CN110903673A - 一种使用棕榈生物质粉为原料的生物基复合材料制备方法 - Google Patents

一种使用棕榈生物质粉为原料的生物基复合材料制备方法 Download PDF

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CN110903673A
CN110903673A CN201911341714.8A CN201911341714A CN110903673A CN 110903673 A CN110903673 A CN 110903673A CN 201911341714 A CN201911341714 A CN 201911341714A CN 110903673 A CN110903673 A CN 110903673A
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palm
parts
bio
biomass
raw material
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范大鹏
齐海群
王育钦
冯钢
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Liaoning Xingfu people Technology Co., Ltd
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HEILONGJIANG XINGFUREN ECOLOGICAL AGRICULTURAL DEVELOPMENT Co Ltd
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Publication of CN110903673A publication Critical patent/CN110903673A/zh
Priority to US16/931,256 priority patent/US11161985B2/en
Priority to MYPI2020003685A priority patent/MY194895A/en
Priority to DE102020121552.5A priority patent/DE102020121552B4/de
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Abstract

本发明提供了一种使用棕榈生物质粉为原料的生物基复合材料制备方法,属于生物基复合材料制备方法技术领域。棕榈微粉的清洗,将100份600~1200目的棕榈微粉置入反应容器,按照浴比1:4或1:5的比例向反应容器中加400~500份丙酮;棕榈微粉的表面处理,将溶剂置换后的反应体系加热至80~100℃,馏出物以3A分子筛除水后回流至反应釜;生物基树脂的共混挤出;本发明解决了棕榈作为生物质原料因油性小分子含量过高导致的杂质迁移以及产品性能不足等问题。打破了只能在水溶液中对生物质进行处理,否则加工成本过高的认识误区,开创了有效的棕榈生物质处理方法。以棕榈残渣为生物基原料,制备出了低成本,高性能,加工性能良好,可以达到食品接触条件的生物基树脂新材料。

Description

一种使用棕榈生物质粉为原料的生物基复合材料制备方法
技术领域
本发明涉及一种使用棕榈生物质粉为原料的生物基复合材料制备方法,属于生物基复合材料制备方法技术领域。
背景技术
石油基树脂,如聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯等通用树脂,在目前的生产和生活中仍然是必不可少的、大规模生产和使用的,短期没有代替产品的重要原材料。由于无可代替,石油基树脂的减量化使用仍然是树脂产业未来几十年重要的发展方向之一。高填充树脂,生物基树脂,生物基复合材料等一系列树脂产品的制备则是这一方向的主要研究内容。
棕榈是热带和亚热带的主要经济作物之一,榨油后的棕榈残渣由于没有食用价值,只能被丢弃或者堆肥,导致了较为严重的环境问题,造成了严重的资源浪费。经济作物棕榈的残渣(棕榈皮,棕榈壳,棕榈渣)具有较高的纤维含量,将其粉碎后制备成生物质微粉,可以用作生物基复合材料的填料使用,既解决了经济作物副产物导致的环境问题,增加了种植经济作物的收入,同时也能减少石油基树脂的使用,降低生物基复合材料(生物基树脂)的生产成本,因而具有良好的经济意义和社会价值。
然而以棕榈残渣作为生物基原料与通用树脂相复合,与其他的优质生物基原材料相比,如木粉、竹粉等,显现出一定的劣势。棕榈残渣中低分子油性物质含量较高,在树脂共混复合的加工过程以及制成品的使用过程中容易因油性物质的迁移而造成产品性能的不足和表面析出等现象。同时棕榈残渣中的营养成分较高,也容易造成制成品的生物侵害,影响制成品的耐久性能。
发明内容
本发明的目的是为了解决上述现有技术存在的问题,进而提供一种使用棕榈生物质粉为原料的生物基复合材料制备方法。
本发明的目的是通过以下技术方案实现的:
一种使用棕榈生物质粉为原料的生物基复合材料制备方法,
步骤一、棕榈微粉的清洗:
①将100份600~1200目的棕榈微粉置入反应容器,按照浴比1:4或1:5的比例向反应容器中加400~500份丙酮,关闭反应容器使体系密封,加热至50~60℃,以500转/min的速度搅拌分散30min,静置使棕榈微粉沉降,使用压板将沉降的固体物轻微压实,抽出压板上方的澄清液,回收澄清液,蒸馏回收丙酮溶剂,剩余的浊溶液过滤后,集中蒸馏回收溶剂;②抬起压板,向反应容器中再次加入500份预热至50℃的丙酮作为分散介质,以500转/min的速度搅拌分散15min,静置使棕榈微粉沉降,使用压板将沉降的固体物轻微压实,抽出压板上方的澄清液;③重复②的操作3~4次后,按照②的方法再以环己烷、正辛烷为分散介质进行溶剂置换,至此完成清洗步骤;
步骤二、棕榈微粉的表面处理:
①将溶剂置换后的反应体系加热至80~100℃,馏出物以3A分子筛除水后回流至反应釜,抽样检测,直至反应容器中的反应体系中水含量低于0.2~0.5mg/L,将3份或5份1,6-亚己基二异氰酸酯、或5份2,4-甲苯二异氰酸酯二异氰酸酯溶于环己烷,加入至反应容器中,回流反应30min;②将正十六醇5份或8份溶于加热的正辛烷,或将正十八醇6份溶于加热的正辛烷,然后加入至反应容器中,在加热和搅拌的条件下继续回流反应2h,再向反应体系中加入3份的乙酰氯,改用4A分子筛和CaO干燥馏出物,回流反应2h后,停止搅拌,使反应体系降温至50℃;③以压板将沉降的棕榈生物质轻微压实,抽出上清液,使用正戊烷进行溶剂置换,在溶剂置换后加热搅拌,抽真空,使反应容器中的液相全部蒸出,得到经过清洗、表面处理和严格除水后的干燥棕榈生物质微粉,至此完成表面处理步骤;
步骤三、生物基树脂的共混挤出:
①将50~60份经过清洗和表面处理的棕榈微粉加入到具有高度气密性和防腐能力的塑料高混设备中,维持高混设备的温度为70℃,向高混设备中加入1份环氧大豆油、或2份聚丙烯蜡和1份环氧大豆油、或1份环氧大豆油,1份聚乙烯醇,混炼5min后,将高混设备的温度升高到95~100℃,加入0.2份马来酸酐或0.2份衣康酸,继续混炼5min;②加入LLDPE树脂颗粒料40份,粒径为500目的碳酸钙7份,粒径为1800目的碳酸钙3份和硬脂酸锌3份、或PP树脂颗粒料30份,粒径为500目的碳酸钙5份,粒径为3000目的碳酸钙5份和硬脂酸钙3份、或PLA树脂颗粒料40份;③将高混设备的温度升高到85~90℃,混炼20min,出料后冷却,得到降解母粒预混料;④预混料通过双阶挤出机组进行共混挤出,为了避免冷却过程中水分的吸入,造成产品的性能损失,采用模面热切及风冷拉条切粒的工艺使物料冷却并造粒,得到棕榈生物基/PE树脂母粒,至此完成共混挤出步骤。
本发明的有益效果:
1、本发明解决了棕榈作为生物质原料,因油性小分子含量过高导致的杂质迁移以及产品性能不足等问题。2、打破了只能在水溶液中对生物质进行处理,否则加工成本过高的认识误区,开创了有效的棕榈生物质处理方法。3、以棕榈残渣为生物基原料,制备出了低成本,高性能,加工性能良好,可以达到食品接触条件的生物基树脂新材料。4、提高了棕榈残渣的利用率,降低了环保压力。
附图说明
图1为表面改性后的棕榈微粉电镜图。
图2为表面改性前后棕榈微粉的红外光谱谱图。
具体实施方式
下面将对本发明做进一步的详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式,但本发明的保护范围不限于下述实施例。
实施例1
步骤一、棕榈微粉的清洗:
一般而言,生物质微粉是一种相对廉价的树脂填料,生物质微粉的成本只有300~800元/吨,而对生物质微粉进行清洗,清洗的成本甚至远高于生物质微粉本身的成本。正因如此,生物基材料行业的从业者通常不会对生物质粉体进行清洗和纯化。然而直接使用棕榈微粉作为生物质填充材料存在着诸多的不利因素,棕榈微粉中蛋白质和油脂的含量过高,容易造成变色、焦化、小分子物质迁移以及生物侵蚀,严重影响了生物基树脂制成品的使用性能。发明人认为,在目前行业对生物质的清洗和表面处理工艺存在严重的认识误区,业内普遍认为生物质的清洗和表面处理应当以水作为介质,因为水作为介质,最为廉价。然而生物质本身具有很强的亲水性,会在水溶液中溶胀,导致分散体系粘度大分散困难,而且水具有较大的表面张力,在清洗和表面处理以后的干燥过程中会造成生物质原料的板结。此外,水与许多种改性剂都可以发生化学反应,限制了对生物质进行表面处理的方法。水因为相对廉价,所以在生产过程中产生的废水往往会直接排放,从而又造成了不可忽略的废水污染。存在上述的种种弊端,然而使用水作为生物质的清洗介质,对油性的污染物的清洗效果却十分不理想。正因如此,行业才普遍认为与其对生物质进行清洗,不如使用更优质的原材料,成本反而更低廉。
有机溶剂的价格远高于水,以价格远高于生物质原料的有机溶剂作为清洗生物质的介质普遍被认为更不具备工艺上的可行性。但上述观点是认识上的误区,有机溶剂因为昂贵,所以在使用过程中都是循环利用,可以有效的控制成本。即使如此,以有机溶剂清洗棕榈生物质微粉的成本,仍然是棕榈生物质微粉自身价格的数倍(约为1000~2000元/吨),但即便如此与树脂的价格相比,清洗和表面处理后的棕榈微粉仍然具有明显的价格优势。而清洗(和表面处理)带来的益处,如大幅的提高材料的力学性能,提高加工过程的工艺性和稳定性,洗除残余农药,提高制成品的安全性,形成良好的界面进而提高制成品中生物质的含量,这些益处不是更换高品质的生物质原料(如木粉、竹粉、变性淀粉)能够达到的效果。所以总体而言,以有机溶剂作为棕榈生物质微粉清洗和表面处理的介质,在工艺上其实是切实可行的,并不会造成环境污染,操作环境恶化,和成本大幅飙升等严重问题,这种看似不可行的工艺选择恰恰是解决现实问题的关键所在。
本发明的清洗步骤,使用丙酮为清洗溶剂,在加热搅拌的条件下对棕榈生物质粉进行较长时间的多次清洗,洗除生物质中的丙酮溶出物,如残余农药,油脂、磷脂和蛋白质。在清洗的过程中,和清洗过程结束后,以抽出上清液,溶剂置换的方式使溶出物与棕榈生物质相分离。不采用过滤,而采用溶剂置换,是因为过滤对于大规模的生产而言效率过低,且操作时难以保证气密性,会造成有机溶剂的消耗。
步骤二、棕榈微粉的表面处理:
对于本发明提供的工艺方法而言,棕榈生物质微粉的处理过程中,主要的成本在于有机溶剂的消耗,以及有机溶剂回收时的能耗。与这两个工艺步骤的成本相比,棕榈微粉的表面处理实际上相对廉价。使用有机溶剂对棕榈生物质进行清洗,却不进行油性介质环境中的表面处理,实际上相当于浪费了耗资得来的良好反应环境,因此有必要对棕榈生物质微粉进行表面处理。
本发明提供的工艺方法,在具体实施过程中,棕榈生物质微粉的清洗和表面处理是连接在一起进行的。以有机溶剂丙酮作为清洗介质对棕榈生物质微粉进行多次的溶剂置换清洗以后,用环己烷、正辛烷等脂肪烃类有机溶剂置换丙酮介质,而后取样,按照国家标准《聚醚多元醇中羟值测定方法GB 12008.3-89》测量生物质的有效羟值。
将反应容器中的混合体系加热至沸腾,以残留的丙酮作为带水剂,在搅拌的条件下进行共沸蒸馏,馏出物经过3A分子筛干燥除水后,回流至反应容器。待除水步骤达到了预期的除水效果后,按照实测的棕榈生物质微粉的有效羟值向反应容器加入一定量的二异氰酸酯,反应一定时间后,将高级脂肪醇溶于环己烷、正辛烷和丙酮的混合溶剂,加入到反应体系中。在整个反应过程中,首先利用二异氰酸酯与生物质表面的羟基之间的化学反应使生物质表面活化,然后再与高级脂肪醇的端羟基发生反应,将非极性的长脂肪链接枝到棕榈生物质的表面上,代替极性的羟基,从而降低棕榈生物质的亲水性和表面能,提高其与树脂基体之间的界面亲和能力,减少后续挤出过程中的界面摩擦,有助于在棕榈生物质和树脂基体之间形成牢固的界面结合,从而大幅的生物基(棕榈)树脂提高制成品的性能。
在表面处理结束后,停止搅拌,使反应体系中的生物质沉降,以低沸点的有机溶剂环己烷或戊烷做溶剂置换后,在反应容器中直接干燥,得到干燥无水的改性棕榈生物质微粉。
改性后的棕榈生物质微粉的电镜照片如图1所示,从图中可以看出改性过程并未导致生物质粉出现严重的团聚。
步骤三、生物基树脂的共混挤出:
将改性处理后的棕榈生物质微粉(30~70份)、通用树脂(30~70份)、润滑剂(0.5~2.5份)、相容剂(0~1.5份)和其他助剂等物料按照指定的配比,置入树脂高速混合机中混合均匀,在冷却混合机中继续搅拌分散并冷却,冷却后的物料经双螺杆挤出机或双阶挤出机共混挤出,即可得到棕榈生物质作为填充材料的生物基树脂颗粒。
检测生物基树脂的性能,其熔融指数可在0.5~20的范围内调整(改变通用树脂的牌号),可满足注塑、压延、吸塑和吹塑的工艺要求。生物质含量为15~30wt%时,其拉伸强度可达15~20MPa,较表面处理前有较大的提高,拉伸强度的提高幅度超过了30%。
其中,通用树脂可以为聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚酯、聚乳酸、PBAT等一种或几种的组合物。润滑剂为硬脂酸钙、硬脂酸镁、硬脂酸锌等物质一种或几种的混合物。相容剂为环氧化的植物油,马来酸酐及其衍生物,其他助剂可为色母、可降解助剂、导电助剂、发泡助剂等。
挤出温度、挤出压力等具体工艺参数视通用树脂的种类和含量而定,挤出后的物料必须采用风冷冷却,以避免挤出的树脂在较高的温度下吸收水分,导致材料性能的降低。挤出,冷却,切粒后的物料密封包装,以供储存,销售和使用。
实施例2
步骤一、棕榈微粉的表面清洗:
将100份600目的棕榈微粉置入反应容器,按照浴比1:5向反应容器中加入500份丙酮,关闭反应容器使体系密封,加热至50℃,以500转/min的速度搅拌分散30min,静置使棕榈微粉沉降,使用压板将沉降的固体物轻微压实,抽出压板上方的澄清液,回收澄清液,蒸馏回收大量的丙酮溶剂,剩余的浊溶液过滤后,集中蒸馏回收溶剂。抬起压板,向反应容器中再次加入500份预热至50℃的丙酮作为分散介质,以500转/min的速度搅拌分散15min,静置使棕榈微粉沉降,使用压板将沉降的固体物轻微压实,抽出压板上方的澄清液。重复此操作3次后,按照同样的方法以环己烷和正辛烷为分散介质进行溶剂置换,至此完成工艺的清洗步骤。
步骤二、棕榈微粉的表面处理:
将溶剂置换后的反应体系加热至100℃,馏出物以3A分子筛除水后回流至反应釜,抽样检测,直至反应容器中的反应体系中水含量低于0.5mg/L,将3份1,6-亚己基二异氰酸酯溶于环己烷,加入至反应容器中,回流反应30min。将正十六醇5份溶于加热的正辛烷,加入至反应容器中,在加热和搅拌的条件下继续回流反应2h,再向反应体系中加入适量的乙酰氯,改用4A分子筛和CaO干燥馏出物,回流反应2h后,停止搅拌,使反应体系降温至50℃,以压板将沉降的棕榈生物质轻微压实,抽出上清液,使用正戊烷进行溶剂置换,在溶剂置换后加热搅拌,抽真空,使反应容器中的液相全部蒸出,得到经过清洗、表面处理和严格除水后的干燥棕榈生物质微粉。至此完成工艺的第二个步骤。检测改性后生物质粉体的表面能由0.047J·m-2变为0.039J·m-2,改性后的生物质微粉的亲水特性被显著改变,与树脂基体的相容性显著提高。(聚乙烯的表面能为0.031J·m-2.)
步骤三、生物基树脂的共混挤出:
将50份经过清洗和表面处理的棕榈微粉加入到具有高度气密性和防腐能力的塑料高混设备中,维持高混设备的温度为70℃,向高混设备中加入1份环氧大豆油,混炼5min后,将高混设备的温度升高到95~100℃,加入0.2份马来酸酐,继续混炼5min。加入LLDPE树脂颗粒料40份,粒径为500目的碳酸钙7份,粒径为1800目的碳酸钙3份,硬脂酸锌3份。将高混设备的温度升高到85℃,混炼20min,出料后冷却,得到降解母粒预混料。预混料通过双阶挤出机组进行共混挤出,为了避免冷却过程中水分的吸入,造成产品的性能损失,采用模面热切及风冷拉条切粒的工艺使物料冷却并造粒,得到棕榈生物基/PE树脂母粒。至此完成整个工艺过程。
实施例3
步骤一、棕榈微粉的表面清洗:
将100份800目的棕榈皮微粉置入反应容器,按照浴比1:4向反应容器中加入400份丙酮,关闭反应容器使体系密封,加热至60℃,以500转/min的速度搅拌分散30min,静置使棕榈微粉沉降,使用压板将沉降的固体物轻微压实,抽出压板上方的澄清液,回收澄清液,蒸馏回收大量的丙酮溶剂,剩余的浊溶液过滤后,集中蒸馏回收溶剂。抬起压板,向反应容器中再次加入500份预热至50℃的丙酮作为分散介质,以500转/min的速度搅拌分散15min,静置使棕榈微粉沉降,使用压板将沉降的固体物轻微压实,抽出压板上方的澄清液。重复此操作4次后,按照同样的方法以环己烷为分散介质进行溶剂置换,至此完成工艺的清洗步骤。
步骤二、棕榈微粉的表面处理:
将溶剂置换后的反应体系加热至80℃,馏出物以3A分子筛除水后回流至反应釜,抽样检测,直至反应容器中的反应体系中水含量低于0.5mg/L,将5份1,6-亚己基二异氰酸酯溶于环己烷,加入至反应容器中,回流反应30min。将正十六醇8份溶于加热的正辛烷,加入至反应容器中,在加热和搅拌的条件下继续回流反应2h,再向反应体系中加入3份的乙酰氯,改用4A分子筛和CaO干燥馏出物,回流反应直至没有HCl产物馏出,加热搅拌,抽真空,使反应容器中的液相全部蒸出,得到经过清洗,表面处理和严格除水后的干燥棕榈生物质微粉。至此完成工艺的第二个步骤。检测表面处理前后生物质粉体的红外光谱,如图2所示,从图中可以看出处理后的生物质在2853cm-1处出现了亚甲基的吸收振动峰,1300cm-1处出现了长脂肪链的扭曲振动峰,虽然由于背景光谱较为复杂,但这两处特征峰的出现可以证明,表面改性确实将长的脂肪链引入到了生物质的表面上。
步骤三、生物基树脂的共混挤出:
将60份经过清洗和表面处理的棕榈微粉加入到具有高度气密性和防腐能力的塑料高混设备中,维持高混设备的温度为70℃,向高混设备中加入2份聚丙烯蜡,1份环氧大豆油,混炼5min后,将高混设备的温度升高到95~100℃,加入0.2份马来酸酐,继续混炼5min。加入PP树脂颗粒料30份,粒径为500目的碳酸钙5份,粒径为3000目的碳酸钙5份,硬脂酸钙3份。将高混设备的温度升高到90℃,混炼20min,出料后冷却,得到降解母粒预混料。预混料通过双阶挤出机组进行共混挤出,为了避免冷却过程中水分的吸入,造成产品的性能损失,采用模面热切及风冷拉条切粒的工艺使物料冷却并造粒,得到棕榈生物基/PP树脂母粒。至此完成整个工艺过程。
实施例4
步骤一、棕榈微粉的表面清洗:
将100份1200目的棕榈微粉置入反应容器,按照浴比1:5向反应容器中加入500份丙酮,关闭反应容器使体系密封,加热至50℃,以500转/min的速度搅拌分散30min,静置使棕榈微粉沉降,使用压板将沉降的固体物轻微压实,抽出压板上方的澄清液,回收澄清液,蒸馏回收大量的丙酮溶剂,剩余的浊溶液过滤后,集中蒸馏回收溶剂。抬起压板,向反应容器中再次加入500份预热至50℃的丙酮作为分散介质,以500转/min的速度搅拌分散15min,静置使棕榈微粉沉降,使用压板将沉降的固体物轻微压实,抽出压板上方的澄清液。重复此操作3次后,按照同样的方法以正辛烷为主要分散介质进行溶剂置换,至此完成工艺的清洗步骤。
步骤二、棕榈微粉的表面处理:
将溶剂置换后的反应体系加热至110℃(加入适量环己烷调整体系的沸点),馏出物以3A分子筛除水后回流至反应釜,抽样检测,直至反应容器中的反应体系中水含量低于0.2mg/L,将5份2,4-甲苯二异氰酸酯二异氰酸酯溶于正辛烷,加入至反应容器中,回流反应30min。将正十八醇6份溶于加热的正辛烷,加入至反应容器中,在加热和搅拌的条件下继续回流反应2h,再向反应体系中加入适量的乙酰氯,改用4A分子筛和CaO干燥馏出物,回流反应2h后,停止搅拌,使反应体系降温至50℃,以压板将沉降的棕榈生物质轻微压实,抽出上清液,使用正戊烷进行溶剂置换,在溶剂置换后加热搅拌,抽真空,使反应容器中的液相全部蒸出,得到经过清洗,表面处理和严格除水后的干燥棕榈生物质微粉。至此完成工艺的第二个步骤。
步骤三、生物基树脂的共混挤出:
将55份经过清洗和表面处理的棕榈微粉加入到具有高度气密性和防腐能力的塑料高混设备中,维持高混设备的温度为70℃,向高混设备中加入1份环氧大豆油,1份聚乙烯醇,混炼5min后,将高混设备的温度升高到95~100℃,加入0.2份衣康酸,继续混炼5min。加入PLA树脂颗粒料40份。将高混设备的温度升高到85℃,混炼20min,出料后冷却,得到降解母粒预混料。预混料通过双阶挤出机组进行共混挤出,为了避免冷却过程中水分的吸入,造成产品的性能损失,采用模面热切及风冷拉条切粒的工艺使物料冷却并造粒,得到棕榈生物基/PLA树脂母粒。至此完成整个工艺过程。
上述实施例中所述的“份”均为重量份。
以上所述,仅为本发明较佳的具体实施方式,这些具体实施方式都是基于本发明整体构思下的不同实现方式,而且本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书的保护范围为准。

Claims (10)

1.一种使用棕榈生物质粉为原料的生物基复合材料制备方法,其特征在于,
步骤一、棕榈微粉的清洗:
①将100份600~1200目的棕榈微粉置入反应容器,按照浴比1:4或1:5的比例向反应容器中加400~500份丙酮,关闭反应容器使体系密封,加热至50~60℃,以500转/min的速度搅拌分散30min,静置使棕榈微粉沉降,使用压板将沉降的固体物轻微压实,抽出压板上方的澄清液,回收澄清液,蒸馏回收丙酮溶剂,剩余的浊溶液过滤后,集中蒸馏回收溶剂;②抬起压板,向反应容器中再次加入500份预热至50℃的丙酮作为分散介质,以500转/min的速度搅拌分散15min,静置使棕榈微粉沉降,使用压板将沉降的固体物轻微压实,抽出压板上方的澄清液;③重复②的操作3~4次后,按照②的方法再以环己烷、正辛烷为分散介质进行溶剂置换,至此完成清洗步骤;
步骤二、棕榈微粉的表面处理:
①将溶剂置换后的反应体系加热至80~100℃,馏出物以3A分子筛除水后回流至反应釜,抽样检测,直至反应容器中的反应体系中水含量低于0.2~0.5mg/L,将3份或5份1,6-亚己基二异氰酸酯、或5份2,4-甲苯二异氰酸酯二异氰酸酯溶于环己烷,加入至反应容器中,回流反应30min;②将正十六醇5份或8份溶于加热的正辛烷,或将正十八醇6份溶于加热的正辛烷,然后加入至反应容器中,在加热和搅拌的条件下继续回流反应2h,再向反应体系中加入3份的乙酰氯,改用4A分子筛和CaO干燥馏出物,回流反应2h后,停止搅拌,使反应体系降温至50℃;③以压板将沉降的棕榈生物质轻微压实,抽出上清液,使用正戊烷进行溶剂置换,在溶剂置换后加热搅拌,抽真空,使反应容器中的液相全部蒸出,得到经过清洗、表面处理和严格除水后的干燥棕榈生物质微粉,至此完成表面处理步骤;
步骤三、生物基树脂的共混挤出:
①将50~60份经过清洗和表面处理的棕榈微粉加入到具有高度气密性和防腐能力的塑料高混设备中,维持高混设备的温度为70℃,向高混设备中加入1份环氧大豆油、或2份聚丙烯蜡和1份环氧大豆油、或1份环氧大豆油,1份聚乙烯醇,混炼5min后,将高混设备的温度升高到95~100℃,加入0.2份马来酸酐或0.2份衣康酸,继续混炼5min;②加入LLDPE树脂颗粒料40份,粒径为500目的碳酸钙7份,粒径为1800目的碳酸钙3份和硬脂酸锌3份、或PP树脂颗粒料30份,粒径为500目的碳酸钙5份,粒径为3000目的碳酸钙5份和硬脂酸钙3份、或PLA树脂颗粒料40份;③将高混设备的温度升高到85~90℃,混炼20min,出料后冷却,得到降解母粒预混料;④预混料通过双阶挤出机组进行共混挤出,为了避免冷却过程中水分的吸入,造成产品的性能损失,采用模面热切及风冷拉条切粒的工艺使物料冷却并造粒,得到棕榈生物基/PE树脂母粒,至此完成共混挤出步骤。
2.根据权利要求1所述的使用棕榈生物质粉为原料的生物基复合材料制备方法,其特征在于,步骤一中,棕榈微粉的目数为600目、800目或1200目。
3.根据权利要求1所述的使用棕榈生物质粉为原料的生物基复合材料制备方法,其特征在于,步骤一的①中,加热温度为50℃、55℃或60℃。
4.根据权利要求1所述的使用棕榈生物质粉为原料的生物基复合材料制备方法,其特征在于,步骤二的①中,反应体系加热温度为80℃、90℃或100℃。
5.根据权利要求1所述的使用棕榈生物质粉为原料的生物基复合材料制备方法,其特征在于,步骤二的①中,将3份1,6-亚己基二异氰酸酯溶于环己烷。
6.根据权利要求1所述的使用棕榈生物质粉为原料的生物基复合材料制备方法,其特征在于,步骤二的①中,将5份1,6-亚己基二异氰酸酯溶于环己烷。
7.根据权利要求1所述的使用棕榈生物质粉为原料的生物基复合材料制备方法,其特征在于,步骤二的①中,将5份2,4-甲苯二异氰酸酯二异氰酸酯溶于环己烷。
8.根据权利要求1所述的使用棕榈生物质粉为原料的生物基复合材料制备方法,其特征在于,步骤三的①中,将50份经过清洗和表面处理的棕榈微粉加入到具有高度气密性和防腐能力的塑料高混设备中。
9.根据权利要求1所述的使用棕榈生物质粉为原料的生物基复合材料制备方法,其特征在于,步骤三的①中,将55份经过清洗和表面处理的棕榈微粉加入到具有高度气密性和防腐能力的塑料高混设备中。
10.根据权利要求1所述的使用棕榈生物质粉为原料的生物基复合材料制备方法,其特征在于,步骤三的①中,将60份经过清洗和表面处理的棕榈微粉加入到具有高度气密性和防腐能力的塑料高混设备中。
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