CN1865288A - 碳水化合物的氢氧自由基改性 - Google Patents
碳水化合物的氢氧自由基改性 Download PDFInfo
- Publication number
- CN1865288A CN1865288A CNA2006100844284A CN200610084428A CN1865288A CN 1865288 A CN1865288 A CN 1865288A CN A2006100844284 A CNA2006100844284 A CN A2006100844284A CN 200610084428 A CN200610084428 A CN 200610084428A CN 1865288 A CN1865288 A CN 1865288A
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- Prior art keywords
- carbohydrate
- starch
- modification
- free radical
- reaction
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- 238000000034 method Methods 0.000 claims abstract description 48
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
用于通过与氢氧自由基反应改性碳水化合物的方法。所述氢氧自由基可由水、过氧化物或其它含氢氧基的合适化学物质通过光反应形成,或通过水、过氧化物或其它含氢氧基的合适化学物质的电化学分解形成。以及,含有本方法改性的碳水化合物的组合物和产品。
Description
技术领域
本发明涉及用氢氧自由基(hydroxyl radical)对碳水化合物的改性。本发明进一步涉及用氢氧自由基改性的碳水化合物。
背景技术
碳水化合物的改性可被分为两种主要类型:化学的和流变学的。化学改性通常是指通过改变碳水化合物的电荷条件或增加其稳定性,用化学基团取代碳水化合物。若更高的干物质含量在溶液中是合适的,则通常使用流变改性,其意味着通过水解或氧化降低其粘度。对于水解,可使用酶或酸。氧化通常包括在碱性含水介质中用溴、氯化物或相应金属次卤酸盐处理碳水化合物。例如,用次氯酸盐如次氯酸钠处理碳水化合物。通过加酸进行酸转化,从而水解淀粉并降低粘度。
至于淀粉,例如,氧化通常包括在淀粉分子中各种联接的断开。淀粉是葡萄糖聚合物,其由葡萄糖单元组成,该单元通过在葡萄糖环上的1,4位醚键连接到一起形成直链主链,在该环的1,6单元连接有聚合物的额外支链。氧化会使这些醚键断裂,降低淀粉分子的分子量。另外,它们还可在2,3单元之间断裂葡萄糖环,并且此外可将这些所得的醛基之一或二者转化为羧基。氧化剂的选择、碱的量、温度和反应时间可导致不同的变稀(thinning)速度,并通过氧化方法改变稀释(thinned)的淀粉中产生羧基的量。其它选择性氧化剂,如高碘酸盐,只攻击淀粉上的某些键,高碘酸化2-3联接。酸改性或稀释是在相对低pH值下进行的,并且是更随机的断裂,但是可以持续降低粘度或将淀粉转化为糖。
氧化和酸转化之间一个主要区别是通过在碳水化合物分子断裂点的氧化形成羧基。羧基影响改性过的碳水化合物的许多性质;影响淀粉糊的稳定性、颜色变化和膜性质。不同的氧化条件产生有不同羧基含量的相似粘度的淀粉,从而导致彼此性质不同的经改性的碳水化合物以及酸转化的碳水化合物。
本说明书中所有份数和百分含量除了特别说明外均基于重量给出。
发明内容
本发明涉及用氢氧自由基改性来改性碳水化合物,如淀粉的方法。在该方法中,氢氧自由基与碳水化合物浆料反应,形成具有降低的粘度及其它性质的改性过的碳水化合物产物。该方法引入如光反应、电化学转化或类似方法来将过氧化物、水或其它合适的化学物质,例如另一含氢氧基化学物质转化为氢氧自由基。如本说明书中所用的碳水化合物意图具有最宽的可能定义并具体包括淀粉和其它多糖,如水状胶质(hydrocolloid)和纤维素,单独地或结合地。
本发明进一步涉及已经被氢氧自由基改性过的碳水化合物,如稀释的改性淀粉,其具有与传统改性或转化淀粉不同的性质。当将改性的碳水化合物加入至少含有水的液体并蒸煮(cooked),通常得到透明的糊,随着其冷却逐步变成不透明亮白色凝胶,并进行回复(setback)。
具体实施方式
本发明的方法涉及通过与氢氧自由基反应,进行碳水化合物的改性。氢氧自由基是不含有多余电子来产生负电荷的OH自由基。该方法包括提供碳水化合物浆料的步骤,如通过至少结合溶剂例如水,和碳水化合物以形成浆料,然后在浆料中通过碳水化合物与氢氧化物自由基反应改性碳水化合物。所述反应可在酸或碱条件下发生。当形成浆料时或形成浆料后,可加入向浆料加入酸或碱来控制pH。氢氧自由基的使用减少了反应时间及需要用于改性碳水化合物的化学物质,并提供了更有效的反应。
在本发明的实施方式中,氢氧化物自由基用紫外光通过水、过氧化物或其它适合的化学物质,如含氢氧基化学物质的光反应得到。可使用的过氧化物的例子有过氧化氢、过氧化钠或其结合。氢氧化物自由基还可通过水、过氧化物或其它合适化学物质如含氢氧基化学物质的电化学离解来得到。
氢氧自由基与碳水化合物的反应可通过使用催化剂,例如二氧化钛来加速。但是,所述反应也可不用催化剂进行。凝胶抑制剂,如硫酸钠或氯化钠,可在氢氧自由基反应之前、期间或之后加入浆料。
在本发明的一个实施方式中,方法中使用的碳水化合物是淀粉。例如,可使用没有蒸煮以及没有胶凝的粒状淀粉。在这个实施方式中,所述方法包括提供淀粉浆料,以及用氢氧自由基与淀粉反应的步骤,其中的氢氧自由基例如那些用紫外光通过水、过氧化物或其它合适化学物质的光反应或电化学离解得到。反应可在存在碱、酸性条件或在中性条件下发生,从而稀释淀粉。蒸煮后的淀粉,如蒸煮后的淀粉糊,可在该方法中用氢氧自由基改性,并可在碱性、中性或酸性条件下稀释。
可用于本发明中的淀粉包括天然未改性的淀粉以及之前用除了本发明氢氧自由基反应以外的方法改性过的淀粉,从而在所述方法中使用的碳水化合物是“预改性过的淀粉”,例如化学改性过的淀粉。碳水化合物还包括其它多糖,如水状胶质和纤维素。另外,碳水化合物包括糊精和麦芽糊精、玉米糖浆和其它糖。使用羧甲基、阳离子或其它改性过的碳水化合物在本发明范围之内。
淀粉是用许多植物的根、茎或果实生产的商业化学品。其为高分子量碳水化合物聚合物,包括直链和支链多糖聚合物,并可具有从约8%至约20%的含水量,更通常为从约11%至约13%。合适的淀粉来自如从玉米、小麦、大麦、木薯、土豆等,以及高粱属品种。也可使用从各种来源得到的淀粉的混合物。可使用珍珠淀粉和粉末状淀粉、粒状或未蒸煮的淀粉,以及蒸煮或预胶凝的淀粉。从玉米的其它遗传形式,如高直链淀粉和蜡质玉米得到的淀粉也是合适的。
根据本发明使用的改性过的淀粉可用机械、化学或热方法改性。与未改性的淀粉相比,改性后的淀粉经常具有出众的物理性质,如增强的溶解性、更好的膜的形成、增加的白度、改善的凝胶强度、粘度稳定性、加强的粘附性、对剪切更高的抵抗力以及对冻融降解更强的抵抗力。可用的改性后的淀粉或碳水化合物包括,例如,羧甲基、乙酸盐或酯、羟乙基、磷酸盐或酯、交联的、辛烯基琥珀酸盐或酯或阳离子淀粉。
本发明中可用的以及市场供应的化学改性淀粉的例子有SUREBOND工业玉米淀粉或STABLEBOND工业玉米淀粉。这些改性淀粉具有残余羧基功能,并且极度均匀,并且可从美国Illinois,Westchester,Corn Products International,Inc.(“CornProducts”)获得。
半纤维素是本发明中有用的水状胶质的例子。美国专利No.5358559中描述了半纤维素,在此全文引入作为参考。其它可用的水状胶质包括阿拉伯树胶、黄原胶、刺梧桐树胶、黄芪胶、藻酸钠、鹿角菜胶、瓜尔胶、刺槐豆胶、tara、果胶、结冷胶(gellan)、纤维素衍生物,如羧甲基、甲基或乙基纤维素,微晶纤维素或其它多糖类水状胶质。也可使用水状胶质的组合。
纤维素是由葡萄糖单体的重复单元构成的直链聚合物。单体通过1,4糖苷键连接在一起。
本方法中可使用的碱物质的例子包括碱金属氢氧化物,如氢氧化钠、氢氧化钾或氢氧化钙。可使用苛性碱的组合物。在该方法中也可使用酸来调整pH值。浆料的pH值可从约2至约11。当淀粉是在本发明方法中改性的碳水化合物,pH值最好从约7至约11,并可用碱材料调整。
本发明方法比改性碳水化合物的传统方法要求使用更少的化学品。本方法不含氯基氧化剂,如产生烷基卤的次氯酸氧化作用。另外,所述方法不包括可能引入潜在腐蚀性氯化物的酸。这样,所述方法没有排放烷基卤,其对废水处理是有利的,并且得到的产物不包含烷基卤或卤素(即氯化物),其扩展了根据本发明的所述方法的改性的碳水化合物的用途。改性的碳水化合物有一些应用,如食品、医药和化妆品的应用,其中烷基卤和卤素是不受欢迎的。本发明的改性的碳水化合物比用传统方法改性的碳水化合物具有更广泛的最终用途应用。另外,可比本领域中典型改性方法更有效地稀释碳水化合物至较高水平,并且蒸煮淀粉可原位稀释。
进一步,在本发明的方法中,可比传统方法更容易地控制改性的程度。例如,当用于水,过氧化物或其它合适的化学品的光反应的紫外光源如紫外线关闭时,反应停止,此时紫外源关闭,并且当紫外光源再次打开时反应可重新开始。同样地,当使用电化学装置时,如电解池,当所述装置关掉,反应将停止,并且当所述装置再次打开时反应将重新开始。用传统次氯酸盐或酸改性方法,一旦反应停止,重新启动反应很困难并且很花时间。
可干燥从所述方法得到的浆料从而形成含有改性淀粉或其它碳水化合物,如纤维素和水状胶质的乳白色改性粉末。可将所述粉末重新与水化合并蒸煮形成清澈的浆糊,特别当所述碳水化合物是玉米淀粉时。当所述浆糊冷却回复,所述浆糊将变成亮白色。通过本发明的所述方法制造的所述改性的碳水化合物的性质与经过用其他方法改性的碳水化合物不同。例如,次氯酸盐改性的淀粉是白色粉末,其浆糊浑浊,随时间变为棕色,并且酸稀释的淀粉会破坏白色浆糊。
改性的碳水化合物产物可与添加剂结合,从而提供功能或贮存稳定性。添加剂包括,例如粘度稳定剂、功能性化学物质和/或交联剂。本发明中有用的粘度稳定剂包括表面活性剂、脂肪酸配合物、肥皂和试剂如单甘油硬脂酸酯(monoglycerol stearate)。本发明中还可使用交联剂如硼砂,以及还有不溶粘料,如那些可从美国Ohio,Fairlawn,Omnova Solutions,Inc.获得的商品名为SEQUAREZ。其它有用的添加剂包括重亚硫酸盐、尿素、碳酸盐等。
氢氧自由基反应可与一个或多个衍生化反应结合,如阳离子化、酯化、醚化、磷酸化、羧甲基化、交联化等,从而根据本发明的所述方法提供改性的碳水化合物的衍生物。所述衍生化反应可在碳水化合物改性之前或之后进行。
改性的碳水化合物具有很多用途,并可引入很多产品中。例如,从改性的碳水化合物制得的浆糊提供降低粘度的碳水化合物,用于波纹板胶粘剂、纸上浆和纸张涂层。粉末或浆糊形式的改性的碳水化合物可在食品中用于增稠剂,以及其它食品应用,如纹饰、凝胶、脂肪替代、除尘等。所述改性的碳水化合物可用于医药和化妆品的凝胶、浆糊和洗液。由该光反应或电化学转化方法产生的从改性的碳水化合物制得的浆糊的白度,以及没有烷基卤化物和卤素,其提供的改性的碳水化合物产物比用传统方法改性的碳水化合物如淀粉具有更广范围的应用。另外,淀粉的回复特性,其中一旦淀粉回复则得到白色的浆糊,其使改性的淀粉产品在优选回复的应用中特别有用,如在石膏板和烘焙或糖果的应用中。
实施例
实施例1
两组单独的中试实验用氢氧自由基制造降低粘度的淀粉,该氢氧自由基用紫外辐射过氧化氢的光反应制造。将含有碳水化合物和水、约30%固体的淀粉浆料,随过氧化氢和氢氧化钠通过连续氢氧自由基反应器(加拿大,Ontario,London,PURIFICSES的Mobil Cat系统)。还将空气、氧气、臭氧和二氧化钛催化剂加入连续氢氧自由基反应器,从而测定它们对稀释和羧基形成的影响。
与具有相似流质特性的次氯酸盐氧化的淀粉相比,连续氢氧化物自由基反应器中制造的改性的淀粉产品在蒸煮时产生更清澈的浆糊和亮白色凝胶。从改性的淀粉制造的浆糊在20%固体和约65.5℃(150)具有约20至25厘泊的Brookfield粘度。另外,当在50℃(122)贮存30分钟,所述浆糊显示出可接受的粘度稳定性。
实施例2
通过与氢氧自由基反应改性的淀粉在中性pH,133.3℃(290)以及约340千帕(50psi)背压下喷射蒸煮(jet cooked)。当倾倒为膜或到纸上时,如在表面上浆或涂层应用中,所述浆糊具有可接受的膜特性。
实施例3
将轻微稀释的氢氧自由基处理过的淀粉作为载体淀粉应用到波纹板胶粘剂,从而增加胶粘煮熟固体,并且提供载体回复来制造更有粘性、更有延展性的胶粘剂。改性的淀粉在高剪切混和器中约37.8℃(100)下用足够的碱来彻底蒸煮淀粉。加入额外的水、未改性淀粉和硼砂,从而完成波纹板胶粘剂。用氢氧自由基处理的淀粉通常占胶粘剂淀粉总量的10-20%。加入碱,从而充分降低胶粘剂的凝胶温度至低于约65.5℃(150),硼砂通常加入胶粘剂中干苛性碱(形式为氢氧化钠)的50-100%。凝胶温度是指胶粘剂为未煮熟的或第二部分,其悬浮在作为载体的未改性淀粉中。波纹板胶粘剂的精确配方和配料比例根据工厂和需要运用的性质变化。
实施例4
氢氧自由基处理的淀粉在约137.8℃(280)和约207千帕(30psi)背压下喷射蒸煮。将经蒸煮的淀粉与浆糊中约0.5%组分重量的表面活性剂(美国Illinois,Morton Grove,Magrabar ChemicalCorporation的VS100)混和。将得到的浆糊冷却至不透明白色凝胶,并具有稳定的粘性。可将这个浆糊随防腐剂引入并作为洗液配方的活性成分。
Claims (21)
1.用于改性碳水化合物的方法,包括在含氢氧自由基的溶剂的浆料中反应碳水化合物的步骤。
2.权利要求1的方法,其中所述溶剂为水。
3.权利要求1的方法,其中所述氢氧自由基是从水、过氧化物或其他含氢氧基化学物质在紫外辐射下反应形成,或由水、过氧化物或其他含氢氧基化学物质的电化学分解形成。
4.权利要求1的方法,其中所述碳水化合物选自淀粉、水状胶质和纤维素。
5.权利要求4的方法,其中所述淀粉是预改性的淀粉。
6.权利要求4的方法,其中所述淀粉是蒸煮的。
7.权利要求1的方法,其中所述过氧化物选自过氧化氢、过氧化钠及其结合。
8.权利要求1的方法,含有在反应步骤之前或期间向浆料加入碱的额外步骤。
9.权利要求8的方法,其中所述碱是碱金属氢氧化物。
10.权利要求9的方法,其中所述碱金属氢氧化物选自氢氧化钠、氢氧化钾及其结合。
11.权利要求1的方法,含有在反应步骤之前或期间向浆料加入酸的额外步骤。
12.权利要求1的方法,含有衍生化反应的额外步骤。
13.权利要求12的方法,其中衍生化反应选自阳离子化、酯化、醚化、磷酸化、羧甲基化和交联化。
14.权利要求1的方法,含有在氢氧自由基反应期间使用催化剂的额外步骤。
15.权利要求1的方法制造的改性的碳水化合物。
16.权利要求12的方法制造的改性的碳水化合物的衍生物。
17.含有改性的碳水化合物粉末的组合物,当其重新水化并加热时,提供清澈的浆糊,在所述碳水化合物回复后变成珍珠白。
18.权利要求17的组合物,其中所述碳水化合物选自淀粉、水状胶质和纤维素。
19.权利要求17的组合物,进一步包括添加剂,其选自粘度稳定剂、功能性化学物质、交联剂及其结合。
20.含有权利要求15的改性的碳水化合物的产品。
21.权利要求20的产品,选自波纹板胶粘剂、纸上浆、纸张涂层、石膏板、食品、凝胶、浆糊和洗液。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/132017 | 2005-05-18 | ||
US11/132,017 US20060263510A1 (en) | 2005-05-18 | 2005-05-18 | Hydroxyl radical modification of carbohydrates |
Publications (1)
Publication Number | Publication Date |
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CN1865288A true CN1865288A (zh) | 2006-11-22 |
Family
ID=37424451
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CNA2006100844284A Pending CN1865288A (zh) | 2005-05-18 | 2006-05-18 | 碳水化合物的氢氧自由基改性 |
Country Status (10)
Country | Link |
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US (1) | US20060263510A1 (zh) |
KR (1) | KR20060119778A (zh) |
CN (1) | CN1865288A (zh) |
AR (1) | AR056988A1 (zh) |
BR (1) | BRPI0601776A (zh) |
CA (1) | CA2537786A1 (zh) |
CO (1) | CO5840254A1 (zh) |
MX (1) | MXPA06004574A (zh) |
PE (1) | PE20070042A1 (zh) |
ZA (1) | ZA200603977B (zh) |
Cited By (1)
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CN102372786A (zh) * | 2010-08-24 | 2012-03-14 | 玉米制品国际有限公司 | 利用不断产生的羟基自由基的碳水化合物的改性 |
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EP1826219A1 (en) * | 2006-02-24 | 2007-08-29 | SOLVAY (Société Anonyme) | Process for the manufacture of oxidized starch, oxidized starch and its use |
US20080277264A1 (en) * | 2007-05-10 | 2008-11-13 | Fluid-Quip, Inc. | Alcohol production using hydraulic cavitation |
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- 2005-05-18 US US11/132,017 patent/US20060263510A1/en not_active Abandoned
-
2006
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- 2006-04-19 CO CO06036795A patent/CO5840254A1/es not_active Application Discontinuation
- 2006-04-25 MX MXPA06004574A patent/MXPA06004574A/es unknown
- 2006-04-25 AR ARP060101639A patent/AR056988A1/es not_active Application Discontinuation
- 2006-05-15 BR BRPI0601776-2A patent/BRPI0601776A/pt not_active IP Right Cessation
- 2006-05-16 PE PE2006000513A patent/PE20070042A1/es not_active Application Discontinuation
- 2006-05-16 KR KR1020060043758A patent/KR20060119778A/ko not_active Application Discontinuation
- 2006-05-17 ZA ZA200603977A patent/ZA200603977B/xx unknown
- 2006-05-18 CN CNA2006100844284A patent/CN1865288A/zh active Pending
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CN102372786A (zh) * | 2010-08-24 | 2012-03-14 | 玉米制品国际有限公司 | 利用不断产生的羟基自由基的碳水化合物的改性 |
Also Published As
Publication number | Publication date |
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PE20070042A1 (es) | 2007-02-05 |
ZA200603977B (en) | 2009-08-26 |
CO5840254A1 (es) | 2007-12-31 |
KR20060119778A (ko) | 2006-11-24 |
AR056988A1 (es) | 2007-11-07 |
BRPI0601776A (pt) | 2007-03-06 |
US20060263510A1 (en) | 2006-11-23 |
MXPA06004574A (es) | 2007-02-08 |
CA2537786A1 (en) | 2006-11-18 |
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