CN105339547B - 处理纤维素纤维以生产含有微原纤化纤维素的组合物的方法和根据所述方法生产的组合物 - Google Patents
处理纤维素纤维以生产含有微原纤化纤维素的组合物的方法和根据所述方法生产的组合物 Download PDFInfo
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Abstract
本发明涉及一种处理纤维素纤维的方法，所述方法包括如下步骤：提供含有纤维素纤维的浆料，在第一步中将具有高摩尔质量的阴离子聚丙烯酰胺(A‑PAM)加入浆料，和在第二步中使含有纤维和A‑PAM的浆料经历机械处理，从而形成含有微原纤化纤维素的组合物。本发明进一步涉及根据所述方法生产的组合物。
Description
技术领域
本发明涉及在阴离子聚丙烯酰胺存在下通过机械处理纤维素纤维生产含有微原纤化纤维素的组合物的方法。本发明进一步涉及根据该方法生产的组合物
背景技术
微原纤化纤维素(MFC)是从木质纤维素纤维制得的材料，其中单独的微原纤维或微原纤化聚集体被部分或全部地彼此解离。MFC通常非常细(～20nm)并且长度一般为100nm到1μm。
微原纤化纤维素可通过多种不同方法制备。可机械处理纤维素纤维，使得形成微原纤维。但是，例如切碎或精制未处理的纤维素纤维以形成微原纤化纤维素是非常耗能的，因此不常使用。还可使用机械和化学处理的组合。可使用的化学品的实例通过化学反应改性(modify)纤维素或者通过将化学品接枝或吸附在纤维之上或之中而改性纤维素的那些。通过在纤维之上或之中引入羧酸基团或例如使用氧化所述纤维的TEMPO，得到改善的原纤化。但是，由于法律、成本或健康/安全风险(这在纸板中尤其重要)，氧化或引入阴离子基团的化学品的使用可受到限制。这是由于法律禁止例如在食品板或液体包装板中使用这些化学品。
在US5,964,983，公开了教导使用糖醛酸例如半乳糖醛酸或葡萄糖醛酸引入电荷或者使主要纤维壁带电的方法，这导致得到改进的MFC。
在为了形成微原纤化纤维素的纤维素纤维的机械处理过程中减少能量的另一方式是在原纤化步骤前加入光学增亮剂(OBA)。OBA已经显示在生产微原纤化纤维素的过程中提高机械设备的运性性能。但是，OBA通常不能用在纸板产品中，因为它不是食品应用中批准的添加剂，即没有被食品药品管理部门(FDA)批准。
WO2011051882A1公开了一种生产微原纤化纤维素的方法。纤维素纤维在挤出机中机械处理以形成微原纤化纤维素。还可向挤压机添加化学品，例如CMC，以生产改性的微原纤化纤维素。
然而，依然存在对于生产微原纤化纤维素的改进方法的需求。
发明内容
本发明的一个目的是提供以改良的且能源有效的方式生产含有微原纤化纤维素的组合物的方法。
本发明的另一目的在于生产一种包含具有高负电荷的微原纤化纤维素的方法。
这些目的和其他优点通过根据本发明的方法实现。通过向含有纤维素纤维的浆料加入阴离子聚丙烯酰胺，已经体现出可以非常有效的方式机械处理所述浆料以生产含有微原纤化纤维素的组合物。这可通过本发明的方法和所述方法的优选实施方式实现。
本发明涉及一种处理纤维素纤维的方法，该方法包含如下步骤：提供含有纤维素纤维的浆料；在第一步中将具有高摩尔质量的阴离子聚丙烯酰胺(A-PAM)加入所述浆料；在第二步中使所述浆料经历机械处理的，由此形成含有微原纤化纤维素的组合物。通过机械处理含有具有高摩尔质量的A-PAM和纤维素纤维的浆料，可以更能量有效得多的方式生产含有微原纤化纤维素的组合物。已经显示，具有高摩尔质量的阴离子聚丙烯酰胺将改善纤维素纤维的原纤化。
加入的A-PAM的摩尔质量优选高于10x 106g/mol。已经表明，具有低于10x 106g/mol的摩尔质量的A-PAM对于纤维素纤维的原纤化和机械处理的运行性能没有效果或具有小的效果。
加入的A-PAM的电荷低于-1.5mekv/g。已经表明，具有低于-1.5mekv/g的负电荷的A-PAM进一步将改善纤维素纤维的原纤化。
加入到浆料中的A-PAM的量优选为150-2500g/t(克每吨)干MFC。加入到浆料中的A-PAM的所需量取决于机械处理和处理的纤维素纤维。
优选将含有纤维和A-PAM的浆料的温度提高到高于50℃。通过提高含有纤维素纤维和A-PAM的浆料温度，已经显示吸收到纤维上的A-PAM的量增加。
还可向浆料中加入电解质。电解质优选具有单价、二价或者多价阳离子，例如为硫酸钠或氯化钙。通过向含有纤维素纤维和A-PAM的浆料中加入电解质，可降低纤维的阴离子电荷，从而提高A-PAM在纤维上的吸收。
浆料的电解质浓度优选为0.0001-0.5M。所需浓度取决于纤维素材料以及使用的A-PAM。
还可以向浆料中加入固定化学品(fixating agent)，例如染料或者光学增亮剂。因此可以将A-PAM吸收到纤维上的方式改性添加的A-PAM。
浆料中的纤维素纤维优选在加入阴离子聚丙烯酰胺前经过预处理。预处理可是机械的，化学的和/或酶促的。
优选地将浆料在高剪切设备中机械处理。已经显示，当在机械处理前将纤维素纤维与A-PAM混合时，使得含有MFC和A-PAM的浆料经历高剪切速率的设备例如流化器或匀化器的运行性能得到改善。
在机械处理过程中，浆料优选具有1-40重量％的浓度(稠度，consistency)。由于阴离子聚丙烯酰胺的加入会提高纤维悬浮液的电荷，所述纤维倾向于抗絮凝，这使得可增加浆料的浓度且仍然以高效方式生产含有微原纤化纤维素的组合物。
所述方法还可进一步包括在第三步中将具有高摩尔质量的阴离子聚丙烯酰胺(A-PAM)加入所述浆料；和在第四步中使含有纤维和A-PAM的浆料经历机械处理，从而形成含有微原纤化纤维素的组合物。因此可以多于一个步骤将阴离子聚丙烯酰胺加入所述浆料，且优选使浆料在A-PAM的每次添加后经历机械处理。
本发明进一步涉及根据上述方法制备的含有微原纤化纤维素和具有高摩尔质量的A-PAM的组合物。由于在制备微原纤化纤维素的过程中加入了阴离子聚丙烯酰胺，生产的含有微原纤化纤维素组合物将表现出提高的负电荷，这将改善组合物的稳定性。
具体实施方式
已经表明，通过在阴离子聚丙烯酰胺的存在下机械处理纤维素纤维，可以非常能量有效的方式生产含有微原纤化纤维素的组合物。
微原纤化纤维素的定义
微原纤化纤维素(MFC)也称为纳米纤维素。它典型地是从木质纤维素纤维(包括阔叶木或针叶木纤维两者)制得的材料。它还可以从微生物源、农业纤维例如麦秸秆浆、竹子或其他非木质纤维源制得。在微原纤化纤维素中，单独的微原纤维已经部分或者全部地互相分离。微原纤化纤维素原纤维一般非常细(～20nm)并且通常长度为100nm到10μm。但是，微原纤维也可较长，例如10-200μm，甚至由于宽的长度分布可找到2000μm长度。在MFC的定义中包括经过原纤化和表面上具有微原纤维的纤维以及分离且位于浆料的水相中的微原纤维。
此外，纤维素晶须、微晶纤维素(MCC)、微纤维素(MC)，微记数纤维素(microdenomimated cellulose)/纳米晶纤维素(NCC)或原纤化再生纤维素纤维和粒子也包含在MFC的定义中。
原纤维还可是聚合物涂覆的原纤维，例如化学或物理改性的原纤维。
本发明涉及处理纤维素纤维的方法，该方法包括如下步骤：提供含有纤维素纤维的浆料；在第一步中浆阴离子聚丙烯酰胺(A-PAM)加入所述浆料，和在第二步中使含有纤维和A-PAM的浆料经历机械处理，其中形成含有微原纤化纤维素和A-PAM的组合物。通过处理机械处理含有A-PAM和纤维素纤维的浆料，可以更能源有效得多的方式生产含有微原纤化纤维素的组合物。这是由于阴离子聚丙烯酰胺的存在将改善原纤化以及所用机械设备的运性性能。已经表明A-PAM提高组合物的电荷，以降低纤维间的摩擦并且降低所用机械设备和纤维间的摩擦，这使得更容易原纤化所述纤维，并改善设备的运性性能。此外，A-PAM是非常成本有效的化学品，并且没有毒性，这使得可用于基于食品的包装材料，例如食品板和液体包装板。
向含有纤维素纤维的浆料加入阴离子聚丙烯酰胺，随后将阴离子聚丙烯酰胺与含有纤维素纤维的浆料混合。优选混合进行至少2分钟。经行纤维素纤维和A-PAM的混合以确保浆料中的组分在机械处理前被良好分散。为了确保将A-PAM和纤维素纤维良好混合，可通过使用高速混合器、挤出机或喷洒设备等加入A-PAM。
由于纤维素纤维通常带有负电荷，仅预期少量加入的阴离子聚丙烯酰胺被纤维吸附。取决于A-PAM的加入量，可控制浆料中游离形式的A-PAM的量。
然而，可希望增加被纤维吸附的A-PAM的量。这可以多种不同方式进行，例如通过调节温度、通过加入电解质、通过加入固定化学品和/或通过改变浆料的pH。
优选将含有纤维和A-PAM的浆料的温度提高到高于50℃、优选高于75℃、甚至更优选高于100℃。通过提高含有纤维素纤维和A-PAM的浆料温度，已经表明吸收到纤维上的A-PAM的量增加。据信提高的温度改性纤维，使得其对A-PAM的亲和力增加，且更多量的A-PAM可被吸收到纤维上。
还可以向浆料中加入电解质。电解质优选具有单价，二价或者多价阳离子，例如硫酸钠或氯化钙。通过向含哟纤维素纤维和A-PAM的浆料中加入电解质，可降低纤维的阴离子电荷，从而提高A-PAM在纤维上的吸收。浆料的电解质浓度优选为0.0001-0.5M，优选0.001-0.4M，其中最终浓度取决于离子的化合价和种类。所需浓度取决于纤维素材料和使用的A-PAM。
还可以向浆料中加入固定化学品，例如染料或者光学增亮剂。通过加入固定化学品，可以增加A-PAM在纤维上的吸收的方式改性加入的A-PAM。
还可改变加入的A-PAM的电荷密度或分子结构以增强A-PAM在纤维上的吸附。
A-PAM的摩尔质量优选高于10x 106g/mol，优选高于12x 106g/mol，或甚至更优选高于15x 106g/mol。令人惊讶地发现具有高摩尔质量的阴离子聚丙烯酰胺改善纤维机械处理的运性性能以生产MFC。预期具有短聚合物链的阴离子聚丙烯酰胺(即具有低摩尔质量的A-PAM)将充当分散剂，从而提高运性性能，而具有长聚合物链的阴离子聚丙烯酰胺(即具有高摩尔质量的A-PAM)将充当絮凝剂从而降低运性性能。但是发现：当将具有长聚合物链(即具有高摩尔质量)的A-PAM加入到纤维素纤维并随后进行机械处理时，其比具有短聚合物链的A-PAM甚至更好的起作用。
加入到浆料的A-PAM可是直连和/或支链的。优选使用具有长聚合物链的A-PAM。但是，也可存在一定量的具有较短聚合物链(即具有较低摩尔质量)的A-PAM，从而提供具有多分散的摩尔质量分布，例如双峰尺寸分布的溶液。如果使用支链的A-PAM，聚合物链可更短但支链的A-PAM的摩尔质量仍然较高。加入的A-PAM的摩尔质量可通过任何已知方法确定。还可使用改性的A-PAM，例如含有其他官能团的A-PAM，例如两性的或疏水改性的A-PAM。阴离子A-PAM还包括两性A-PAM，例如共聚物型两性A-PAM，其含有阴离子和阳离子电荷两者。
加入的A-PAM的电荷优选低于-1.5mekv/g。已经表明，具有负电荷的A-PAM进一步将改善纤维素纤维的原纤化。电荷可通过任何已知方法测定。
加入浆料中的A-PAM的量优选为150-2500g/t干MFC，优选800-1500/t干MFC。加入到浆料中的A-PAM的所需量取决于机械处理和浆料中的纤维素纤维。但是，取决于含有MFC和A-PAM的组合物的最终用途，更高剂量的A-PAM可为必须的。如果组合物应当用于强度增强，可使用5-50kg/t的量，优选使用5-15kg/t的量。
浆料中的纤维素纤维优选在加入阴离子聚丙烯酰胺之前经行预处理。所述预处理可是机械的、化学的和/或酶促。根据本发明，处理经预处理的纤维可为更能量有效的。
含有纤维素纤维和A-PAM的浆料优选在高剪切速率的机械设备(例如流化器、匀化器、挤出机如锥形挤压机、高剪切精制机、高剪切原纤化器如穿孔锥(cavitron)转子/定子系统或任何其他使得浆料经历高剪切速率的设备)中进行机械处理。高剪切速率机械设备的喷嘴或缝一般具有高的被塞住的趋势，即它们被处理的纤维阻塞。但是向待在高剪切速率机械设备中处理的含有纤维的浆料加入A-PAM降低阻塞或堵塞喷嘴和/或缝的趋势，并且高剪切速率机械设备的运性性能得到改善。但是，还可以使用其他机械设备例如精制机、纤维分离机、打浆机、摩擦式磨机、分散器或其他已知机械纤维处理装置。
优选在多于一个步骤中机械处理含有纤维和A-PAM的浆料，即使所述浆料多于一次地穿过机械设备，优选二次，三次或更多次，以生产含有微原纤化纤维素的组合物。
在机械处理过程中，浆料优选具有1-40重量％、优选1-5重量％的浓度。由于加入阴离子聚丙烯酰胺会提高纤维悬浮液的电荷，使纤维倾向于抗絮凝，这使得可增加浆料的浓度且仍然能够以有效方式生产含有微原纤化纤维素的组合物。生产的含有微原纤化纤维素的组合物的浓度也因此会具有更高的浓度。因此可生产具有高浓度的含有MFC的组合物，从而存进组合物向使用地点的运输。
所述方法可进一步包括：在第三步中将具有高摩尔质量的阴离子聚丙烯酰胺(A-PAM)加入浆料；和在第四步中使含有纤维和A-PAM的浆料经历机械处理，从而形成含有微原纤化纤维素的组合物。因此可以多于一个步骤将阴离子聚丙烯酰胺加入浆料，并且优选使浆料在A-PAM的每一次添加后经历机械处理。还可以多于两步、例如三步、四步或更多步将具有高摩尔质量的A-PAM加入浆料。因此还可以多于两步例如三步、四步或更多步机械处理含有纤维素纤维和A-PAM的浆料。各步加入的A-PAM的量取决于机械处理，例如所用设备、机械处理的条件、以及处理的纤维。加入浆料的A-PAM的总含量应为150-2500g/t干MFC。如下是优选的：在第一次机械处理前的第一步加入少量的A-PAM，然后在第二次机械处理前的第三步加入较大量的A-PAM。
本发明进一步涉及根据上述方法制得的含有微原纤化纤维素和具有高摩尔质量的A-PAM的组合物。由于在生产微原纤化纤维素的过程中加入阴离子聚丙烯酰胺，生产的组合物将具有提高的负电荷。含有MFC的组合物中负电荷的提高将给予组合物更高的阳离子需求和在造纸工艺中改善的助留性两者。组合物中的A-PAM的存在还会降低生产的MFC的絮凝作用，这将改善MFC与其他材料和添加剂混合的能力。
可将生产的含有MFC和A-PAM的组合物在纸或纸板的生产中用作添加剂。众所周知，A-PAM提高例如纸或纸板的干强度。但是，通常不易将MFC和A-PAM在加入到例如造纸或纸板机的湿端之前混合。本发明的优点在于，可生产含有MFC和A-PAM的稳定组合物，所述A-PAM由此还可用作添加剂以增强纸或纸板强度。
还可将含有MFC和A-PAM的组合物在例如番茄酱或接合剂中用作粘度控制添加剂。组合物中的MFC的粘度性能相比于不含A-PAM的MFC组合物更稳定。这是由于A-PAM可充当MFC的微原纤维的抗絮凝剂。
本发明的优点在于加入的A-PAM在组合物中可为游离形式，即组合物的微原纤化纤维素没有吸附全部加入的A-PAM，即MFC没有被化学改性。从而，使组合物的MFC例如作为食物添加剂获得批准是更容易的。
还可将所述组合物用作废水净化添加剂。此外，还可将所述组合物用于任何已知的其中可使用MFC或可使用A-PAM的终端用途。
本发明方法中使用的纤维素纤维优选为硫酸盐浆的纤维，即它们已经根据硫酸盐法进行处理。但是，也可使用其他化学浆、机械浆或化学-机械浆，一个实例是亚硫酸盐浆。纤维也可为漂白的或未漂白的。纤维素纤维可是阔叶木和/或针叶木纤维。还可以使用来自农业材料或再生纤维素纤维的纤维。
实施例：
使用具有3％浓度的经预处理的纸浆。将不同种类的阴离子聚丙烯酰胺以不同量加入到纸浆浆料中，随后在微流化器中经历机械处理。作为参比样品，在将纸浆浆料在微流化器中处理前不向其加入A-PAM。
将纤维悬浮液首先用酶进行预处理，然后将阴离子聚丙烯酰胺加入到所述悬浮液中并混合10分钟(31000转)。混合后，使样品运行通过微流化器M-110EH-30(MicrofluidicsCorp.)三次，在前两次运行中使用400和200um的腔室，且随后在第三次运行中使用200/100腔室。
使用的化学品是具有不同阴离子带电量和摩尔质量的不同的阴离子聚丙烯酰胺(Fennopol A3092，Fennopol A302，和Fennopol A392,所有产品来自于Kemira)。
运性性能在此处定义为流化器的堵塞的趋势，这由此限制在较高固体含量下的运行。
表1：显示在微流化器中加入和不加入不同种类的阴离子聚丙烯酰胺的情况下的运性性能测试
微流化器的运性性能根据目视评价。取决于微流化器的喷嘴的阻塞量，运性性能被分级为差、合格、好和非常好。从上面测试可以看出，加入具有高摩质量的A-PAM显著改善微流化器的运性性能。
鉴于对本发明上述具体的描述，其他改变和变化对所属领域人员而言将变得明显。但是，显然，这些其他的改变和变化可在不离开本发明的精神和范围的情况下实现。
Claims (13)
1.生产含有微原纤化纤维素的组合物的方法，所述方法包括：
-提供含有纤维素纤维的浆料，
-在第一步中将具有高摩尔质量的阴离子聚丙烯酰胺(A-PAM)加入所述浆料，和
-在第二步中使含有纤维和A-PAM的浆料经历机械处理，从而形成含有微原纤化纤维素的组合物，其中A-PAM的摩尔质量高于10x106g/mol。
2.根据前述权利要求1所述的方法，其中A-PAM具有低于-1.5mekV/g的电荷。
3.根据前述权利要求中任一项所述的方法，其中加入到所述浆料中的A-PAM的量为150-2500g/t干MFC。
4.根据权利要求1或2所述的方法，其中将含有纤维和A-PAM的浆料的温度提高到高于50℃。
5.根据权利要求1或2所述的方法，其中将电解质加入到浆料中。
6.根据权利要求5所述的方法，其中所述浆料中电解质的浓度为0.0001-0.5M。
7.根据权利要求1或2所述的方法，其中将固定化学品加入到浆料中。
8.根据权利要求7所述的方法，其中所述固定化学品选自染料或光学增亮剂。
9.根据权利要求1或2所述的方法，其中将浆料中的纤维素纤维在加入阴离子聚丙烯酰胺之前进行预处理。
10.根据权利要求1或2所述的方法，其中使浆料在高剪切速率机械装置中进行机械处理。
11.根据权利要求1或2所述的方法，其中，在机械处理过程中，所述浆料具有1-40重量％的浓度。
12.根据权利要求1或2所述的方法，其中所述方法进一步包括：
-在第三步中将具有高摩尔质量的阴离子聚丙烯酰胺(A-PAM)加入所述浆料；和
-在第四步中使含有纤维和A-PAM的浆料经历机械处理，从而形成含有微原纤化纤维素的组合物。
13.根据权利要求1-12中任一项的方法制备的含有微原纤化纤维素和具有高摩尔质量的A-PAM的组合物。
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| SE1350512A SE537949C2 (sv) | 2013-04-25 | 2013-04-25 | Förfarande för behandling av cellulosafibrer för att framställa en komposition innefattande mikrofibrillerad cellulosa,samt en komposition framställd enligt förfarandet |
| SE1350512-8 | 2013-04-25 | ||
| PCT/IB2014/060890 WO2014174429A1 (en) | 2013-04-25 | 2014-04-22 | Process for treating cellulose fibres in order to produce a composition comprising microfibrillated cellulose and a composition produced according to the process |
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| CN105339547B true CN105339547B (zh) | 2018-04-27 |
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| US (1) | US20160060815A1 (zh) |
| EP (1) | EP2989247B1 (zh) |
| CN (1) | CN105339547B (zh) |
| BR (1) | BR112015027014B1 (zh) |
| NO (1) | NO2989247T3 (zh) |
| PL (1) | PL2989247T3 (zh) |
| SE (1) | SE537949C2 (zh) |
| WO (1) | WO2014174429A1 (zh) |
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| FI127014B (en) * | 2013-05-15 | 2017-09-29 | Upm Kymmene Corp | Process for the manufacture of nanofibrillar cellulose and for the manufacture of a paper product |
| FI20135773L (zh) * | 2013-07-16 | 2015-01-17 | Stora Enso Oyj | |
| US9970159B2 (en) | 2014-12-31 | 2018-05-15 | Innovatech Engineering, LLC | Manufacture of hydrated nanocellulose sheets for use as a dermatological treatment |
| US9816230B2 (en) * | 2014-12-31 | 2017-11-14 | Innovatech Engineering, LLC | Formation of hydrated nanocellulose sheets with or without a binder for the use as a dermatological treatment |
| US10240290B2 (en) * | 2015-06-04 | 2019-03-26 | Gl&V Usa, Inc. | Method of producing cellulose nanofibrils |
| EP3456639A1 (en) * | 2017-09-19 | 2019-03-20 | Borregaard AS | Compact system for packaging microfibrillated cellulose |
| SE543616C2 (en) * | 2019-06-17 | 2021-04-20 | Stora Enso Oyj | A method to produce a fibrous product comprising microfibrillated cellulose |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335856A (zh) * | 1999-02-10 | 2002-02-13 | 赫尔克里士公司 | 微纤维状多糖衍生物 |
| CN102317542A (zh) * | 2009-02-13 | 2012-01-11 | 芬欧汇川集团 | 制造改性纤维素的方法 |
| CN102472015A (zh) * | 2009-07-07 | 2012-05-23 | 斯托拉恩索公司 | 生产微纤纤维素的方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2216345B1 (en) * | 2007-11-26 | 2014-07-02 | The University of Tokyo | Cellulose nanofiber, production method of same and cellulose nanofiber dispersion |
| WO2011051882A1 (en) * | 2009-10-26 | 2011-05-05 | Stora Enso Oyj | Process for production of microfibrillated cellulose in an extruder and microfibrillated cellulose produced according to the process |
| FI126513B (fi) * | 2011-01-20 | 2017-01-13 | Upm Kymmene Corp | Menetelmä lujuuden ja retention parantamiseksi ja paperituote |
| JP2012180602A (ja) * | 2011-02-28 | 2012-09-20 | Mitsubishi Chemicals Corp | セルロース繊維分散液、セルロース繊維分散液の製造方法および微細セルロース繊維の製造方法 |
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2013
- 2013-04-25 SE SE1350512A patent/SE537949C2/sv unknown
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2014
- 2014-04-22 EP EP14788480.3A patent/EP2989247B1/en active Active
- 2014-04-22 US US14/786,449 patent/US20160060815A1/en not_active Abandoned
- 2014-04-22 WO PCT/IB2014/060890 patent/WO2014174429A1/en active Application Filing
- 2014-04-22 NO NO14788480A patent/NO2989247T3/no unknown
- 2014-04-22 PL PL14788480T patent/PL2989247T3/pl unknown
- 2014-04-22 BR BR112015027014-0A patent/BR112015027014B1/pt active IP Right Grant
- 2014-04-22 CN CN201480023617.3A patent/CN105339547B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335856A (zh) * | 1999-02-10 | 2002-02-13 | 赫尔克里士公司 | 微纤维状多糖衍生物 |
| CN102317542A (zh) * | 2009-02-13 | 2012-01-11 | 芬欧汇川集团 | 制造改性纤维素的方法 |
| CN102472015A (zh) * | 2009-07-07 | 2012-05-23 | 斯托拉恩索公司 | 生产微纤纤维素的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| PL2989247T3 (pl) | 2018-08-31 |
| BR112015027014A2 (pt) | 2017-07-25 |
| CN105339547A (zh) | 2016-02-17 |
| SE537949C2 (sv) | 2015-12-01 |
| SE1350512A1 (sv) | 2014-10-26 |
| EP2989247A4 (en) | 2016-11-23 |
| EP2989247A1 (en) | 2016-03-02 |
| NO2989247T3 (zh) | 2018-10-13 |
| EP2989247B1 (en) | 2018-05-16 |
| BR112015027014B1 (pt) | 2021-11-16 |
| US20160060815A1 (en) | 2016-03-03 |
| WO2014174429A1 (en) | 2014-10-30 |
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