CN1191278C - 改性纤维素醚 - Google Patents
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/20—Organic compounds containing oxygen
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Abstract
本发明涉及一种用通式(I)的烷基或链烯基乙烯酮二聚体疏水改性的纤维素醚：其中R1和R2为烷基或链烯基链，如具有5至22个，优选13至20个，最优选14至18个碳原子的链。例如，该产品可用于水基产品中控制流变性能。使用的对象包括例如洗涤剂、纸张涂布剂、涂料、分散剂、和石油钻探泥浆。
Description
发明背景
本发明涉及疏水改性纤维素醚及其用途。
纤维素醚如羧甲基纤维素在很多领域中特别用于处理水溶液的流变性能。使用的对象包括例如食品、药物、化妆品制剂、洗涤剂、农业化学品、织物、印刷油墨、纸张涂布剂、结构材料、粘合剂、涂料、陶瓷材料、和聚合物添加剂。
纤维素醚可通过将不同的取代基与纤维素中的羟基连接改性。按照这种方式，特别可改变纤维素醚的溶解性或疏水性。
有很多文献涉及多糖的疏水改性。
US4228277描述了通过使用具有长度10至24个碳原子的烷基的环氧链烷对非离子纤维素醚如甲基纤维素、甲基羟丙基纤维素、羟丙基纤维素，特别是羟乙基纤维素进行改性的方法。根据该专利，这种改性方法的一个优点是，甚至少量的疏水改性纤维素醚可使水溶液的粘度升高，这样可降低纤维素醚的剂量。如此改性的纤维素醚可用于涂料中。该改性通过使用纤维素醚作为原料进行，且反应时间长达2至5小时。然而，使用环氧化合物不适宜，因为它们对健康有害。
在FI95138中，通过0.1至4wt％的具有8至25个碳原子的烷基对羧甲基羟乙基纤维素进行改性。该产品也适用于涂料。烷基试剂可为卤化物、卤化氢或环氧化物，所有这些烷基化试剂都对环境和身体有害。羟乙基化、疏水改性和羧甲基化顺序进行，因此反应时间长达4小时以上。
US5302196描述通过3-24个碳原子的含氟烷基改性的纤维素醚，氟含量为0.05至5wt％。纤维素醚特别为羟乙基纤维素、羟乙基羧甲基纤维素或甲基羟乙基纤维素。含氟烷基试剂优选为环氧化物、溴化物或全氟烯烃。该产品还用于涂料中。该反应时间长，改性需要6小时反应时间。
在EP专利申请384167中，纤维素醚，特别是羟乙基纤维素用具有至少10个碳原子的芳族烷基改性，其含量为0.001至0.1mol/mol纤维素醚葡萄糖重复单元。该烷基试剂可为例如卤化物、环氧乙烷、酸、(硫)异氰酸酯或卤代醇。该产品可用于胶乳涂料中。该制造方法还具有6或最长到12小时的长反应时间。
发明概述
根据独立权利要求1，还发明了疏水改性纤维素醚。从属权利要求公开了本发明的某些优选实施方案。
本发明引入了一类新的疏水改性纤维素醚，其中改性试剂为烷基乙烯酮二聚体。所述纤维素醚优选为羧甲基纤维素或羧甲基纤维素钠(CMC，NaCMC)。
用烷基乙烯酮二聚体改性的纤维素醚容易制造。本发明方法安全、简单、快速。改性还可改善纤维素醚在水中的分散性。
本发明产品适用于任何水基应用。疏水基团使例如洗涤剂、纸涂布混合物、涂料、分散剂和石油钻探泥浆具有有利的物质性能。
发明详述
根据本发明，将烷基乙烯酮二聚体(AKD)用于改性纤维素醚。AKD的通式为：
其中R1和R2是具有5至22个碳原子，优选13至20个碳原子的烷基或链烯基链，R1或R2还可被取代或它们可在链中含杂原子，R1或R2特别可具有直链并含14至18个碳原子。
AKD与纤维素或纤维素醚的羟基反应，形成如下通式：
高温，如30-120℃，优选50-90℃，最优选60-85℃可增强反应，这样在高温下AKD首先熔化。高温和碱性pH改进了AKD与纤维素醚的反应性。AKD可与取代基，例如纤维素醚中的羧甲基反应。AKD还可与含有OH基团的其它化合物反应。这些化合物包括水、醇和在制备CMC时生成的甘醇酸钠。如此生成的化合物对产品的疏水性也有影响。
纤维素醚中的反应AKD浓度可通过使用气相色谱分析。用合适的溶剂萃取未反应的AKD或与含OH的其它化合物反应的AKD。该样品水解导致烷基乙烯酮基团裂解。已反应的AKD用合适的溶剂萃取并用气相色谱分析。
AKD可为固态或分散于水或其它溶剂中。
AKD在纤维素醚中的含量可为0.001-10wt％。其含量优选为0.01-2wt％。
纤维素醚的分子量(Mw)可为10000-1000000，优选20000-700000。纤维素醚可为例如烷基、羟烷基或羧烷基取代的或这些基团取代的混合醚。
根据本发明，通过AKD改性的纤维素醚可用于任何水基应用中。例如它可用于纸或纸板涂布混合物中、以最终湿产品的形式用于纸或纸板制造、涂料、结构材料、粘合剂、石油钻探泥浆、洗涤剂、化妆品产品中，和作为分散剂。
纤维素醚优选为羧甲基纤维素醚(CMC)。其取代度(DS，即葡萄糖环中的取代羟基的平均数)可为例如0.2-2.0，优选0.4-1.5，最优选0.4-1.2。其分子量优选为40000-500000。该纤维素醚适用于所有上述目的。
该纤维素醚还可为例如羟乙基纤维素(HEC)。其分子量可为例如90000-1300000，其摩尔取代度(MS)可为1.5-4。HEC特别可用于涂料、结构材料和化妆品制剂中。
纤维素醚还可为例如羟丙基纤维素(HPC)。其分子量可为例如80000-1150000，摩尔取代度(MS)为1.5-4。HPC特别可用于食品、药物制剂和涂料中。
有很多关于制备纤维素醚的文献。通常，这些纤维素醚通过木材基或棉毛基原料与反应介质如醇或丙酮混合，并通过用碱性物质如氢氧化钠对其进行丝光处理使纤维素活化的方式制备。加入醚化化学品并使其反应。最终产品是中性的。若需要，可降低粘度。例如当制备纯化的纤维素醚时，将副产品，如反应中生成的盐用醇洗掉，但它们也可留在产品中或仅部分除去(工业级或粗纤维素醚)。将所用的溶剂分离并将产品干燥。颗粒尺寸和堆密度可通过将该产品研磨成粉末或通过将其造粒调节。还可将产品过筛。
纤维素醚可用AKD通过各种方法改性。可将AKD在生产的任何阶段，例如在丝光处理、醚化或干燥时加入纤维素醚中。AKD可以固体形式或作为分散体加入。高温和碱性pH可改进AKD与纤维素醚的反应性。
AKD还可以照这样加入纤维素醚中。该纤维素醚可用例如固体AKD或AKD分散体涂布。在这种情况下，可将合适量的AKD喷涂于纤维素醚的表面上或与其混合。将该产品用高温处理以引发反应。
本发明的疏水改性纤维素醚的制备方法简单且快速。既不需要复杂的溶剂也不需要长反应时间。此外，AKD是安全的化学品。它既不燃烧也不爆炸；因此，它既不会使方法危险也不危害环境。AKD不危险或刺激，且不会造成变应性；因此，它对方法的操作人员或最终用户不存在任何危险。
疏水改性纤维素醚特别适用于洗涤剂组合物中。纤维素优选为羧甲基纤维素(CMC)。其取代度最优选为0.4-0.6。该组合物通常包括约0,1-5wt％的纤维素基织物处理组分，优选0,5-4％，最优选0,75-3％。洗涤剂组合物可为液态、糊状或颗粒形式。这些组合物包括约1-80wt％，优选5-50％的去污表面活性剂，这些表面活性剂可为阴离子、非离子、两性离子、两性或离子类型。这些组合物还可包括约0,1-80wt％的洗涤剂助洗剂，优选1-10％的液态形式的洗涤剂助洗剂和1-50％的颗粒形式的助洗剂。洗涤剂助洗剂可包括例如磷酸盐以及各种有机和无机非磷助洗剂。除了表面活性剂、助洗剂和纤维素基物质外，这些洗涤剂组合物还可包括例如酶和酶稳定剂、泡沫促进剂或抑泡剂、防锈剂和防腐蚀剂、污物悬浮剂、去污剂、杀菌剂、pH调节剂、非助洗剂碱源、螯合剂、有机和无机填料、溶剂、水溶助长剂、荧光增白剂、染料和香料。
颗粒状洗涤剂组合物通常通过将基本组分合并为淤浆，并将所得淤浆喷雾干燥至低残余含水量制备。剩余组分可以干态形式掺混，或为液态形式时喷涂于所得颗粒上。液体洗涤剂组合物可通过将这些组分以任何所需顺序掺混制备。
在含疏水改性纤维素醚的洗涤溶液中洗涤织物和纺织品、接着漂洗和干燥，赋予如此处理的织物和纺织制品织物外观益处。这种益处可包括改进的整体外观、降低起球/起毛、防褪色、改进的耐磨性和/或增强的柔软性。
实施例
所有实施例使用烷基乙烯酮二聚体，烷基的长度为16至18个碳原子(Raisio Chemicals)
实施例1
将100g具有平均分子量180000和取代度0.65的CMC(MetsaSpeciality Chemicals)倒入钢制容器中。将1g具有AKD含量10wt％、用50g水稀释的烷基乙烯酮二聚体分散体喷涂于CMC上，同时搅拌粉末。将该产品在80℃下干燥至含水量低于8％。最终产品的AKD含量为0.1wt％。
实施例2-6
通过使用上述步骤，制备下列疏水改性CMC样品(实施例2-6)
表1
| 实施例 | CMC的分子量 | CMC的取代度 | CMC中的AKD含量，wt％ |
| 2 | 60000 | 0.72 | 0.05 |
| 3 | 300000 | 0.80 | 0.05 |
| 4 | 220000 | 0.87 | 0.1 |
| 5 | 305000 | 1.15 | 1.0 |
| 6 | 80000 | 0.75 | 0.01 |
样品5含0.02wt％的与CMC反应的AKD。
实施例7
将100g具有平均分子量40000和取代度0.79的CMC倒入钢筒中。加入5g固体烷基乙烯酮二聚体。将该粉末在烘箱中在60℃下搅拌120分钟并在105℃下搅拌15分钟。最终产品的AKD含量为5.0wt％。
实施例8
按照实施例7描述的步骤制备具有平均分子量400000和取代度0.86，及AKD含量10.0wt％的疏水改性CMC。
实施例9
将47g木浆(Metsa-Botnia)、175g乙醇和20g水在密闭玻璃烧瓶中混合在一起，该烧瓶设有混合器和任选的氮气气氛。将烧瓶放入水浴中。加入用18g水稀释的18g氢氧化钠，将该纤维素在20℃下进行丝光处理30分钟。加入用6g水稀释的22g单氯乙酸、和具有AKD含量20wt％的1.25g烷基乙烯酮二聚体分散体，并将温度在55分钟内升至65℃。将该纤维素在65℃下醚化60分钟。回收乙醇并将该产品在80℃下干燥至含水量低于8％。最终产品的AKD含量为0.3wt％，平均分子量150000，羧甲基的DS为0.57。该样品含0.02wt％的与纤维素反应的AKD。
实施例10-15
按照实施例9描述的步骤制备样品10-15。在实施例10和15中，将该产品醚化后用盐酸中和。在实施例10中，中和后加入AKD并使其在70℃下反应5分钟。
表2
| 实施例 | CMC的分子量 | CMC的取代度 | CMC中的AKD含量，wt％ |
| 10 | 180000 | 0,46 | 0,6 |
| 11 | 120000 | 0,48 | 0,6 |
| 12 | 140000 | 0,52 | 0,06 |
| 13 | 150000 | 0,55 | 1,1 |
| 14 | 140000 | 0,56 | 2,7 |
| 15 | 270000 | 0,52 | 0,06 |
样品12含＜0.01wt％的与CMC反应的AKD。
实施例16
将100g木浆(Metsa-Botnia)、1270g异丙醇和162g水在密闭玻璃烧瓶中混合在一起，该烧瓶设有混合器和氮气气氛。将烧瓶放入水浴中。加入用40g水稀释的40g氢氧化钠，将该纤维素在20℃下进行丝光处理90分钟。加入用11g水稀释的44g单氯乙酸、和具有AKD含量10wt％的1g烷基乙烯酮二聚体分散体，并将温度在45分钟内升至70℃。将该纤维素在70℃下醚化90分钟。将CMC用盐酸中和。用75％甲醇将反应副产品氯化钠和甘醇酸钠洗掉，并将该产品在80℃下干燥至含水量低于8％。最终产品的AKD含量为0.08wt％，平均分子量270000，羧甲基的DS为0.59。
实施例17-19
样品17-19按照实施例16描述的步骤制备。在实施例19中，在丝光处理期间加入AKD。
表3
| 实施例 | 原料 | CMC的分子量 | CMC的取代度 | CMC中的AKD含量，wt％ |
| 17 | 木浆(Metsa-Botnia) | 60000 | 0,77 | 0,07 |
| 18 | 木浆(Borregaard) | 240000 | 0,89 | 0,07 |
| 19 | 棉绒(Buckeye，Temming) | 380000 | 0,80 | 0,7 |
实施例20
本发明的颗粒洗涤剂组合物具有如下基本配方：
表4
| 组分 Wt.％ |
| C12直链烷基苯磺酸盐 9.31 |
| C14-15烷基醚(0.35 EO)硫酸盐 12.74 |
| 沸石助洗剂 27.79 |
| 碳酸钠 27.31 |
| PEG4000 1.60 |
| 分散剂 2.26 |
| C12-13醇乙氧基化物(9EO) 1.5 |
| 过硼酸钠 1.03 |
| 去污聚合物 0.41 |
| 酶 0.59 |
| 疏水改性纤维素醚 3.0 |
| 香料、增白剂、抑泡剂、其它微量组分、水分、硫酸盐 平衡量 |
| 100％ |
Claims (21)
1.一种疏水改性纤维素醚，其特征在于疏水改性通过使用如下通式的烷基或链烯基乙烯酮二聚体进行：
其中R为具有5至22个碳原子的烷基或链烯基链。
2.根据权利要求1的改性纤维素醚，其中R为具有13至20个碳原子的烷基或链烯基链。
3.根据权利要求1的改性纤维素醚，其中R为具有14至18个碳原子的烷基或链烯基链。
4.根据权利要求1的改性纤维素醚，其具有如下通式：
其中R为上面定义的。
5.根据权利要求1的改性纤维素醚，其中纤维素醚的分子量为10,000-1,000,000。
6.根据权利要求1的改性纤维素醚，其中纤维素醚的分子量为20,000-700,000。
7.根据权利要求1的改性纤维素醚，其中纤维素醚的分子量为40,000-500,000。
8.根据权利要求1的改性纤维素醚，其中烷基或链烯基乙烯酮二聚体在纤维素醚中的含量为0.001-10wt％。
9.根据权利要求1的改性纤维素醚，其中烷基或链烯基乙烯酮二聚体在纤维素醚中的含量为0.01-2wt％。
10.根据权利要求1的改性纤维素醚，其中纤维素醚为羧甲基纤维素。
11.根据权利要求10的改性纤维素醚，其中羧甲基纤维素的取代度为0.2-2。
12.根据权利要求10的改性纤维素醚，其中羧甲基纤维素的取代度为0.4-1.5。
13.根据权利要求10的改性纤维素醚，其中羧甲基纤维素的取代度为0.4-1.2。
14.一种制备疏水改性纤维素醚的方法，在该方法中，使纤维素醚与烷基或链烯基乙烯酮二聚体反应，其中纤维素醚具有如下通式：
其中R1和R2分别为具有5至22个碳原子的烷基或链烯基链。
15.根据权利要求14的方法，其中反应在30-120℃下进行。
16.根据权利要求14的方法，其中反应在50-90℃下进行。
17.根据权利要求14的方法，其中反应在60-85℃下进行。
18.一种拟用于与水混合的组合物或含水组合物，其特征在于该组合物含有权利要求1至13任何一项的疏水改性纤维素醚或根据权利要求14至17任何一项的方法制备的疏水改性纤维素醚。
19.根据权利要求18的组合物或含水组合物，其中该组合物是一种洗涤剂组合物。
20.根据权利要求19的组合物或含水组合物，其中组合物含疏水改性羧甲基纤维素。
21.根据权利要求20的组合物或含水组合物，其中羧甲基纤维素的取代度为0.4-0.6。
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| FI981149A FI107385B (fi) | 1998-05-25 | 1998-05-25 | Modifioitujen selluloosaeetterien valmistus |
| FI981149 | 1998-05-25 |
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| US6677427B1 (en) | 2000-06-13 | 2004-01-13 | Hercules Incorporated | Enzyme-catalyzed polyamides and compositions and processes of preparing and using the same |
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| GB0227242D0 (en) * | 2002-11-21 | 2002-12-31 | Unilever Plc | Improvements relating to fabric laundering |
| JP5007985B2 (ja) * | 2004-06-25 | 2012-08-22 | 国立大学法人 東京大学 | ポリマーブラシ化合物及びその調製方法 |
| GB0419689D0 (en) | 2004-09-04 | 2004-10-06 | Unilever Plc | Improvements relating to fabric laundering |
| WO2007056070A2 (en) * | 2005-11-04 | 2007-05-18 | Hercules Incorporated | Ether derivatives of raw cotton linters for water-borne coatings |
| EP2085070A1 (en) * | 2008-01-11 | 2009-08-05 | Procter & Gamble International Operations SA. | Cleaning and/or treatment compositions |
| EP2302025B1 (en) * | 2009-09-08 | 2016-04-13 | The Procter & Gamble Company | A laundry detergent composition comprising a highly water-soluble carboxmethyl cellulose particle |
| CN102443067B (zh) * | 2011-10-28 | 2013-03-20 | 东北林业大学 | 一种羰基化改性纳米纤维素的制备方法 |
| CN104629508B (zh) * | 2015-03-11 | 2018-03-06 | 马清浩 | 一种耐水耐擦洗内外墙乳胶漆 |
| DE17784205T1 (de) | 2016-09-28 | 2019-11-28 | Cp Kelco Oy | Waschmittelzusammensetzungen mit polysacchariden mit extrem niedrigem molekulargewicht |
| CN108048236B (zh) * | 2017-12-01 | 2020-11-06 | 纳爱斯浙江科技有限公司 | 一种含有羧甲基纤维素的液体洗涤剂及其制备方法 |
| JP2019099822A (ja) * | 2017-12-06 | 2019-06-24 | 花王株式会社 | 繊維製品用洗浄剤組成物 |
| US11872711B2 (en) | 2019-05-10 | 2024-01-16 | The Gillette Company Llc | Lubricating member for razor cartridges |
| CN110563855A (zh) * | 2019-10-12 | 2019-12-13 | 山东省食品发酵工业研究设计院 | 一种自组装纳米粒子材料——十八烷酰十八烷酸普鲁兰多糖酯的合成方法 |
| CN111995691A (zh) * | 2020-08-21 | 2020-11-27 | 南京林业大学 | 纤维素醚类衍生物、制备方法及用途 |
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| US2627477A (en) * | 1949-10-06 | 1953-02-03 | Hercules Powder Co Ltd | Higher alkyl ketene dimer emulsion |
| SE361908B (zh) * | 1972-07-14 | 1973-11-19 | Kema Nord Ab | |
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| US4228277A (en) | 1979-02-12 | 1980-10-14 | Hercules Incorporated | Modified nonionic cellulose ethers |
| GB8621680D0 (en) * | 1986-09-09 | 1986-10-15 | Du Pont | Filler compositions |
| US4826970A (en) | 1987-09-17 | 1989-05-02 | Hercules Incorporated | Carboxymethyl hydrophobically modified hydroxyethylcellulose |
| BR9000379A (pt) | 1989-01-31 | 1990-12-04 | Union Carbide Chem Plastic | Polissacarideo soluvel em agua,processo para producao de um polissacarideo soluvel em agua,composicao de latex e processo para producao de uma composicao de latex |
| DE4028746A1 (de) | 1990-09-11 | 1992-03-12 | Hoechst Ag | Modifizierte celluloseether und ihre verwendung in dispersionsfarben |
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