CN101222973A - 乳化剂 - Google Patents
乳化剂 Download PDFInfo
- Publication number
- CN101222973A CN101222973A CNA2006800254815A CN200680025481A CN101222973A CN 101222973 A CN101222973 A CN 101222973A CN A2006800254815 A CNA2006800254815 A CN A2006800254815A CN 200680025481 A CN200680025481 A CN 200680025481A CN 101222973 A CN101222973 A CN 101222973A
- Authority
- CN
- China
- Prior art keywords
- starch
- emulsifying agent
- succinic acid
- emulsion
- esterification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 61
- 229920002472 Starch Polymers 0.000 claims abstract description 110
- 235000019698 starch Nutrition 0.000 claims abstract description 110
- 239000008107 starch Substances 0.000 claims abstract description 109
- 238000005886 esterification reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000006260 foam Substances 0.000 claims abstract description 12
- 239000002537 cosmetic Substances 0.000 claims abstract description 9
- 235000013305 food Nutrition 0.000 claims abstract description 9
- 239000000839 emulsion Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 34
- -1 alkyl succinic acid Chemical compound 0.000 claims description 32
- 230000002209 hydrophobic effect Effects 0.000 claims description 26
- 230000032050 esterification Effects 0.000 claims description 23
- 108010043797 4-alpha-glucanotransferase Proteins 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 230000002255 enzymatic effect Effects 0.000 claims description 14
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 108700023372 Glycosyltransferases Proteins 0.000 claims description 11
- 102000051366 Glycosyltransferases Human genes 0.000 claims description 11
- 239000001384 succinic acid Substances 0.000 claims description 11
- 229920000945 Amylopectin Polymers 0.000 claims description 10
- GUOCOOQWZHQBJI-UHFFFAOYSA-N 4-oct-7-enoxy-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OCCCCCCC=C GUOCOOQWZHQBJI-UHFFFAOYSA-N 0.000 claims description 9
- 229940014800 succinic anhydride Drugs 0.000 claims description 9
- 102100040894 Amylo-alpha-1,6-glucosidase Human genes 0.000 claims description 8
- 108010025880 Cyclomaltodextrin glucanotransferase Proteins 0.000 claims description 8
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 8
- 229920000856 Amylose Polymers 0.000 claims description 7
- 108090000344 1,4-alpha-Glucan Branching Enzyme Proteins 0.000 claims description 6
- 102000003925 1,4-alpha-Glucan Branching Enzyme Human genes 0.000 claims description 6
- 229920000310 Alpha glucan Polymers 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 244000068988 Glycine max Species 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 3
- 240000003183 Manihot esculenta Species 0.000 claims description 3
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 3
- 244000061456 Solanum tuberosum Species 0.000 claims description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 3
- 230000009435 amidation Effects 0.000 claims description 3
- 238000007112 amidation reaction Methods 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
- WSFYPFLCEFLXOZ-UHFFFAOYSA-N 2-decylbutanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)CC(O)=O WSFYPFLCEFLXOZ-UHFFFAOYSA-N 0.000 claims description 2
- HLWLFKQBSHRRCB-UHFFFAOYSA-N 2-nonylbutanedioic acid Chemical compound CCCCCCCCCC(C(O)=O)CC(O)=O HLWLFKQBSHRRCB-UHFFFAOYSA-N 0.000 claims description 2
- 240000005979 Hordeum vulgare Species 0.000 claims description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 244000098338 Triticum aestivum Species 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- YLAXZGYLWOGCBF-UHFFFAOYSA-N 2-dodecylbutanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)CC(O)=O YLAXZGYLWOGCBF-UHFFFAOYSA-N 0.000 claims 1
- 235000010716 Vigna mungo Nutrition 0.000 claims 1
- 235000005072 Vigna sesquipedalis Nutrition 0.000 claims 1
- 244000090207 Vigna sesquipedalis Species 0.000 claims 1
- 240000001417 Vigna umbellata Species 0.000 claims 1
- 235000011453 Vigna umbellata Nutrition 0.000 claims 1
- 125000004450 alkenylene group Chemical group 0.000 claims 1
- 235000021278 navy bean Nutrition 0.000 claims 1
- 102000004190 Enzymes Human genes 0.000 abstract description 31
- 108090000790 Enzymes Proteins 0.000 abstract description 31
- 229940088598 enzyme Drugs 0.000 description 30
- 239000000243 solution Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- KCYQMQGPYWZZNJ-BQYQJAHWSA-N hydron;2-[(e)-oct-1-enyl]butanedioate Chemical compound CCCCCC\C=C\C(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-BQYQJAHWSA-N 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 229920001685 Amylomaize Polymers 0.000 description 6
- 229920002245 Dextrose equivalent Polymers 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 4
- 108090000637 alpha-Amylases Proteins 0.000 description 4
- 102000004139 alpha-Amylases Human genes 0.000 description 4
- 229940024171 alpha-amylase Drugs 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000019197 fats Nutrition 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 2
- YOWKKGPNCDIFFB-UHFFFAOYSA-N 3-decyloxolane-2,5-dione Chemical compound CCCCCCCCCCC1CC(=O)OC1=O YOWKKGPNCDIFFB-UHFFFAOYSA-N 0.000 description 2
- PMSSUODTFUHXHO-UHFFFAOYSA-N 3-nonyloxolane-2,5-dione Chemical compound CCCCCCCCCC1CC(=O)OC1=O PMSSUODTFUHXHO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 241000204666 Thermotoga maritima Species 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000002036 drum drying Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 235000015243 ice cream Nutrition 0.000 description 2
- 230000000937 inactivator Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002453 shampoo Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003900 succinic acid esters Chemical group 0.000 description 2
- VRMCZMSNFPRPQA-UHFFFAOYSA-N (1-chloro-2-hydroxypropyl)-dimethyl-octadecylazanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C(Cl)C(C)O VRMCZMSNFPRPQA-UHFFFAOYSA-N 0.000 description 1
- NTWLQOMOKLYGMH-UHFFFAOYSA-N (1-chloro-2-hydroxypropyl)-dimethyl-tetradecanoylazanium Chemical class CCCCCCCCCCCCCC(=O)[N+](C)(C)C(Cl)C(C)O NTWLQOMOKLYGMH-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 1
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- YZUMRMCHAJVDRT-UHFFFAOYSA-N 2-(hexadecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCCCOCC1CO1 YZUMRMCHAJVDRT-UHFFFAOYSA-N 0.000 description 1
- ZXJBWUAALADCRI-UHFFFAOYSA-N 2-(octadecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCCCCCOCC1CO1 ZXJBWUAALADCRI-UHFFFAOYSA-N 0.000 description 1
- CWNOEVURTVLUNV-UHFFFAOYSA-N 2-(propoxymethyl)oxirane Chemical compound CCCOCC1CO1 CWNOEVURTVLUNV-UHFFFAOYSA-N 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- 241000193375 Bacillus alcalophilus Species 0.000 description 1
- CSKIOBVGCJKFBL-UHFFFAOYSA-N ClC(C(C)O)[N+](CCCCCCCCCCCCCCCC)(C)C Chemical class ClC(C(C)O)[N+](CCCCCCCCCCCCCCCC)(C)C CSKIOBVGCJKFBL-UHFFFAOYSA-N 0.000 description 1
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及乳化剂、制备所述乳化剂的方法、以及其在各种应用、主要是在食品和化妆品应用中的用途。本发明也涉及所述乳化剂用于生成有弹性的胶状泡沫的用途。本发明的乳化剂是基于用特殊类型的酶进行酶转化并在特殊的酯化反应中进行修饰的淀粉。
Description
本发明涉及乳化剂、制备所述乳化剂的方法、以及所述乳化剂在各种应用、主要是食品和化妆品应用中的用途。
日常生活遇到的许多产品、特别是食品和化妆品都是胶状系统的实例。胶状系统的特征是存在均匀地分布在整个载体容积中的固体、液体或气体的小颗粒。颗粒常常被称作胶状系统的分散相或不连续相，而载体通常被称作连续相。胶状系统的常见实例包括冰淇淋和面包，其中小气泡组成了分散相；以及沙拉酱，其中分散相是由分散在水性、液态连续相中的小滴液态油组成的。
其中分散相和连续相都为液体的胶状系统被分类为乳剂。乳剂是两种不混溶的液体的紧密混合物，其中一液相以小液滴的形式分散在另一液相中。根据相的组成来分类传统乳剂。如果连续相是水而不连续相是油时，乳剂被分类为水包油(O/W)型乳剂。反过来的情况则被分类为油包水(W/O)型乳剂。O/W型乳剂一般都是白色和奶油色的，而W/O型乳剂一般都是深色并具有油脂的质地。
所有的胶状系统(包括乳剂)的共同点是它们通常都需要稳定化，以避免分离成两相。固体和液体乳剂对稳定化有着不同的要求。例如，在涂脂例如人造奶油中，主要通过三维网络的结晶脂肪稳定W/O型乳剂。液体乳剂系统是更加动态的系统。当将油强烈地搅拌于水中时，就形成了粗制的乳剂形式。这种乳剂是非常不稳定的，该系统将在短时间内分离成为油层和水层。要稳定该系统，就要使用乳化剂。
在食品和化妆品工业中，多种化学产品和组合物都被用作乳化剂。在其多种功能中，乳化剂也作为乳剂连续相的粘度或流动性的稳定剂。通常需要乳剂是耐储存的，而乳化剂有助于实现这个目标。
由于其耐储存性，阿拉伯胶优选地用于多种应用，特别是用于乳剂的冷冻或冰冻储存。它已经被用作食品例如糖果、糖浆、香料油乳剂、冰淇淋和饮料中的乳化剂和稳定剂。它是支链的、取代的杂多糖，其特征是极好的水溶性、低粘度、以及无臭味、无色和无香味。它是中东和非洲产的天然存在的树胶。但是，它是一种昂贵的产品，其供应和质量都不可预见。
在多种应用中，都可以用烷基琥珀酸酯化淀粉或烯基琥珀酸酯化淀粉取代阿拉伯胶。特别地，辛烯基琥珀酸酯化淀粉已经被广泛地用作乳化剂。这些淀粉的应用可以降低成本并提高供应的稳定性。
淀粉本身并不适用作乳化剂，因为它缺少必需的亲脂性基团。因此，它与包含水不溶性物质的系统不相容。通过用环状二羧酸酐如辛烯基琥珀酸酐处理淀粉形成烷基或烯基二羧酸淀粉可以给淀粉引入两亲特性。作为这种改性的结果，淀粉在水溶液中被稳定，因此可以阻碍退减作用(retrogradation)。这些淀粉的显著优点是保留了它们的亲水性，同时引入了疏水性。
对于许多应用而言，迫切地需要进一步提高乳剂稳定性，因此需要改良的乳化剂。本发明正是在这种情况下作出的。
本发明提供了具有提高了的稳定乳剂性能的乳化剂。具体地，本发明提供了乳化剂，所述乳化剂包含通过疏水试剂对淀粉的醚化作用、酯化作用或酰胺化作用以及利用糖基转移酶(E.C.2.4)的酶转化获得的疏水性淀粉，其中疏水试剂包括具有从7到24个碳原子的烷基或烯基链。本发明的乳化剂不仅可以用于稳定由两个不混溶的液相组成的乳剂，也可以用于稳定其他类型的胶状系统，最明显的实例是由分散于液体、油或水的连续相中的气态分散相组成的泡沫。从下面详细的描述和附录的实施例中可以清楚地看到本发明的其他优点。
值得注意的是，在现有技术中已经提出了用不同的酶处理辛烯基琥珀酸酯化淀粉。
在欧洲专利申请0 913 406中，提出了葡萄糖淀粉酶的用途。其描述了该酶优选地造成淀粉被降解到获得了包裹剂而不是乳化剂的程度的用途。在本发明中，并不需要这种降解。
欧洲专利申请0 332 027披露了β-淀粉酶的用途。但是，值得注意的是所获得的产品的55％具有约50的右旋糖当量(DE)(麦芽糖)。其余的产品是稳定的、所谓的β-极限糊精。这意味着所获得的产品中只有约45％可以被用于乳化作用，因为众所周知DE超过20的产品不足以稳定乳剂。
本发明的乳化剂所基于的淀粉理论上可以源自所有的植物来源。可以使用根或块茎淀粉例如木薯淀粉或马铃薯淀粉、和谷类淀粉及果实淀粉例如玉米、水稻、小麦或大麦淀粉。也可以使用豆类淀粉例如豌豆淀粉或大豆淀粉。
天然淀粉通常具有更高或更低固定比例的淀粉的两个组分：直链淀粉和支链淀粉。在一些淀粉例如玉米淀粉或水稻淀粉中，存在着天然发生的变体，其主要只包含支链淀粉。也可以使用这些通常被称作蜡状淀粉的淀粉。在其他的淀粉例如马铃薯或木薯淀粉中，有着遗传学修饰的或突变的变体，其也主要只包含支链淀粉。应理解这些变体的用途也在本发明的范围之内，所述变体通常包含超过80重量％、优选地超过95重量％淀粉干重的支链淀粉。最后，高直链淀粉的淀粉变体(例如高直链淀粉马铃薯淀粉)也可以用于制备本发明的乳化剂。在本发明中，可以使用有着各种直链淀粉与支链淀粉比值的淀粉。
为了制备本发明的乳化剂，淀粉必须进行两种处理。淀粉必须进行糖基转移酶(E.C.2.4)的酶转化以及必须与疏水试剂反应。已经发现可以按任何次序实施这些处理，以便获得高的产品质量。当首先用酶处理淀粉然后使淀粉与疏水试剂反应时，已经发现可以获得疏水作用(hydrophobation)中更高的取代度(DS)，这造成了乳剂中更大的稳定能力。同样，如果按此次序处理淀粉，通常获得了更为均匀的产物。另一方面，当首先使淀粉与疏水试剂反应，然后进行酶的作用时，获得了更纯的产物，这需要相对少的纯化和洗涤处理。
本发明中被用于酶转化淀粉的酶是E.C.2.4类糖基转移酶。优选的酶是那些属于己糖基转移酶(E.C.2.4.1)类的酶。
在本发明的一个优选实施方式中，用来自4-α-葡聚糖转移酶(E.C.2.4.1.25)类的酶或其活性对应于所述酶的酶在水性介质中处理淀粉。这类酶的一般和相关的活性是其将一个片段的1，4-α-D-葡聚糖转移到了受体中的新的4-位点，这可以是葡萄糖或1，4-α-D-葡聚糖，如EP-A-O932 444所述。
可以从各种生物体中获得4-α-葡聚糖转移酶。从文献中得知这些酶存在于真核和细菌的代表种类中。还知道这些酶存在于古细菌的代表种类中。优选地使用能耐受相当高的温度例如约70℃的4-α-葡聚糖转移酶。常见实例包括来自极端嗜热菌(Thermus thermophilus)、海栖热袍菌(Thermotoga maritima)、和来自古细菌的嗜热性代表种类中的4-α-葡聚糖转移酶。但是，也可以使用分别来自例如马铃薯或大肠杆菌的非热稳定型4-α-葡聚糖转移酶如D酶和淀粉麦芽糖酶。4-α-葡聚糖转移酶应当没有α-淀粉酶活性，本领域技术人员通过例如纯化可以容易地实现这一点。
在本发明的另一个优选的实施方式中，用来自环麦芽糖糊精葡聚糖转移酶(E.C.2.4.1.19)类的酶或其活性对应于所述酶的酶在水性介质中处理淀粉。这类酶通过形成1，4-α-D-糖苷键环化了部分1，4-α-D-葡聚糖链，如WO-A-89/01043、WO-A-92/13962、和EP-A-O 690 170所披露。
可以从各种来源中获得环麦芽糖糊精葡聚糖转移酶，如R.L.Whistleret al.，″Starch：Chemistry and Technology″，2nd Ed.，1984，Academic Press，pp.143-144；
″Minutes of the Fifth International Symposium onCyclodextrins″，Editions de Santé，Paris 1990，pp.19-61；和A.R.Hedges，″Minutes of the Sixth International Symposium on Cyclodextrins″，Editionsde Sante，Paris，1992，pp.23-58所披露的那样。
在本发明的又一个优选的实施方式中，用来自1，4-α-葡聚糖分支酶(E.C.2.4.1.18)类的酶或其活性对应于所述酶的酶在水性介质中处理淀粉。这类酶将一个片段的1，4-α-D-葡聚糖链转移到相似葡聚糖链的伯羟基上，如EP-A-O690 170所披露的那样。
1，4-α-葡聚糖分支酶可以源自很多来源，例如源自脂肪嗜热芽孢杆菌(Bacillus stearothermophilus)的细菌。在EP-A-O418 945中披露了这种1，4-α-葡聚糖分支酶的具体实例。
可以用胶化淀粉和仍为颗粒形式、但已经被处理成膨胀状态即部分胶化状态的淀粉实施酶转化。但是，优选的是淀粉为胶化状态。可以在蒸汽注射装置(例如喷射式蒸煮器)中分批地或连续地进行胶凝作用。可以在胶凝作用之前、或优选地在胶凝作用之后加入酶。
进行酶转化的反应条件将取决于所用的淀粉和糖基转移酶的类型，例如依据上面引用的涉及4-α-葡聚糖转移酶、环麦芽糖糊精葡聚糖转移酶、和1，4-α-葡聚糖分支酶的文献，本领域技术人员可以容易地确定出反应条件。在实践中，通常在或接近酶具有最佳活性和稳定性的pH值和温度下进行反应。所用酶的量不是特别关键的，主要取决于转化所要占用的时间。
酶转化的进程也取决于所选酶的类型，通过测定粘度或凝胶强度可以跟踪酶转化的进程。通常当达到平衡状态以及没有进一步的转化发生时，酶转化就终止了。
在已经发生了所需的酶转化之后，如果需要，例如可以通过加热反应混合物来灭活酶。在利用部分胶化淀粉进行酶转化的情况下，在经加热灭活酶之后，就完成了胶凝作用。如果需要，通过已知的分离技术例如透析可以从淀粉中去除酶。
在本发明中，通过醚键、酯键或酰胺键可以连接疏水性取代基和淀粉。
当疏水基经醚键与淀粉相连时，疏水试剂优选地包含作为反应位点的卤化物、卤代醇、环氧化物或缩水甘油基。疏水试剂的烷基链可以从4到24个碳原子不等，优选地是从7到20个碳原子。提供醚键的疏水试剂的合适实例是十六烷基溴化物、十二烷基溴化物、环氧丁烷、环氧化大豆脂肪醇、环氧化亚麻子脂肪醇、烯丙基缩水甘油醚、丙基缩水甘油醚、丁基缩水甘油醚、癸烷缩水甘油醚、月桂缩水甘油醚、月桂苯基缩水甘油醚、肉豆蔻酰缩水甘油醚、鲸蜡基缩水甘油醚、棕榈酰缩水甘油醚、硬脂酰缩水甘油醚、亚油酰缩水甘油醚及其混合物。可以用于和本发明的淀粉反应的其他醚化剂是包含至少4个碳原子的卤代烃，例如1-溴癸烷、10-溴-1-癸醇、和1-溴十二烷。
在本发明一个实施方式中，引入了带电荷的疏水基。通过淀粉和包含季铵基的试剂(例如1-氯-2-羟丙基三烷基铵盐或缩水甘油三烷基铵盐)的反应可以经醚键连接疏水性阳离子基团。该季铵基的烷基链可以有1到24个碳原子不等，优选的是从7到20个碳原子，其中季铵基的烷基链中的至少一个包含4到24个碳原子。优选地，其他烷基链有不到7个碳原子。例如1-氯-2-羟丙基二甲基月桂基铵盐、1-氯-2-羟丙基二甲基肉豆蔻酰铵盐、1-氯-2-羟丙基二甲基鲸蜡基铵盐、1-氯-2-羟丙基二甲基硬脂基铵盐、缩水甘油二甲基月桂基铵盐、缩水甘油二甲基肉豆蔻酰铵盐、缩水甘油二甲基鲸蜡基铵盐、缩水甘油二甲基硬脂基铵盐、二烷基氨乙基卤化物、或上述物质的混合物都可以被用作疏水性阳离子化试剂。通过与季铵基例如氯乙基二烷基铵氯化氢盐的反应可以引入疏水性阳离子基团。该季铵基的烷基链可以从1到24个碳原子不等。与EP-A-O189 935披露的方法类似，可以实施用于引入疏水性阳离子基团的反应。例如与EP-A-O689 829所述的方法类似，通过用2-氯-氨基二烷基酸作为试剂可以连接疏水性阴离子基团。
当疏水基经酯键与淀粉相连时，可以使用几种试剂(例如烷基酸酐)。烷基链可以从4到24个碳不等，优选地是从7到20个碳。特别地，混合酸酐例如辛酸乙酸酐、癸酸乙酸酐、月桂酸乙酸酐、肉豆蔻酸乙酸酐是合适的烷基酸酐。
在本发明的一个优选的实施方式中，疏水性阴离子基团可以与支链淀粉相连。通过具体的淀粉和烷基琥珀酸酐或烯基琥珀酸酐的反应可以实现这一点。烷基链可以从4到24个碳不等，优选的是从7到20个碳。最常使用的是辛烯基琥珀酸酐、壬基琥珀酸酐、癸基琥珀酸酐、十二碳烯基琥珀酸酐。可以用任何已知的方式(例如与US-A-5,776,476所披露的方法类似的方式)进行酯化反应以引入所需的烷基琥珀酸酯基或烯基琥珀酸酯基。优选地，淀粉与包含具有8到12个碳原子的烷基或链烯基的烷基琥珀酸酐或烯基琥珀酸酐反应。辛烯基琥珀酸酐、壬基琥珀酸酐、癸基琥珀酸酐、十二碳烯基琥珀酸酐是特别优选的，而最为优选的是辛烯基琥珀酸酐。因此，烷基琥珀酸酯化淀粉或烯基琥珀酸酯化淀粉优选地是辛烯基琥珀酸酯化淀粉、壬基琥珀酸酯化淀粉、癸基琥珀酸酯化淀粉、或十二碳烯基琥珀酸酯化淀粉，甚至更优选的是辛烯基琥珀酸酯化淀粉。
为了制备出经酰胺基与羧甲基支链淀粉相连的疏水基，可以类似地应用WO-A-94/24169所述的方法。用于引入酰胺基的合适的试剂的实例包括包含具有8到30个碳原子的饱和或不饱和烃基的脂肪胺。并不排除支链烃基，但是直链是优选的。脂肪基优选地源自C12到C24脂肪胺。如果脂肪胺选自正-十二烷胺、正-十六胺、正-十八胺、可可胺、牛油脂肪胺、氢化N-牛脂基-1，3-二氨基丙烷、N-氢化牛脂基-1，3-二氨基丙烷、和N-油基-1，3-二氨基丙烷，则可获得特别有利的结果。这些脂肪胺已知的商品名为Armeen和Duomeen(AKZO Chemicals)。
疏水取代度(即DS)被定义为每摩尔葡萄糖单位的疏水性取代基的平均摩尔数，在本发明的方法中获得的DS可以有所不同，主要取决于产品的预期应用。DS一般都大于0，优选的是从0.005到约0.5，更优选的是从0.01到0.1。令人惊奇地注意到，甚至非常小的DS都会产生相当大的作用。
可以在淀粉悬浮液即使用未被预胶凝化的淀粉、淀粉悬浮液或在半干状态下进行与疏水试剂的反应。当在酶转化后进行疏水作用时，淀粉通常已经被胶凝化。
当在悬浮液或溶液中进行反应时，水被用作溶剂。当所用的疏水试剂具有低水溶性时，可以采用水和合适的可与水混合的有机溶剂的组合。合适的有机溶剂包括但不限于甲醇、乙醇、异-丙醇、正-丙醇、叔-丁醇、仲-丁醇、甲乙酮、四氢呋喃、二烷和丙酮。优选地用包含超过20重量％的淀粉和小于80重量％的溶剂的反应混合物进行溶液中的反应。更优选地，反应混合物中的淀粉含量是在20和40重量％之间，而溶剂含量优选地是在80和60重量％之间。如果需要，例如可以利用透析、超滤、超离心等浓缩和/或纯化溶液。联合干燥器(转鼓式干燥器、喷雾式干燥器)的高压灭菌器可以用作反应容器。还可以在公知的用于类似反应的条件下进行所述反应。pH值优选地是在7和13之间。优选地，在存在腐蚀性催化剂(例如碱金属氢化物等)的条件下实施本发明的方法。在具体的实施方式中，可以使用腐蚀性催化剂，其量使得其事实上是作为试剂。
本发明的乳化剂可以被用于多种应用，特别是食品和化妆品工业。应理解本发明也包括如上所述的乳化剂用于稳定乳剂、以及稳定包含乳剂或具有乳剂形式的食品和化妆品的用途，其中上述乳化剂作为乳化剂存在。本发明的乳化剂在化妆品中可以被用作例如护发素、洗发剂、润肤剂、洗剂和乳膏中的乳化剂、增稠剂、或表面活性剂。
在一个优选的实施方式中，本发明的乳化剂可以被用于取代基于蛋白(如酪蛋白或酪蛋白酸盐)的乳化剂、或其他乳化剂(如单硬脂酸甘油酯或双硬脂酸甘油酯)，或者用于取代焙烤食品或乳化调料中的鸡蛋。值得注意的是，本发明的乳化剂在这个方面通常是更为多能的，因为它甚至在高温下都能保持其乳化性能，而蛋黄在超过65℃的温度下变性。并且，本发明的乳化剂的用途也减少了引入常常存在于鸡蛋内的细菌如沙门氏菌的危险。
进一步已经发现本发明的乳化剂可以用于生成有弹性的、胶状泡沫，特别是当所述乳化剂是基于具有高直链淀粉含量的淀粉时。根据这个实施方式，优选地使用具有高直链淀粉含量的淀粉，高直链淀粉含量是例如从20到70重量％，更优选的是从30到50重量％的淀粉干重。通过在水中强烈地混合例如20重量％的混合物重的量的淀粉可以制备出这种泡沫。这些泡沫可以在食品和化妆品工业找到它们的应用，例如作为如生奶油、蛋糖霜、洗发剂、刮胡霜、沐浴胶(bath or shower gel)、和液体肥皂中的泡沫促进剂。
在另一个实施方式中，本发明的乳化剂可以用于造纸。在这个方面的优选的应用是本发明的乳化剂用于稳定烯基琥珀酸酐(ASA)和/或烯基烯酮二聚体(AKD)乳剂的用途。在这个方面的另一个优选的应用是本发明的乳化剂在生成可以用于表面施胶纸或表面涂层纸的乳剂的乙烯基单体的乳液聚合中的用途。
现将通过下面的非限制性实施例阐明本发明。
实施例1：辛烯基琥珀酸酯化的附加分支淀粉的制备
在160℃下喷射式制熟5摩尔常规马铃薯淀粉(20％干物质)的水悬浮液。将对应于250g淀粉(干物质)量的溶液转移到5L双壁玻璃反应器内，并将温度设定到65℃。调整pH值到6.5，并加入每克淀粉200U酶(Rhodothermus Marinas分支酶，供应商TNO Food-Groningen)。在65℃下持续搅拌48个小时进行反应。
然后将溶液冷却到30℃，通过加入4.4重量％的NaOH水溶液将溶液的pH值设定到8.5。向溶液内缓慢地加入一定量的辛烯基琥珀酸酐，以获得Ds最大值为0.028。在加料期间，反应混合物的pH值保持恒定于8.5。在4个小时的反应之后，混合物的pH值被中和到6.2。
用乙醇絮凝产物。给搅拌器装满800ml乙醇(95％)。缓慢地加入200ml淀粉溶液，同时搅拌器按其最大速度的50％进行搅拌混合。然后，混合速度增加到全速30秒钟，并用布氏漏斗过滤混合物。将产物重悬于800ml乙醇，以最大速度混合，过滤并干燥。
实施例2：辛烯基琥珀酸酯化淀粉麦芽糖酶淀粉的制备
在160℃的温度下喷射式制熟含有10摩尔常规马铃薯淀粉(20％干物质)的水悬浮液。然后通过测定溶液的质量和浓度(白利糖度％)可以计算出溶液中的干物质的量。将溶液转移到10L双壁玻璃反应器内，并将温度设定到70℃。调整pH值到6.2，并加入每克淀粉2U酶(淀粉麦芽糖酶，供应商TNO Food-Groningen)。在70℃下持续搅拌24个小时进行反应。然后通过在160℃的温度下喷射式蒸煮溶液灭活酶。通过测定溶液的质量和浓度(白利糖度％)再次计算出溶液中的干物质的量。
然后将溶液冷却到30℃，通过加入4.4重量％的NaOH水溶液将溶液的pH值设定到8.5。向溶液缓慢地加入一定量的辛烯基琥珀酸酐，使得获得Ds最大值为0.028。在加料期间，反应混合物的pH值保持恒定于8.5。在4个小时的反应之后，混合物的pH值被中和到6.2，用220℃的入口温度和103℃的出口温度喷射干燥溶液。
实施例3：经淀粉麦芽糖酶处理过的辛烯基琥珀酸酯化淀粉的制备
用自来水制备出包含15摩尔直链淀粉含量为36重量％的马铃薯淀粉的淀粉悬浮液(39％，W/W)，并通过加入4.4重量％的NaOH水溶液将悬浮液的pH值设定到8.5。将温度设定到20℃，向溶液缓慢地加入一定量的辛烯基琥珀酸酐，以获得Ds最大值为0.02。在反应期间，用4.4％NaOH(W/V)将pH值维持在8.5。在4个小时的反应之后，混合物的pH值被中和到6.2，并利用布氏漏斗以15L自来水洗涤混合物。将作为36％(W/W)悬浮液的产物在8巴和6rpm(4筒，隙缝宽度0.3mm)进行转鼓式干燥，并研碎(Peppink，250μm筛)。
然后在70℃的温度下，在搅拌式Terlet反应器中，将10摩尔转鼓式干燥的辛烯基琥珀酸酯化淀粉溶解于自来水中，浓度为10％(W/W)。对于均质溶液，在加入酶之前搅拌浆糊至少4个小时。将溶液的pH值设定到6.2，并加入每克淀粉(干物质)2单位的酶(淀粉麦芽糖酶，供应商TNO Food-Groningen)。通过在160℃下喷射式蒸煮溶液终止反应。在此之后，用220℃的入口温度和103℃的出口温度喷射干燥溶液。
实施例4：乳化性能
如实施例1到3所述制备产物。将6克淀粉悬浮于10ml向日葵油内，并加入190ml 0.02％的叠氮化钠溶液。利用Silverston匀浆器以最大速度匀浆1分钟制备出预乳剂。之后，根据表1的方案用微流化床装置制备乳剂。表2概述了结果。
表1：微流化床装置的匀浆作用
| 循环 | 限制 | 压力(巴) |
| 1 | 0 | ＜50 |
| 2 | 2 | 400 |
| 3 | 2 | 400 |
表2：乳剂的稳定性
| 乳化剂 | 稳定期 | DS | DE |
| 马铃薯淀粉的经α淀粉酶处理过的辛烯基琥珀酸衍生物 | 3天 | 0.022 | 4.4 |
| 马铃薯淀粉的脱支的辛烯基琥珀酸衍生物 | 13天 | 0.021 | 6.5 |
| 马铃薯淀粉的经淀粉麦芽糖酶处理过的辛烯基琥珀酸衍生物 | 20天 | 0.018 | ＜0.5 |
| 马铃薯淀粉的附加分支的辛烯基琥珀酸衍生物 | 34天 | 0.018 | ＜0.5 |
| 中高直链淀粉马铃薯淀粉的经α淀粉酶处理过的辛烯基琥珀酸衍生物 | 2天 | 0.023 | 3.9 |
| 中高直链淀粉马铃薯淀粉的经淀粉麦芽糖酶处理过的辛烯基琥珀酸衍生物 | 20天 | 0.023 | ＜0.5 |
| 支链淀粉马铃薯淀粉的经α淀粉酶处理过的辛烯基琥珀酸衍生物 | 6天 | 0.021 | 4.7 |
| 支链淀粉马铃薯淀粉的附加分支的辛烯基琥珀酸衍生物 | 41天 | 0.019 | ＜0.5 |
表2显示出淀粉的附加分支的辛烯基琥珀酸衍生物和经淀粉麦芽糖酶处理过的辛烯基琥珀酸衍生物可以开发出更加稳定的乳剂。通过皂化作用和酸碱滴定测定出取代度(DS)，用Luff-Schoorl测定出右旋糖当量(DE)。
实施例5：泡沫试验
在Hobart混合器中，用搅乳器(whisk)以最大速度搅打40克实施例1到3所述的产物和160克去离子水2到3分钟。混合时间为2到3分钟之间不等，这取决于产物的泡沫生成。
中高直链淀粉马铃薯淀粉的经淀粉麦芽糖酶处理过的辛烯基琥珀酸衍生物生成了有弹性的胶状泡沫。未经处理的(blank)中高直链淀粉马铃薯淀粉生成了多少有些破碎的胶状泡沫。
Claims (21)
1.一种乳化剂，包含疏水性淀粉，所述疏水性淀粉是通过疏水试剂对淀粉的醚化作用、酯化作用或酰胺化作用以及利用糖基转移酶(E.C.2.4)的酶转化而获得的，其中所述疏水试剂包含具有7到24个碳原子的烷基链或烯基链。
2.权利要求1的乳化剂，其中所述疏水性淀粉是烷基琥珀酸酯化淀粉或烯基琥珀酸酯化淀粉。
3.权利要求2的乳化剂，其中所述烷基琥珀酸酯化淀粉或烯基琥珀酸酯化淀粉是辛烯基琥珀酸酯化淀粉、壬基琥珀酸酯化淀粉、癸基琥珀酸酯化淀粉、或月桂基琥珀酸酯化淀粉。
4.权利要求3的乳化剂，其中所述淀粉是辛烯基琥珀酸酯化淀粉。
5.前述权利要求中任一项的乳化剂，其中所述烷基琥珀酸酯化淀粉或烯基琥珀酸酯化淀粉的取代度(DS)是从0.005到0.5，优选地是从0.01到0.1。
6.前述权利要求中任一项的乳化剂，其中所述糖基转移酶是4-α-葡聚糖转移酶(E.C.2.4.1.25)。
7.权利要求1到5中任一项的乳化剂，其中所述糖基转移酶是环麦芽糖糊精葡聚糖转移酶(E.C.2.4.1.19)。
8.权利要求1到5中任一项的乳化剂，其中所述糖基转移酶是1，4-α-葡聚糖分支酶(E.C.2.4.1.18)。
9.前述权利要求中任一项的乳化剂，其中所述淀粉是马铃薯、木薯、小麦、大麦、玉米、水稻、豌豆、或大豆淀粉。
10.权利要求9的乳化剂，其中以所述淀粉的干重计，所述淀粉的直链淀粉含量为20到70重量％、优选地30到50重量％。
11.权利要求9的乳化剂，其中以所述淀粉的干重计，所述淀粉的支链淀粉含量为高于80重量％、优选地高于95重量％。
12.制备前述权利要求中任一项的乳化剂的方法，包括用疏水试剂对淀粉的醚化作用、酯化作用或酰胺化作用以及利用糖基转移酶(E.C.2.4)的酶转化，所述疏水试剂包含具有7到24个碳原子的烷基链。
13.权利要求12的方法，用包含具有7到24个碳原子的烷基或烯基的疏水试剂酯化所述淀粉。
14.权利要求12或13的方法，其中首先用糖基转移酶(E.C.2.4)对所述淀粉进行酶转化，随后用烷基琥珀酸酐或烯基琥珀酸酐进行酯化。
15.权利要求12或13的方法，其中首先用烷基琥珀酸酐或烯基琥珀酸酐酯化所述淀粉，随后用糖基转移酶(E.C.2.4)进行酶转化。
16.一种食品或化妆品，包含乳剂或为乳剂形式，其中以权利要求1到11中任一项的乳化剂作为乳化剂。
17.权利要求1到11中任一项的乳化剂用于稳定乳剂的用途。
18.权利要求1到11中任一项的乳化剂用于生成有弹性的、凝胶状泡沫的用途。
19.权利要求1到11中任一项的乳化剂用于稳定烯基琥珀酸酐(ASA)和/或烯基烯酮二聚体(AKD)乳剂的用途。
20.权利要求1到11中任一项的乳化剂在乙烯基单体的乳液聚合中的用途。
21.包含权利要求1到11中任一项的乳化剂的泡沫。
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| EP05076605.4 | 2005-07-12 | ||
| EP05076605.4A EP1743693B1 (en) | 2005-07-12 | 2005-07-12 | Emulsifier |
| PCT/NL2006/000347 WO2007008066A1 (en) | 2005-07-12 | 2006-07-10 | Emulsifier |
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| CN101222973A true CN101222973A (zh) | 2008-07-16 |
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| EP (1) | EP1743693B1 (zh) |
| JP (1) | JP5936802B2 (zh) |
| CN (1) | CN101222973B (zh) |
| AU (1) | AU2006267170B8 (zh) |
| BR (1) | BRPI0613448B1 (zh) |
| CA (1) | CA2615120C (zh) |
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| CN101716476B (zh) * | 2009-11-13 | 2012-08-08 | 华南理工大学 | 一种淀粉烷基苷表面活性剂的制备方法 |
| CN104395347A (zh) * | 2012-06-21 | 2015-03-04 | 不二制油株式会社 | 豆科种子多糖类琥珀酸衍生物酯及其制造方法 |
| CN110885403A (zh) * | 2018-09-11 | 2020-03-17 | 上海东升新材料有限公司 | 一种改性淀粉乳化剂及采用该乳化剂制备的akd乳液 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102028632A (zh) * | 2009-10-07 | 2011-04-27 | 强生消费者公司 | 含有超亲水两亲性共聚物的组合物及其应用方法 |
| CN101716476B (zh) * | 2009-11-13 | 2012-08-08 | 华南理工大学 | 一种淀粉烷基苷表面活性剂的制备方法 |
| CN101891830A (zh) * | 2010-07-06 | 2010-11-24 | 华南理工大学 | 一种淀粉基高分子表面活性剂及其制备方法 |
| CN104395347A (zh) * | 2012-06-21 | 2015-03-04 | 不二制油株式会社 | 豆科种子多糖类琥珀酸衍生物酯及其制造方法 |
| CN110885403A (zh) * | 2018-09-11 | 2020-03-17 | 上海东升新材料有限公司 | 一种改性淀粉乳化剂及采用该乳化剂制备的akd乳液 |
Also Published As
| Publication number | Publication date |
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| EP1743693A1 (en) | 2007-01-17 |
| WO2007008066A1 (en) | 2007-01-18 |
| BRPI0613448A2 (pt) | 2012-11-06 |
| AU2006267170A1 (en) | 2007-01-18 |
| CN101222973B (zh) | 2013-03-27 |
| JP2009501076A (ja) | 2009-01-15 |
| ES2625898T3 (es) | 2017-07-20 |
| CA2615120A1 (en) | 2007-01-18 |
| JP5936802B2 (ja) | 2016-06-22 |
| MX2008000444A (es) | 2008-03-10 |
| US8178323B2 (en) | 2012-05-15 |
| EP1743693B1 (en) | 2017-03-29 |
| AU2006267170B2 (en) | 2010-07-29 |
| AU2006267170B8 (en) | 2010-09-23 |
| US20100029928A1 (en) | 2010-02-04 |
| CA2615120C (en) | 2013-12-31 |
| BRPI0613448B1 (pt) | 2017-07-04 |
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