CN105531421A - 用于排水剂和干强剂的聚环氧乙烷处理 - Google Patents
用于排水剂和干强剂的聚环氧乙烷处理 Download PDFInfo
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- D21H17/33—Synthetic macromolecular compounds
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- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
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- D—TEXTILES; PAPER
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
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- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
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- D—TEXTILES; 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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- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
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- D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
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Abstract
公开了一种处理纤维素浆料来改善排水性的方法，该方法包括将PEO以从0.1-10磅/吨的量添加到纤维素配料和将合成聚合物以0.1-10磅/吨的量添加至该配料中，使得该配料脱水并形成纸产品。
Description
本申请要求2013年8月9日提交的美国临时申请号61/864262的权益，其整个内容通过引用结合在此。
背景技术
纸和纸板是由通过纤维素纤维的含水浆料生产的，将这种浆料沉积在移动的造纸网(wire)或织物上，通过排水从浆料的固体组分形成纸片。这个次序之后是压制和干燥所述纸片，以进一步脱除水分。
在造纸网或织物上的纤维浆的排水或脱水经常是实现更快的纸机速度的限制步骤。改进的脱水还可以导致在压榨部和干燥部的形成更干的纸片，从而减少能源消耗。化学品往往在它到达造纸网或织物之前被添加到纤维浆中，以改善排水性/脱水性和固体留着；这些化学物质被称为助留剂和/或助滤剂。
干强添加剂用于造纸厂来增加纸张的强度。它通过增加内部键的形成来增加纸的强度。此外干强添加剂改善了耐破强度、撕裂强度、蜡选值、耐折性、刚度、纸机的运行性能，增加造纸填料的利用水平等。干强度添加剂也可减少掉毛和喷粉。
助留剂和助滤剂在一些含有高含量的可溶性有机物和盐的配料(furnish)基底中具有降低的效率。这些配料的两个这样的例子是中性亚硫酸盐半化学品(NSSC)和原生的牛皮纸挂面纸板，其中存在高含量的可溶性木质素和含有高阴离子电荷的其它有机材料。这些高度阴离子性的材料中和了常规助留剂和助滤剂上的电荷，显著降低其有效性。
发明详述
已经发现用聚环氧乙烷均聚物或共聚物(“PEO”)处理纤维素配料可以提高排水剂或强度剂在含有高含量的水溶性木质素的纤维素配料中的性能，其中该排水剂或强度剂通常是不活泼的。在这些纤维素配料中可溶性木质素含量为从25份/百万份(ppm)直至500ppm。
不希望受理论的束缚，据认为该PEO与在纤维素配料中过量的木质素和其它多余的阴离子材料反应，由此允许排水剂或增强剂来起作用，而不会受到与不希望的材料反应的阻碍。
分子量(Mw)是粘均分子量，如从特性粘度测定来确定的。
PEO可以是环氧乙烷的均聚物，或环氧乙烷的共聚物。合适的共聚单体包括环氧丙烷或环氧丁烷。最优选的是聚环氧乙烷的均聚物。另外用于制造PEO共聚物的合适的共聚单体可以是阳离子、阴离子、非离子的或疏水单体，以及它们的任何混合物。PEO的均聚物或共聚物的分子量范围可以为从1000道尔顿直至25,000,000道尔顿或100,000至15,000,000道尔顿或1,000,000至10,000,000道尔顿。含有环氧乙烷的均聚物或共聚物的实例是UcarflocTM300、302、304和309(可从密歇根州Midland的DowChemical得到)。
PEO处理的进料点可包括浓浆料(thickstock)，稀浆料，白水，或加工水。PEO处理可以在配浆槽，成浆池、风机水泵、净化器、离心筛、白水回收装置、白水盘和白水仓进行添加。
PEO的处理用量范围可以基于每吨配料固体为从0.01磅(lbs)至10磅的PEO聚合物。该用量也可以基于配料体积，基于每配料或基底水的体积从0.01ppm至10,000ppm的PEO。PEO通常以干粉或粒状产品提供，其中，将其在施用部位溶解。为了便于使用，它也可以以浆料或分散体提供给最终用户，在那里它可以稀释并送入工艺流。
排水剂或强度剂将由于PEO处理而发挥作用，其通常是水溶性的或水分散性合成聚合物(“合成高分子”)。所述合成聚合物可以是非离子聚合物，阳离子共聚物或阴离子共聚物。
用于制造所述合成聚合物的非离子单体包括但不限于，丙烯酰胺；甲基丙烯酰胺；N-烷基丙烯酰胺，例如N-甲基丙烯酰胺；N，N-二烷基丙烯酰胺，如N，N-二甲基丙烯酰胺、甲基丙烯酸甲酯、丙烯酸甲酯；丙烯腈、N-乙烯基甲基乙酰胺、N-乙烯基甲酰胺、N-乙烯基甲基甲酰胺、乙酸乙烯酯、N-乙烯基吡咯烷酮和任何上述物质的混合物。本发明预期其它类型的非离子单体都可以使用。一种以上的非离子型单体可用于制造合成聚合物。优选使用的非离子单体是丙烯酰胺；甲基丙烯酰胺，N-乙烯基甲酰胺。
用于制造合成聚合物的阳离子单体包括但不限于阳离子烯键式不饱和单体，例如二烯丙基二烷基卤化物如二烯丙基二甲基氯化铵、二烷基氨基烷基化合物的(甲基)丙烯酸酯如二甲基氨基乙基(甲基)丙烯酸酯、二乙基氨基乙基(甲基)丙烯酸酯、二甲基氨基丙基(甲基)丙烯酸酯、2-羟基二甲基氨丙基(甲基)丙烯酸酯、氨基乙基(甲基)丙烯酸酯、及其盐和季铵盐；N，N-二烷基氨基烷基(甲基)丙烯酰胺，如N，N-二甲基氨基乙基丙烯酰胺，及其盐和季铵盐，以及前述的混合物。一种以上的非离子型单体的可用于制造所述合成聚合物。最优选的是二烯丙基二甲基氯化铵和二甲基氨基乙基(甲基)丙烯酸酯及其盐和季铵盐，以及前述的混合物。
聚(乙烯胺)也是用于本发明的合适的阳离子合成聚合物。聚乙烯胺可以是均聚物或共聚物。生产聚乙烯聚合物的一种方法是通过单体聚合，然后进行水解。水解的水平可以表示为“％水解度”或“水解度％”，以摩尔计。水解聚合物因此可以被描述为“％水解的。”此外水解的水平可以是近似的。就申请人的发明目的而言，被称为“50％水解的”聚(乙烯基胺)是指从40％至60％水解的。同样地，约100％水解的聚(乙烯基胺)表示80％至100％的水解度。水解反应导致的一些或全部单体转化成胺，因为通过控制水解反应，就可以改变所得到的具有胺官能度的单体的百分比。
用于制造聚(乙烯基胺)的单体的实例包括但不限于，N-乙烯基甲酰胺，N-乙烯基甲基甲酰胺、N-乙烯基邻苯二甲酰亚胺、N-乙烯基琥珀酰亚胺、N-乙烯基-叔丁基氨基甲酸酯、N-乙烯基乙酰胺和任何前述的混合物。最优选的是通过N-乙烯基甲酰胺的水解所制备的聚合物。在共聚物的情况中，例如上述那些的非离子单体是优选的共聚单体。或者，聚(乙烯基胺)可以通过聚合物的衍生化来制备。该方法的实例包括但不限于，聚丙烯酰胺的霍夫曼反应。可以预期，可以使用聚(乙烯基胺)或多胺的其他合成途径。
非离子单体对阳离子单体的摩尔百分比可以落入约100∶1至1∶100，或80∶20至20∶80，或75∶25至25∶75或40∶60至60∶40的范围内，其中非离子单体和阳离子单体的摩尔百分比加起来必须为100％。但是应该理解的是，多于一种的非离子或阳离子单体可以存在于合成聚合物中。
用于制造合成聚合物的阴离子单体包括但不限于丙烯酸；甲基丙烯酸；马来酸；衣康酸、丙烯酰胺乙醇酸、2-丙烯酰胺-2-甲基1-丙磺酸、3-烯丙氧基-2-羟基-1-丙磺酸、苯乙烯磺酸、乙烯基磺酸、乙烯基膦酸、2-丙烯酰胺-2-甲基丙烷膦酸的游离酸和盐、和任何上述物质的混合物。最常见的是丙烯酸、甲基丙烯酸和2-丙烯酰胺-2-甲基1-丙磺酸的游离酸或盐。当酸的盐形式用于制造阴离子聚合物时，该盐选自Na+，K+或NH4。多于一种类型的阴离子性单体可用于制造合成聚合物。
非离子单体与阴离子单体的摩尔百分比可落入大约100∶1至1∶100或90∶10至30∶70或40∶60至70∶30的范围内，其中非离子单体与阴离子单体的摩尔百分比必须相加达到100％。应该理解多于一种类型的非离子单体可存在。也可以理解多于一种类型的阳离子单体可以存在。
合成的水溶性或水分散的聚合物也可以被改性来赋予合成聚合物额外的属性，或改变合成聚合物结构。单体的聚合可以在多官能试剂存在下进行，或该多官能试剂可以用于处理聚合物的后聚合。有用的多官能试剂包括具有至少两个双键，一个双键和一个反应性基团，或两个反应性基团的化合物。含有至少两个双键的那些化合物的示例是N，N-亚甲基双丙烯酰胺、N，N-亚甲基双甲基丙烯酰胺、聚乙二醇二丙烯酸酯、聚乙二醇酯二甲基丙烯酸酯；N-乙烯基丙烯酰胺、二乙烯基苯、三烯丙基铵盐、和N-甲基烯丙基丙烯酰胺。含有至少一个双键和至少一个反应性基团的多官能支化剂包括丙烯酸缩水甘油酯；甲基丙烯酸缩水甘油酯；丙烯醛；和羟甲基丙烯酰胺。含有至少两个反应性基团的多官能支化剂包括二醛类，如乙二醛；与二环氧化合物；表氯醇。
在本发明中使用的合成聚合物的实例包括但不限于聚乙烯胺，乙醛酸化的阳离子聚丙烯酰胺和阳离子聚丙烯酰胺。优选的是100％水解的聚乙烯基胺，50％水解的聚乙烯基胺与含有至少10摩尔％的阳离子单体的阳离子聚丙烯酰胺。一个例子可以是含有至少10摩尔％二烯丙基二甲基氯化铵或10摩尔％二甲基氨基乙基(甲基)丙烯酸酯的阳离子聚丙烯酰胺。本发明的另外有用的聚合物包括PerformTM产品如SP7200(阴离子型聚丙烯酰胺聚合物)，(Hercules公司，WilmingtonDE；HercobondTM6350(聚乙烯胺共聚物聚合物)，HercobondTM6363(聚乙烯胺共聚物)，HercobondTM6950(聚乙烯胺共聚物)，HercobondTM1307(改性的阳离子聚丙烯酰胺)，PerformTMPC8181(阳离子聚丙烯酰胺)，PerformTMPC8179(阳离子聚丙烯酰胺)。
非离子，阳离子或阴离子聚合物的分子量范围可以为10,000至50,000,000道尔顿，或1,000,000至25,000,000道尔顿，或5,000,000至20,000,000道尔顿。
处理是通过在造纸系统中的进料点将PEO添加到纤维素配料(浆料)，以及加入水溶性或水分散性合成聚合物到经过处理的浆料中来进行的。所述PEO和所述合成聚合物可以在相同的进料点或不同的进料点加入。所述PEO和合成聚合物可以同时、单独或作为混合物加入。在一个实施方案中，PEO和合成聚合物可以按顺序加入到造纸系统中。然后将浆料在造纸网上排水，使纤维浆脱水和形成纸片。当PEO和合成聚合物彼此结合使用时，可以观察到改善的排水性。
当PEO与合成聚合物一起使用时，可以使用更少的合成聚合物，并且仍然保持相同的性能水平(排水性)。
合成聚合物的进料点可以包括浓浆料或稀浆料。合成聚合物的可能的添加点可以包括配浆槽，成浆池、风机水泵，净化器，以及在离心筛之前或之后。合成聚合物的用量范围可以基于每吨配料固体为从0.01磅至10磅的活性聚合物，或基于每吨配料固体为0.01至5，或0.05至5，或0.1至2磅所述聚合物。合成聚合物可以以干燥的或粒状的粉末、水溶液或分散体或反相乳液形式制造，并提供给最终用户。
PEO与合成的水溶性聚合物的重量比的范围可以从100∶1到1∶100，或80∶20至20∶80或50∶50至10∶90。
用于本发明方法的合适的纤维素配料或纤维纸浆包括常规的造纸浆料，如传统的化学纸浆。例如，可以使用漂白和未漂白的硫酸盐浆和亚硫酸盐纸浆，机械纸浆如磨木浆，热磨机械纸浆，化学-热磨机械纸浆，再生纸浆如旧瓦楞箱，新闻纸，办公废纸，杂志纸和其他非脱墨废物，脱墨废物，以及它们的混合物。纤维素配料或浆料的pH范围可以是4至8。
实施例
利用包括中性亚硫酸盐半化学品(NSSC)，原生牛皮纸，和旧瓦楞纸箱(OCC)的造纸机浆进行了一系列的排水实验。使用真空试验来对本发明方法的排水性能进行评价，其中将布氏漏斗固定在量筒顶上。将500毫升(ml)纸浆浆料在烧杯中使用机械顶置式混合器混合，并将注明的(noted)聚合物处理依次加入。记录收集滤液的注明量所需的时间，其中较低的时间代表了所期望的更快的排水。PEO是一种高分子量(7百万)的均聚物，HercobondTM6950是阳离子改性的聚胺水溶性聚合物(Hercules，WilmingtonDE)。表1中的数据证明，与未处理的系统相比，HercobondTM6950没有排水响应。PEO的排水响应是显著的。注意到本发明方法具有高的排水响应性，其中纸浆浆料首先用PEO处理，接着加入HercobondTM6950。
表1
| PEO | Hercobond 6950 | |||
| 运行号 | #/T | #/T | 200ml | 250ml |
| 1 | 0 | 0 | 720 | n/a |
| 2 | 0.2 | 0 | 29 | 52 |
| 3 | 0.2 | 0.5 | 13 | 19 |
| 4 | 0.2 | 0.25 | 14 | 22 |
| 5 | 0.1 | 0 | 150 | 360 |
| 6 | 0.1 | 0.5 | 10 | 13 |
| 7 | 0 | 0.5 | 780 | n/a |
| 8 | 0.2 | 0.5 | 23 | 45 |
Claims (16)
1.一种处理纤维素浆料来改善排水性的方法，其包括以0.1-10磅/吨的量将PEO添加到纤维素配料中，和以0.1-10磅/吨的量将合成聚合物添加至所述配料中，使该配料脱水并形成纸产品。
2.如权利要求1的方法，其中所述的PEO选自环氧乙烷的均聚物，环氧乙烷与环氧丙烷的共聚物，和环氧乙烷与环氧丁烷的共聚物。
3.如权利要求1或2的方法，其中该合成聚合物是阴离子聚合物。
4.如权利要求1-3中任一项的方法，其中该合成聚合物是阴离子聚丙烯酰胺。
5.如权利要求1或2的方法，其中该合成聚合物是阳离子聚丙烯酰胺。
6.如权利要求1-3中任一项的方法，其中该合成聚合物是包含聚乙烯基胺或聚乙烯基甲酰胺的均聚物或共聚物。
7.如权利要求1-6中任一项的方法，其中该PEO具有介于100,000和15,000,000道尔顿的分子量。
8.如权利要求1-7中任一项的方法，其中该合成聚合物具有1,000,000-25,000,000道尔顿的分子量。
9.如权利要求3或4的方法，其中所述阴离子聚合物是使用至少一种阴离子单体制成的，该阴离子单体单体选自丙烯酸、甲基丙烯酸、马来酸、衣康酸、丙烯酰胺乙醇酸、2-丙烯酰胺-2-甲基-1-丙磺酸、3-烯丙氧基-2-羟基-1-丙磺酸、苯乙烯磺酸、乙烯基磺酸、乙烯基膦酸、2-丙烯酰胺-2-甲基丙烷膦酸的游离酸和盐、和任何上述物质的混合物。最常用的是丙烯酸、甲基丙烯酸、和2-丙烯酰胺-2-甲基-1-丙磺酸的游离酸或盐。
10.如权利要求5或6的方法，其中该阳离子聚合物是使用至少一种阳离子单体制成的，该阳离子单体选自二烯丙基二烷基卤化铵，例如二烯丙基二甲基氯化铵；二烷基氨基烷基化合物的(甲基)丙烯酸酯，例如二甲基氨基乙基(甲基)丙烯酸酯、二乙基氨基乙基(甲基)丙烯酸酯、二甲基氨基丙基(甲基)丙烯酸酯、2-羟基二甲基氨基丙基(甲基)丙烯酸酯、氨基乙基(甲基)丙烯酸酯、及其盐和季铵盐；N，N-二烷基氨基烷基(甲基)丙烯酰胺，例如N，N-二甲基氨基乙基丙烯酰胺、以及其盐和季铵盐，和前述的混合物。
11.如权利要求1-10中任一项的方法，其中PEO对合成水溶性聚合物的重量比在从约100∶1-约1∶100的范围内。
12.如权利要求1-11中任一项的方法，其中PEO与合成水溶性聚合物的比例为约80∶20-约20∶80。
13.如权利要求1-12中任一项的方法，其中PEO与合成水溶性聚合物的比例为约50∶50-约10∶90。
14.如权利要求1-10中任一项的方法，其中加入到所述配料中的合成聚合物的量是每吨配料固体约0.05磅-约5磅的合成聚合物。
15.如权利要求1-14中任一项的方法，其中加入到所述配料中的合成聚合物的量是每吨配料固体0.1磅-2磅的合成聚合物。
16.如权利要求1-15中任一项的方法，其中所述纤维素配料的可溶性木质素含量是25ppm-500ppm。
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- 2014-08-07 CA CA2918468A patent/CA2918468A1/en active Pending
- 2014-08-07 KR KR1020167006151A patent/KR20160040297A/ko not_active Withdrawn
- 2014-08-07 CN CN201480045034.0A patent/CN105531421A/zh active Pending
- 2014-08-07 BR BR112016002152A patent/BR112016002152A2/pt not_active IP Right Cessation
- 2014-08-07 MX MX2016000879A patent/MX2016000879A/es unknown
- 2014-08-07 US US14/453,662 patent/US20150041090A1/en not_active Abandoned
- 2014-08-07 WO PCT/IB2014/002506 patent/WO2015063585A2/en active Application Filing
- 2014-08-07 CA CA2922074A patent/CA2922074A1/en not_active Abandoned
- 2014-08-07 AU AU2014343348A patent/AU2014343348A1/en not_active Abandoned
- 2014-08-07 EP EP14843177.8A patent/EP3030716A2/en not_active Withdrawn
- 2014-08-11 TW TW103127538A patent/TW201512491A/zh unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4070236A (en) * | 1974-11-15 | 1978-01-24 | Sandoz Ltd. | Paper manufacture with improved retention agents |
| CA2119842A1 (en) * | 1993-03-25 | 1994-09-26 | Elliott Echt | Phenolic compound/polyethylene oxide retention system |
| US5645731A (en) * | 1993-04-30 | 1997-07-08 | Hercules Incorporated | Aqueous suspensions of poly(ethylene oxide) useful as a flocculent |
| CN1088777C (zh) * | 1996-02-13 | 2002-08-07 | 希巴特殊化学水处理有限公司 | 加填料纸的生产方法及其所用的组合物 |
| CN1275116A (zh) * | 1997-09-30 | 2000-11-29 | 纳尔科化学公司 | 胶态硼硅酸盐及其在造纸生产中的应用 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112218930A (zh) * | 2018-04-04 | 2021-01-12 | 索理思科技公司 | 将强度添加剂泡沫辅助施用到纸制产品 |
| CN112218930B (zh) * | 2018-04-04 | 2023-11-14 | 索理思科技公司 | 将强度添加剂泡沫辅助施用到纸制产品 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2922074A1 (en) | 2015-05-07 |
| WO2015063585A3 (en) | 2015-07-16 |
| CA2918468A1 (en) | 2015-05-07 |
| KR20160040297A (ko) | 2016-04-12 |
| MX2016000879A (es) | 2016-05-05 |
| TW201512491A (zh) | 2015-04-01 |
| WO2015063585A2 (en) | 2015-05-07 |
| US20150041090A1 (en) | 2015-02-12 |
| BR112016002152A2 (pt) | 2017-08-29 |
| EP3030716A2 (en) | 2016-06-15 |
| AU2014343348A1 (en) | 2016-02-04 |
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