生产过程中需要加入大量甲醛类的胶贴剂,因此对环境和人身均有害,且由木材制成的板也极易发生火灾,人们的生活环境时刻存在着隐患。
发明内容
本发明的目的是提供一种木质素酚醛树脂环保板材,具有阻燃性好、耐水耐潮、耐腐蚀、耐高温、绝缘的特点。
本发明所述的木质素酚醛树脂环保板材,包括由上到下依次设置的上涂层、上板材、中间涂层、下板材和下涂层五层结构,其中:
(1)上涂层由以下重量份数的原料制成:木质素酚醛树脂30-40份、空心玻璃微球20-30份、钛白粉10-20份、脲醛树脂颗粒15-20份、竹篾15-20份、乙醇1-5份、纳米天青石粉1-4份、天然橡胶25-40份、邻苯二甲酸酯0.5-0.9份、槽法碳黑2-6份、氧化锌1-4份、三氧化二锑10-15份、丁苯橡胶10-30份、三盐1-5份;
(2)中间涂层由以下重量份数的原料制成:木质素酚醛树脂30-40份、氧化钙20-30份、硅酸铝20-30份、硅酸铝9-15份、邻苯二甲酸二环己酯8-12份、聚四氟乙烯树脂10-18份、羟丙基甲基纤维素5-14份、乙酸乙酯10-16份;
(3)下涂层由以下重量份数的原料制成:木质素酚醛树脂30-40份、玻纤粉15-25份、云母粉9-14份、刚玉粉5-8份、硬脂酸钙12-19份、玻璃纤维1-3份、抗氧剂11-16份、固化剂1-5份;
所述的上涂层、中间涂层和下涂层中的木质素酚醛树脂的制备方法如下:先将木质素50-300份、苯酚100-150份、酸性半纤维素液2-25份、碱性半纤维素液50-100份、10-50份软水、50-70份植酸磷树脂和1-15份沸石固体酸加入到反应釜中,在温度为150-250℃、压力为2-4MPa下反应2~10h,得到反应液,再向反应液中依次加入40-190份甲醛、1-15份纳米复合催化剂,在50~120℃下反应1-6h,得到粘稠物,然后将粘稠物用50~80℃的水进行洗涤,干燥后粉碎至200目,最后加入2-20份凝胶型离子交换树脂进行搅拌,得到木质素酚醛树脂。
所述的上涂层是将配比量的原料在常温下混合均匀后而制得。
所述的中间涂层的制备方法如下:将氧化钙、硅酸铝加入到反应釜中,升温至60-80℃后加入木质素酚醛树脂、氧化钙、硅酸铝、邻苯二甲酸二环己酯搅拌均匀,继续升温至75-100℃后加入羟丙基甲基纤维素、乙酸乙酯、聚四氟乙烯树脂进行搅拌,得到中间涂层;
所述的下涂层的制备方法如下:将配方量的木质素酚醛树脂、玻纤粉、云母粉、刚玉粉、硬脂酸钙、抗氧剂加入到容器内进行搅拌,得到胶液,加入固化剂后进行搅拌,得到树脂糊,将树脂糊加入到浸胶槽中,然后将玻璃纤维以20-100r/min的速度通过浸胶槽,使得树脂糊均匀涂布在玻璃纤维上,得到下涂层。其中,所述的固化剂为间苯二甲胺,抗氧剂为抗坏血酸棕榈酸酯或异抗坏血酸钠。
所述的木质素酚醛树脂中的木质素的制备方法包括以下步骤:
(1)以秸秆作为原料,先通过粉碎机进行切断、除尘,再于2.0~5.0MPa下汽爆2~6min,固液分离后向得到的固形物中加碱液,在78~135℃下蒸煮分离0.5~2h,得到木质素黑液;
(2)向木质素黑液中加入15~90ppm的Ca(OH)2进行絮凝沉淀,经过滤精度为18~23μm的过滤器进行过滤,得到木质素清液;
(3)将木质素清液送入管式超滤膜中,控制超滤膜堆压力为5.0~8.0MPa、温度为30~60℃、通量为50~90m3,得到超滤浓液和超滤清液,将超滤浓液送入超滤单效蒸发分离器中,控制蒸发负压为-0.85~-0.89MPa、温度为70~90℃、通量为10~20m3,得到超滤浓黑液,将超滤清液通过卷式纳滤膜进行过滤分离,控制纳滤膜堆压力为15.0~20.0MPa、温度为30~60℃、通量为10~20m3,得到纳滤浓液和纳滤清液,将纳滤浓液送入纳滤单效蒸发分离器,控制蒸发压力为-0.85~-0.89MPa、温度为70~90℃、通量4~10m3,得到纳滤浓黑液;
(4)将超滤浓黑液和纳滤浓黑液分别通过输送装置送入喷雾干燥器,控制干燥负压为-0.21~-0.53MPa、进风温度为200~300℃、出风温度90~180℃,最终得到粒度为200~230目的木质素;
其中:
植酸磷树脂的制备方法如下:将80~100份植酸磷加入到反应器中,向其中加入去离子水调节pH值为10~13,然后加入200~700份二乙胺基丙胺调节pH值为8~13,升温至70~100℃,加入碳酸钠反应10~22h,调节pH值为1~6,于100℃下加入多钒酸铵反应1~4h,离心过滤后得到植酸磷树脂。
凝胶型离子交换树脂为市售330-弱碱性环氧系阴离子交换树脂;纳米复合催化剂为纳米矿晶。
酸性半纤维素液为秸秆经粉碎机切断后,于2.0~5.0MPa下汽爆2~6min,固液分离后向得到的固形物中加酸液,于78~135℃下蒸煮0.5~2h而产生的发酵废液,主要含有液体酸、酸性络合物、硅铝酸盐、酸性氧化物等。
碱性半纤维素液为秸秆经粉碎机切断后,于2.0~5.0MPa下汽爆2~6min,固液分离后向得到的固形物中加碱液,于78~135℃下蒸煮0.5~2h而产生的发酵废液,主要含有Ca(OH)2、活性白泥、硅藻土、活性碳、饱和碱溶液、木聚糖、碱土金属氧化物等。
本发明的木质素酚醛树脂环保板材采用常规办法进行生产,步骤如下:
(1)将上板材和下板材用自动打磨机进行打磨制平,然后将调配好的专用板材封闭剂均匀涂刷到上、下板材上,可以有效地对板材进行封闭,防止板材受到污染,板材封闭可以防止板材过度吸湿、散湿以及板材变形,增强漆膜与板材之间的附着力,节约漆用量,增强漆膜硬度;
(2)上涂层采用刷涂或喷涂方式。上涂层施工的作用是填平木孔,增加漆膜厚度,施工时注意上涂层实干后,必须用自动打磨机彻底打磨后,再涂下一遍底漆,要求做到均匀涂刷,无流挂,木眼填充平整。
(3)砂磨处理用自动打磨机打磨板材是贯穿整个板材涂漆施工过程的步骤。板材处理时要砂磨,涂层施工要砂磨,面漆施工前后也要砂磨。砂磨的步骤非常关键。砂磨处理使得板材更加光滑,平整,利于上漆。上漆后砂磨,又使得漆膜表面平整,光滑,不过注意砂磨处理的时候避免横砂,不能采用过粗的磨砂轮。
(4)中间涂层在施工前一定要再一次清洁板材表面,除掉灰尘颗粒,使得漆膜表面能有更好的涂装效果;
(5)下涂层作为板材的下表面层,在施工前一定要再一次清洁板材表面,除掉灰尘颗粒,涂漆过程直接影响到漆膜的最终效果,涂漆过程要求必须涂刷均匀、无流挂、光泽度好,无明显刷痕,手感光滑细腻。
本发明的有益效果如下:
(1)本发明的木质素酚醛树脂环保板材的表层密度高、强度大、不易变形,生产工艺简单,不必在密封容器中对人工林软质木材进行处理,生产效率较高;工艺参数明确,可操作性强;可直接作为家具、室内装饰装修用材料;
(2)具有很好的保温节能、高强抗震、阻燃性能、低烟无毒、耐水耐潮、耐腐蚀、耐高温绝缘、轻质、安装快捷、防老化以及耐磨损等特点,无污染安全又环保,同时使用寿命长。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
木质素酚醛树脂环保板材,包括由上到下依次设置的上涂层、上板材、中间涂层、下板材和下涂层五层结构,其中:
(1)上涂层由以下重量份数的原料制成:木质素酚醛树脂35份、空心玻璃微球25份、钛白粉15份、脲醛树脂颗粒17份、竹篾16份、乙醇2份、纳米天青石粉3份、天然橡胶30份、邻苯二甲酸酯0.5份、槽法碳黑4份、氧化锌2份、三氧化二锑11份、丁苯橡胶15份、三盐1份;
制备方法:将配比量的原料在常温下混合均匀后而制得。
(2)中间涂层由以下重量份数的原料制成:木质素酚醛树脂38份、氧化钙26份、硅酸铝26份、邻苯二甲酸二环己酯9份、聚四氟乙烯树脂16份、羟丙基甲基纤维素7份、乙酸乙酯13份;
制备方法:将氧化钙、硅酸铝加入到反应釜中,升温至75℃后加入木质素酚醛树脂、氧化钙、硅酸铝、邻苯二甲酸二环己酯搅拌均匀,继续升温至95℃后加入羟丙基甲基纤维素、乙酸乙酯、聚四氟乙烯树脂进行搅拌,得到中间涂层;
(3)下涂层由以下重量份数的原料制成:木质素酚醛树脂35份、玻纤粉17份、云母粉10份、刚玉粉6份、硬脂酸钙15份、玻璃纤维2份、异抗坏血酸钠11份、间苯二甲胺3份;
制备方法:将配方量的木质素酚醛树脂、玻纤粉、云母粉、刚玉粉、硬脂酸钙、异抗坏血酸钠加入到容器内进行搅拌,得到胶液,加入间苯二甲胺后进行搅拌,得到树脂糊,将树脂糊加入到浸胶槽中,然后将玻璃纤维以20-100r/min的速度通过浸胶槽,使得树脂糊均匀涂布在玻璃纤维上,得到下涂层。
其中:
上涂层、中间涂层和下涂层中的木质素酚醛树脂的制备方法如下:先将木质素200份、苯酚110份、酸性半纤维素液12份、碱性半纤维素液50份、107份软水、55份植酸磷树脂和3份沸石固体酸加入到反应釜中,在温度为160℃、压力为2MPa下反应4h,得到反应液,再向反应液中依次加入45份甲醛、3份纳米矿晶,在70℃下反应2h,得到粘稠物,然后将粘稠物用60℃的水进行洗涤,干燥后粉碎至200目,最后加入8份市售330-弱碱性环氧系阴离子交换树脂进行搅拌,得到木质素酚醛树脂。
上述木质素酚醛树脂中的木质素的制备方法包括以下步骤:
(1)以小麦秸秆作为原料,先通过粉碎机进行切断、除尘,再于3.0MPa下汽爆4min,固液分离后向得到的固形物中加碱液,在85℃下蒸煮分离1h,得到木质素黑液;
(2)向木质素黑液中加入60ppm的Ca(OH)2进行絮凝沉淀,经过滤精度为20μm的过滤器进行过滤,得到木质素清液;
(3)将木质素清液送入管式超滤膜中,控制超滤膜堆压力为6.0MPa、温度为40℃、通量为60m3,得到超滤浓液和超滤清液,将超滤浓液送入超滤单效蒸发分离器中,控制蒸发负压为-0.87MPa、温度为70℃、通量为11m3,得到超滤浓黑液,将超滤清液通过卷式纳滤膜进行过滤分离,控制纳滤膜堆压力为18MPa、温度为33℃、通量为12m3,得到纳滤浓液和纳滤清液,将纳滤浓液送入纳滤单效蒸发分离器,控制蒸发压力为-0.87MPa、温度为60℃、通量5m3,得到纳滤浓黑液;
(4)将超滤浓黑液和纳滤浓黑液分别通过输送装置送入喷雾干燥器,控制干燥负压为-0.53MPa、进风温度为210℃、出风温度110℃,最终得到粒度为200目的木质素;
植酸磷树脂的制备方法如下:将80份植酸磷加入到反应器中,向其中加入去离子水调节pH值为11,然后加入300份二乙胺基丙胺调节pH值为1,升温至75℃,加入碳酸钠反应12h,调节pH值为4,于100℃下加入2份多钒酸铵反应2h,离心过滤后得到植酸磷树脂。

Claims (9)

1.一种木质素酚醛树脂环保板材,包括由上到下依次设置的上涂层、上板材、中间涂层、下板材和下涂层五层结构,其特征在于:
(1)上涂层由以下重量份数的原料制成:木质素酚醛树脂30-40份、空心玻璃微球20-30份、钛白粉10-20份、脲醛树脂颗粒15-20份、竹篾15-20份、乙醇1-5份、纳米天青石粉1-4份、天然橡胶25-40份、邻苯二甲酸酯0.5-0.9份、槽法碳黑2-6份、氧化锌1-4份、三氧化二锑10-15份、丁苯橡胶10-30份、三盐1-5份;
(2)中间涂层由以下重量份数的原料制成:木质素酚醛树脂30-40份、氧化钙20-30份、硅酸铝20-30份、硅酸铝9-15份、邻苯二甲酸二环己酯8-12份、聚四氟乙烯树脂10-18份、羟丙基甲基纤维素5-14份、乙酸乙酯10-16份;
(3)下涂层由以下重量份数的原料制成:木质素酚醛树脂30-40份、玻纤粉15-25份、云母粉9-14份、刚玉粉5-8份、硬脂酸钙12-19份、玻璃纤维1-3份、抗氧剂11-16份、固化剂1-5份;
所述的上涂层、中间涂层和下涂层中的木质素酚醛树脂的制备方法如下:先将木质素50-300份、苯酚100-150份、酸性半纤维素液2-25份、碱性半纤维素液50-100份、10-50份软水、50-70份植酸磷树脂和1-15份沸石固体酸加入到反应釜中,在温度为150-250℃、压力为2-4MPa下反应2~10h,得到反应液,再向反应液中依次加入40-190份甲醛、1-15份纳米复合催化剂,在50~120℃下反应1-6h,得到粘稠物,然后将粘稠物用50~80℃的水进行洗涤,干燥后粉碎至200目,最后加入2-20份凝胶型离子交换树脂进行搅拌,得到木质素酚醛树脂。
2.根据权利要求1所述的木质素酚醛树脂环保板材,其特征在于:上涂层是将配方量的原料在常温下混合均匀后而制得。
3.根据权利要求1所述的木质素酚醛树脂环保板材,其特征在于:中间涂层的制备方法如下:将氧化钙、硅酸铝加入到反应釜中,升温至60-80℃后加入木质素酚醛树脂、氧化钙、硅酸铝、邻苯二甲酸二环己酯搅拌均匀,继续升温至75-100℃后加入羟丙基甲基纤维素、乙酸乙酯、聚四氟乙烯树脂进行搅拌,得到中间涂层。
4.根据权利要求1所述的木质素酚醛树脂环保板材,其特征在于:下涂层的制备方法如下:将配方量的木质素酚醛树脂、玻纤粉、云母粉、刚玉粉、硬脂酸钙、抗氧剂加入到容器内进行搅拌,得到胶液,加入固化剂后进行搅拌,得到树脂糊,将树脂糊加入到浸胶槽中,然后将玻璃纤维以20-100r/min的速度通过浸胶槽,使得树脂糊均匀涂布在玻璃纤维上,得到下涂层;其中,所述的固化剂为间苯二甲胺,抗氧剂为抗坏血酸棕榈酸酯或异抗坏血酸钠。
5.根据权利要求1所述的木质素酚醛树脂环保板材,其特征在于:木质素的制备方法包括以下步骤:
(1)以秸秆作为原料,先通过粉碎机进行切断、除尘,再于2.0~5.0MPa下汽爆2~6min,固液分离后向得到的固形物中加碱液,在78~135℃下蒸煮分离0.5~2h,得到木质素黑液;
(2)向木质素黑液中加入15~90ppm的Ca(OH)2进行絮凝沉淀,经过滤精度为18~23μm的过滤器进行过滤,得到木质素清液;
(3)将木质素清液送入管式超滤膜中,控制超滤膜堆压力为5.0~8.0MPa、温度为30~60℃、通量为50~90m3,得到超滤浓液和超滤清液,将超滤浓液送入超滤单效蒸发分离器中,控制蒸发负压为-0.85~-0.89MPa、温度为70~90℃、通量为10~20m3,得到超滤浓黑液,将超滤清液通过卷式纳滤膜进行过滤分离,控制纳滤膜堆压力为15.0~20.0MPa、温度为30~60℃、通量为10~20m3,得到纳滤浓液和纳滤清液,将纳滤浓液送入纳滤单效蒸发分离器,控制蒸发压力为-0.85~-0.89MPa、温度为70~90℃、通量4~10m3,得到纳滤浓黑液;
(4)将超滤浓黑液和纳滤浓黑液分别通过输送装置送入喷雾干燥器,控制干燥负压为-0.21~-0.53MPa、进风温度为200~300℃、出风温度90~180℃,最终得到粒度为200~230目的木质素。
6.根据权利要求1所述的木质素酚醛树脂环保板材,其特征在于:植酸磷树脂的制备方法如下:将80~100份植酸磷加入到反应器中,向其中加入去离子水调节pH值为10~13,然后加入200~700份二乙胺基丙胺调节pH值为8~13,升温至70~100℃,加入碳酸钠反应10~22h,调节pH值为1~6,于100℃下加入多钒酸铵反应1~4h,离心过滤后得到植酸磷树脂。
7.根据权利要求1所述的木质素酚醛树脂环保板材,其特征在于:凝胶型离子交换树脂为市售330-弱碱性环氧系阴离子交换树脂;纳米复合催化剂为纳米矿晶。
8.根据权利要求1所述的木质素酚醛树脂环保板材,其特征在于:酸性半纤维素液为为秸秆经粉碎机切断后,于2.0~5.0MPa下汽爆2~6min,固液分离后向得到的固形物中加酸液,于78~135℃下蒸煮0.5~2h而产生的发酵废液。
9.根据权利要求1所述的木质素酚醛树脂环保板材,其特征在于:碱性半纤维素液为秸秆经粉碎机切断后,于2.0~5.0MPa下汽爆2~6min,固液分离后向得到的固形物中加碱液,于78~135℃下蒸煮0.5~2h而产生的发酵废液。
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