CN111648160A - 一种环保型无氟杯子及其制备方法 - Google Patents
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- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/186—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof from or via fluosilicic acid or salts thereof by a wet process
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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- D21J5/00—Manufacture of hollow articles by transferring sheets, produced from fibres suspensions or papier-mâché by suction on wire-net moulds, to couch-moulds
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Abstract
本发明公开了一种非木植物纤维全降解无氟不渗漏杯子的生产制备方法,将直接原料配比后疏解得均匀的浆料,加入防水剂、湿强剂、干强剂等助剂制得混合浆料,然后将制得的改性纳米二氧化硅和丙烯酸共聚物的共混物喷涂在纸浆模塑湿坯上,最后对纸浆模塑湿坯进行脱水、热压定型、切边制成模塑杯子制品。本发明提供的非木植物纤维全降解无氟不渗漏杯子的生产方法制备的产品为绿色环保全降解材料,其废弃后可直接丢弃并自然降解成种植用土壤;或经破碎还原成种植用土壤进行复用或丢弃。
Description
技术领域
本发明属于全降解植物纤维杯子制造技术领域。
背景技术
随着饮料等商业的发展,一次性纸杯子的用量越来越大,为了赋予纸杯产品防水防油功能,最常见的是使用氟系防水防油剂,例如PFOA(全氟辛酸及盐)和PFOS(全氟辛烷磺酰基化合物)等,但它们在环境中很难被降解,具有生物累积性和多种毒性,同时具备持久性有机污染物的共同特性,被认为是21世纪里需要重点关注的新型持久性环境污染物。
纸浆模塑是一种立体造纸技术。它以废纸、木浆或其它植物纤维为原料,在模塑机上由特殊的模具塑造出具有一定形状的纸浆制品。它具有四大优势:1.原料为废纸、木浆或其它植物纤维,包括板纸、废纸箱纸、废白边纸、针叶木浆、阔叶木浆、竹浆、蔗渣浆等,来源广泛;2.其制作过程由制浆、吸附成型、干燥定型等工序完成,流程较短,对环境无害;3.产品可以回收再生利用;4.体积比发泡塑料小,质量轻,可重叠,交通运输方便。
发明内容
本发明的目的就是针对现有技术存在的上述问题,提供一种新的非木植物纤维全降解无氟环保型纸浆模塑杯子及其制备方法。
本发明是这样实现的,一种环保型无氟杯子的制备方法,包括以下步骤:
步骤1:将原料按配比计量,用水力碎浆机进行碎浆获得浆料,碎浆浓度为3.5%~4.0%;
步骤2:将处理好的浆料用双功能疏解机进行疏解,经过疏解机的切断、分丝、细纤维化,获得均匀的浆料;
步骤3:将浆料与白水混合,加入防水剂、湿强剂和干强剂等化学药品,搅拌均匀,制得混合浆料;
步骤4:将混合浆料经管道运送至杯子模塑成型机,经真空抽滤脱水制得纸浆模塑杯子湿胚;
步骤5:将改性纳米二氧化硅与丙烯酸共聚物的共混物喷涂在纸浆模塑湿胚上;
步骤6:将纸浆模塑湿胚进行脱水、热压定型、转移切边制成模塑杯子成品。
进一步,步骤1中,所述的原料由白色甘蔗浆和白色竹浆按照30-~40:60~70重量比例组成。
进一步,步骤2中控制浆料质量:湿重14~17g,打浆度20~23°SR,粘度为60~70Pa·s。
进一步,步骤3中,所述的防水剂为不含氟树脂,湿强剂是聚酰胺聚环氧氯丙烷树脂,干强剂是淀粉及其改性物,均选用食品级市售产品。所述的防水剂、干强剂和湿强剂等化学药品根据配浆量的多少按绝干浆比例来确认添加量,所述的防水剂、干强剂和湿强剂等化学药品与绝干纸浆纤维的比例进一步选择为:防水剂0.8%~1.6%,干强剂0.6%~1.2%,湿强剂0.6%~1.2%。
进一步,步骤3中,浆料与白水按照DCS设置进行配浆,配浆浓度0.27%~0.32%,配浆时间15~25min。
进一步,步骤4中纸浆模塑湿坯脱水处理的操作参数:真空度-0.03MPa~-0.035MPa抽吸负压下脱水15~20s,至含水率为65~75%。步骤4中,所述的纸浆模塑杯子湿坯脱水处理,优选的操作参数:真空度-0.03MPa~-0.035MPa抽吸负压下脱水15~20s,至含水率为65~75%。
进一步,步骤5所述的改性纳米二氧化硅与丙烯酸共聚物的制备方法如下:
(1)纳米二氧化硅的合成
将乙醇和水倒入正硅酸四乙酯中,三者体积比为50:2~3:5~6,用氨水调节pH值为9.5~10.0,在50~55℃下搅拌4.0~4.5小时,冷却至室温得白色产物;
(2)纳米二氧化硅的改性
将纳米二氧化硅颗粒加入乙醇水溶液(含水比例15%~20%)中,固液比=1.0~1.5g:100mL,超声处理20~30分钟。然后加入十六烷基三甲氧基硅烷(纳米二氧化硅:十六烷基三甲氧基硅烷=1g:80~100mL),用氨水调节pH值为9.5~10.0,搅拌混合物并冷凝回流,70~80℃下加热10~12小时,室温冷却后过滤;
(3)丙烯酸共聚物制备
油浴搅拌并冷凝回流条件下,在二甲基甲酰胺内加入甲基丙烯酸甲酯、甲基丙烯酸月桂酯和偶氮二异丁腈,二甲基甲酰胺:甲基丙烯酸甲酯:甲基丙烯酸月桂酯:偶氮二异丁腈的投料比为=10~15mL:1.5~2.0g:1.5~2.0g:0.10~0.15g,70~80℃下反应10~12小时,冷却至室温,将混合物倒入甲醇溶液(体积为二甲基甲酰胺2~2.5倍),析出的共聚物再用甲醇溶液洗涤3~4次,50~60℃下干燥10~12小时,得到目标产物。
进一步,步骤5所述的喷涂步骤,是指:
将丙烯酸共聚物溶于有机溶剂,然后加入改性纳米二氧化硅,丙烯酸共聚物与改性纳米二氧化硅的重量比=40~60:60~40,控制共混物的固形物质量浓度在45%~55%,超声处理10~15分钟,采用喷涂方式喷涂到纸浆模塑杯子湿胚上。共混物喷涂量:纸浆绝干纤维重量=1~5:100。
进一步,步骤6所述的热压定型条件是:压强在50~70kg/cm2、温度为170~230℃、时间为20~40s。
本发明的另一方面提供了一种利用所述环保型纸浆模塑杯子制备方法得到的纸浆杯子成品。
本发明的有益效果:
本发明采用竹子和普通农作物废料为浆料原料,制备得到的产品为绿色环保全降解材料,做到从源头到成品均无环境压力。产品使用废弃后可直接丢弃并自然降解成种植用土壤;或经破碎还原成种植用土壤进行复用或丢弃。利用纳米复合材料制备了超疏水涂层代替氟系防水防油剂如PFOA(全氟辛酸及盐)和PFOS(全氟辛烷磺酰基化合物)等,获得更好的抗水防渗透效果,并可有效保护使用者健康安全。
具体实施方式
下面结合实施例对本发明的具体实施方法作详细举例说明。下述实施例中没有特别说明的技术参数和助剂,本领域技术人员可以根据本技术领域的知识进行常规和适应性选择。
本发明提供的化学品制备方法实施例如下1-6所示:
实施例1:纳米二氧化硅的合成
将乙醇和水倒入正硅酸四乙酯中,三者体积为50:2:6,用氨水调节pH值为9.5,在50~55℃下搅拌4.5小时,冷却至室温,将所得白色产物离心,用乙醇溶液洗涤3次,然后在50~55℃下干燥。
实施例2:纳米二氧化硅的合成
将乙醇和水倒入正硅酸四乙酯中,三者体积为50:3:6,用氨水调节pH值为10.0,在50~55℃下搅拌4.5小时,冷却至室温,将所得白色产物离心,用乙醇溶液洗涤3次,然后在50~55℃下干燥。
实施例3:纳米二氧化硅的改性
将纳米二氧化硅颗粒加入15%的乙醇水溶液中,固液比=1.2g:100mL,超声处理25分钟。然后加入十六烷基三甲氧基硅烷(纳米二氧化硅:十六烷基三甲氧基硅烷=1g:90mL),用氨水调节pH值为9.5,搅拌混合物并冷凝回流,70~80℃下加热10小时,室温冷却后过滤,用乙醇溶液洗涤3次,然后在50~55℃下干燥。
实施例4:纳米二氧化硅的改性
将纳米二氧化硅颗粒加入20%乙醇水溶液中,固液比=1.0g:100mL,超声处理30分钟。然后加入十六烷基三甲氧基硅烷(纳米二氧化硅:十六烷基三甲氧基硅烷=1g:100mL),用氨水调节pH值为9.5,搅拌混合物并冷凝回流,70~80℃下加热10小时,室温冷却后过滤,用乙醇溶液洗涤3次,然后在50~55℃下干燥。
实施例5:丙烯酸共聚物制备
油浴搅拌并冷凝回流条件下,在二甲基甲酰胺内加入甲基丙烯酸甲酯、甲基丙烯酸月桂酯和偶氮二异丁腈,二甲基甲酰胺:甲基丙烯酸甲酯:甲基丙烯酸月桂酯:偶氮二异丁腈=10mL:1.5g:1.5g:0.10g,70~80℃下反应12小时,冷却至室温,将混合物倒入一定量的甲醇溶液(体积为二甲基甲酰胺2倍),析出的共聚物再用甲醇溶液洗涤3次,55℃下干燥10小时。
实施例6:丙烯酸共聚物制备
油浴搅拌并冷凝回流条件下,在二甲基甲酰胺内加入甲基丙烯酸甲酯、甲基丙烯酸月桂酯和偶氮二异丁腈,二甲基甲酰胺:甲基丙烯酸甲酯:甲基丙烯酸月桂酯:偶氮二异丁腈=15mL:2.0g:2.0g:0.15g,70~80℃下反应12小时,冷却至室温,将混合物倒入一定量的甲醇溶液(体积为二甲基甲酰胺2.5倍),析出的共聚物再用甲醇溶液洗涤4次,50℃下干燥11小时。
本发明提供的环保型纸浆模塑成形方法实施例包括以下步骤:
步骤1:将漂白竹浆和甘蔗浆原料进行解包、除杂、按照30-~40:60~70重量比称量配比,用水力碎浆机进行碎解获得粉碎料,碎浆浓度为3.5%~4.0%;
步骤2:将处理好的粉碎料用双功能疏解机进行疏解,经过疏解机的切断、分丝、细纤维化,获得均匀的浆料;湿重14~17g,打浆度20~23°SR,粘度为60~70Pa·s;
步骤3:将浆料与白水混合,加入防水剂、湿强剂和干强剂等化学药品,搅拌均匀,制得混合浆料;浆料与白水按照DCS设置进行配浆,配浆浓度0.27%~0.32%,配浆时间15~25min;所述的防水剂、干强剂和湿强剂等化学药品与绝干纸浆纤维的比例:防水剂0.8%~1.6%,干强剂0.6%~1.2%,湿强剂0.6%~1.2%;
步骤4:将混合浆料经管道运送至杯子模塑成型机,经真空抽滤脱水制得纸浆模塑杯子湿胚;纸浆模塑湿坯脱水处理的操作参数:真空度-0.03MPa~
-0.035MPa抽吸负压下脱水15~20s,至含水率为65~75%;
步骤5,将改性纳米二氧化硅与丙烯酸共聚物的共混物喷涂在纸浆模塑湿胚上:将丙烯酸共聚物加入二氯甲烷,然后加入改性纳米二氧化硅;丙烯酸共聚物:改性纳米二氧化硅=40~60:60~40,控制混合料浓度为45%~55%,超声处理10~15分钟,采用喷涂方式喷涂到纸浆模塑杯子湿胚上;共混物喷涂量:纸浆绝干纤维重量=1~5:100;
步骤6:将纸浆模塑杯子湿坯进行脱水处理、热压定型、切边制成模塑杯子制品;脱水处理条件:真空度-0.03MPa~-0.035MPa抽吸负压下脱水15~20s,含水率为65~75%。热压定型条件:压强在50~70kg/cm2、温度为170~230℃、时间为20~40s。
下面具体实施例7~9采用以上的生产方法,可热压定型成一次性环保杯子。
实施例7
本实施例提供的原料按照质量份数由白色竹浆60、白色甘蔗浆40组成。
本实施例中,防水剂、干强剂、湿强剂按绝干浆质量比例添加量为:0.8%、0.9%和0.6%。
本实施例采用的防水剂为不含氟树脂(德科纳米,LZ-XR88),湿强剂是聚酰胺聚环氧氯丙烷树脂(杭化哈利玛,WS-1C),干强剂是淀粉及其改性物(杭化哈利玛,HM-2800)。
本实施例采用的丙烯酸共聚物:改性纳米二氧化硅=40:60,喷涂量:纸浆绝干纤维重量=2:100。
最终非木植物纤维杯子目标产品吸水性为3.2g/m2,接触角为85.2°。
实施例8
本发明实施例提供的原料按照质量份数由竹浆70%、甘蔗浆30%组成。
本实施例中,防水剂、干强剂和湿强剂按绝干浆质量比例添加量为:1.0%、0.8%和1.1%。
本实施例采用的防水剂为不含氟树脂(庄杰化工,ZJ-XR88),湿强剂是聚酰胺聚环氧氯丙烷树脂(泰安鑫泉,XQ-1001),干强剂是淀粉及其改性物(杭化哈利玛,HM-2650B)。
本实施例采用的丙烯酸共聚物:改性纳米二氧化硅=50:50,喷涂量:纸浆绝干纤维重量=5:100。
所得非木植物纤维杯子产品吸水性为2.3g/m2,接触角为88.6°。
实施例9
本发明实施例提供的原料按照质量份数由竹浆65%、甘蔗浆35%组成。
本实施例中,防水剂、干强剂和湿强剂按绝干浆质量比例添加量为:1.2%、1.0%和0.7%。
本实施例采用的防水剂为不含氟树脂(HOLPOSON,ECO-0C),湿强剂是聚酰胺聚环氧氯丙烷树脂(同创精细化工,PAE-01),干强剂是淀粉及其改性物(杭化哈利玛,HM-2800)。
本实施例采用的丙烯酸共聚物:改性纳米二氧化硅=60:40,喷涂量:纸浆绝干纤维重量=3.5:100。
所得非木植物纤维杯子产品吸水性为2.9g/m2,接触角为87.3°。
以上实施例得到的纸浆模塑杯子产品为绿色环保全降解材料,其废弃后可直接丢弃并自然降解成种植用土壤;或经破碎还原成种植用土壤进行复用或丢弃。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种非木植物纤维全降解无氟杯子的制备方法,包括以下步骤:
步骤1:将原料按配比计量,用水力碎浆机进行碎浆获得浆料,碎浆浓度为3.5%~4.0%;
步骤2:将处理好的浆料用双功能疏解机进行疏解,经过疏解机的切断、分丝、细纤维化,获得均匀的浆料;
步骤3:将浆料与白水混合,加入防水剂、湿强剂和干强剂等化学药品,搅拌均匀,制得混合浆料;
步骤4:将混合浆料经管道运送至杯子模塑成型机,经真空抽滤脱水制得纸浆模塑杯子湿胚;
步骤5:将改性纳米二氧化硅与丙烯酸共聚物的共混物喷涂在纸浆模塑湿胚上;
步骤6:将纸浆模塑湿胚进行脱水、热压定型、转移切边制成模塑杯子成品。
2.如权利要求1所述的非木植物纤维全降解无氟杯子的制备方法,其特征在于:步骤1中,所述的原料为白色甘蔗浆和白色竹浆按照30-~40:60~70重量比例组成。
3.如权利要求1所述的非木植物纤维全降解无氟杯子的制备方法,其特征在于:步骤2中,所获浆料质量:湿重14~17g,打浆度20~23°SR,粘度为60~70Pa·s。
4.如权利要求1所述的非木植物纤维全降解无氟杯子的制备方法,其特征在于:所述的步骤3中,浆料与白水按照DCS设置进行配浆,配浆浓度0.27%~0.32%,配浆时间15~25min。
5.如权利要求1所述的非木植物纤维全降解无氟杯子的制备方法,其特征在于:步骤4中纸浆模塑湿坯脱水处理的操作参数:真空度-0.03MPa~-0.035MPa抽吸负压下脱水15~20s,至含水率为65~75%。
6.如权利要求1所述的非木植物纤维全降解无氟杯子的制备方法,其特征在于:所述的步骤5中改性纳米二氧化硅与丙烯酸共聚物由如下方法得到:
(1)纳米二氧化硅的合成
将乙醇和水倒入正硅酸四乙酯中,三者体积比为50:2~3:5~6,用氨水调节pH值为9.5~10.0,在50~55℃下搅拌4.0~4.5小时,冷却至室温,得白色产物;
(2)纳米二氧化硅的改性
将纳米二氧化硅颗粒加入乙醇水溶液中,固液比=1.0~1.5g:100mL,超声处理20~30分钟;然后加入十六烷基三甲氧基硅烷,用氨水调节pH值为9.5~10.0,搅拌混合物并冷凝回流,70~80℃下加热10~12小时,室温冷却后过滤;
(3)丙烯酸共聚物制备
油浴搅拌并冷凝回流条件下,在二甲基甲酰胺内加入甲基丙烯酸甲酯、甲基丙烯酸月桂酯和偶氮二异丁腈,二甲基甲酰胺:甲基丙烯酸甲酯:甲基丙烯酸月桂酯:偶氮二异丁腈=10~15mL:1.5~2.0g:1.5~2.0g:0.10~0.15g,70~80℃下反应10~12小时,得到目标产物。
7.如权利要求1所述的非木植物纤维全降解无氟杯子的制备方法,其特征在于:步骤5所述的喷涂是指:将丙烯酸共聚物溶于有机溶剂后加入改性纳米二氧化硅,丙烯酸共聚物:改性纳米二氧化硅=40~60:60~40;控制所得共混物溶液的固形物质量浓度在45%~55%,超声处理10~15分钟,采用喷涂方式喷涂到纸浆模塑杯子湿胚上;共混物喷涂量:纸浆绝干纤维重量=1~5:100。
8.如权利要求1所述的非木植物纤维全降解无氟杯子的制备方法,其特征在于:所述的热压定型条件是:压强在50~70kg/cm2、温度为170~230℃、时间为20~40s。
9.如权利要求1所述的非木植物纤维全降解无氟杯子成形方法,其特征在于:所述的防水剂、干强剂和湿强剂等化学药品与绝干纸浆纤维的比例:防水剂0.8%~1.6%,干强剂0.6%~1.2%,湿强剂0.6%~1.2%。
10.采用权利要求1-9任一所述的非木植物纤维全降解无氟杯子制备方法得到的纸浆模塑杯子产品。
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