CN104292343A - Polyamino starch and preparation method thereof - Google Patents
Polyamino starch and preparation method thereof Download PDFInfo
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- CN104292343A CN104292343A CN201410492113.8A CN201410492113A CN104292343A CN 104292343 A CN104292343 A CN 104292343A CN 201410492113 A CN201410492113 A CN 201410492113A CN 104292343 A CN104292343 A CN 104292343A
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- 229920002472 Starch Polymers 0.000 title claims abstract description 98
- 235000019698 starch Nutrition 0.000 title claims abstract description 98
- 239000008107 starch Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920000768 polyamine Polymers 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 19
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 125000003277 amino group Chemical group 0.000 claims abstract description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 30
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 22
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 13
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical group CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 6
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000021962 pH elevation Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 239000000945 filler Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000008247 solid mixture Substances 0.000 abstract 1
- 229920000881 Modified starch Polymers 0.000 description 10
- 235000019426 modified starch Nutrition 0.000 description 10
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 9
- 239000004368 Modified starch Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- -1 3-chloro-hydroxypropenyl Chemical group 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
本发明公开了一种多胺基淀粉及其制备方法。本发明中的多胺基淀粉是由淀粉、交联剂与含两个端伯胺基的有机化合物通过交联反应制备而成的；多胺基淀粉是通过干法制备的，其特征是将含两个端伯胺基的有机化合物和交联剂加入到碱化淀粉中，在搅拌机中混合均匀，然后将固态混合物在一定温度下反应制备多胺基淀粉。由于胺基的引入而使多胺基淀粉具有一些新的性质；通过调整多胺、交联剂与淀粉的比例可以调整多胺基淀粉的氮含量、吸附性、稳定性等。该发明所涉及的多胺基淀粉的制备方法具备工艺简单、环境友好、反应条件温和等特点，所生产的多胺基淀粉具有成本低、吸附性与稳定性可调等特点，可应用于纯化分离、废水处理、填充剂等领域。The invention discloses a polyamine-based starch and a preparation method thereof. The polyamine-based starch in the present invention is prepared from starch, a cross-linking agent and an organic compound containing two terminal primary amino groups through a cross-linking reaction; the polyamine-based starch is prepared by a dry method, and is characterized in that The organic compound containing two terminal primary amino groups and the cross-linking agent are added to the alkalized starch, mixed evenly in a mixer, and then the solid mixture is reacted at a certain temperature to prepare the polyamine-based starch. Due to the introduction of amine groups, the polyamine-based starch has some new properties; the nitrogen content, adsorption, and stability of the polyamine-based starch can be adjusted by adjusting the ratio of polyamine, cross-linking agent and starch. The preparation method of polyamine-based starch involved in this invention has the characteristics of simple process, environment-friendly, mild reaction conditions, etc. The produced polyamine-based starch has the characteristics of low cost, adjustable adsorption and stability, etc., and can be applied to purification Separation, wastewater treatment, fillers and other fields.
Description
技术领域 technical field
本发明属于淀粉改性产品的制备技术领域，尤其涉及通过干法反应制备多胺基淀粉。 The invention belongs to the technical field of preparation of modified starch products, and in particular relates to the preparation of polyamine-based starch through dry reaction.
背景技术 Background technique
淀粉是植物中普遍存在的储藏多糖，是一种来源既便宜又广泛的天然高分子。改性淀粉具有无毒、原料来源广、价格低、易于生物降解等优点，近年来得到重视和发展应用。国内外生产变性淀粉方法主要有湿法、干法等；目前我国变性淀粉生产绝大多数都是采用湿法工艺。湿法也称浆法，即将淀粉分散在水或其它液体介质中，配成一定浓度悬浮液，在一定温度条件下与化学试剂进行反应，生成变性淀粉。其优点是反应均匀、产品质量稳定、生产控制容易；缺点是产品不易回收、生产耗水量大、污水需处理，因而成本较高。在国外，干法工艺已逐渐成为生产变性淀粉主要方法。干法生产变性淀粉一般是在淀粉含少量水（通常20%左右）情况下，将反应试剂喷到淀粉上，经充分混合后，在一定条件下反应并得到干燥产品；具有工艺简单、反应效率高、环境污染小、生产成本低等优点。 Starch is a storage polysaccharide ubiquitous in plants and a natural polymer with cheap and wide sources. Modified starch has the advantages of non-toxic, wide source of raw materials, low price, easy biodegradation, etc., and has been paid attention to and developed in recent years. The production methods of modified starch at home and abroad mainly include wet method and dry method; at present, most of the modified starch production in my country adopts wet method. The wet method is also called the slurry method, that is, the starch is dispersed in water or other liquid media to form a suspension with a certain concentration, and reacts with chemical reagents at a certain temperature to generate modified starch. The advantages are uniform reaction, stable product quality, and easy production control; the disadvantages are that the product is not easy to recycle, the production consumes a lot of water, and the sewage needs to be treated, so the cost is high. In foreign countries, the dry process has gradually become the main method of producing modified starch. The dry method of producing modified starch is generally to spray the reaction reagent on the starch when the starch contains a small amount of water (usually about 20%), and after being fully mixed, react under certain conditions to obtain a dry product; it has simple process and high reaction efficiency. High, low environmental pollution, low production costs and other advantages.
多胺基淀粉是改性淀粉的一种重要衍生物。多胺基淀粉是指在淀粉大分子中引入多个胺基。由于胺基的引入，使改性淀粉具有特殊的活性，多胺基淀粉可用于复合材料的添加剂、纯化分离、废水处理等领域。由于可选择的多胺和交联剂有多种类型，所以多胺基淀粉品种繁多；不同类型的多胺基淀粉可根据吸附性、稳定性等应用在不同的领域。 Polyamine starch is an important derivative of modified starch. Polyamine-based starch refers to the introduction of multiple amine groups into the starch macromolecule. Due to the introduction of amine groups, the modified starch has special activity, and the polyamine-based starch can be used in additives for composite materials, purification and separation, wastewater treatment and other fields. Since there are many types of polyamines and cross-linking agents that can be selected, there are many kinds of polyamine-based starches; different types of polyamine-based starches can be used in different fields according to their adsorption properties and stability.
有关制备多胺基淀粉的报道不是很多，几乎所有方法都是湿法。曲荣君等在碱性水溶液中将可溶性淀粉、环氧氯丙烷与二乙烯三胺通过一步反应法制备了多胺基淀粉树脂[曲荣君, 孙言志, 王春华, 新型球状胺基淀粉树脂的合成及性能, 材料研究学报, 2009, 15, 473-478]；相波等在水溶液中通过三步法制备了交联氨基淀粉，先在碱性介质中将淀粉与环氧氯丙烷反应制备交联淀粉，再以高氯酸为引发剂在交联淀粉上引入3-氯-羟基丙烯基，最后将上述中间产物在碱性水溶液中分别与二乙烯三胺、三乙烯四胺、四乙烯戊胺反应得到相应的交联氨基淀粉[相波, 李义久, 倪亚明, 氨基淀粉絮凝剂合成工艺, 化工环保, 2003, 23, 300-303; 相波, 李义久, 倪亚明, 交联氨基淀粉的制备及其螯合性能研究, 工业水处理, 2003, 23, 26-28; 相波, 李义久, 倪亚明, 交联氨基淀粉的制备及对铜离子的吸附性能, 上海环境科学, 2003, 22, 828-831]。相波等所制备的多胺基淀粉只反应多胺上的一个胺基。上述两种方法均为湿法制备多胺基淀粉，且工艺比较复杂。通过交联剂、多胺直接与淀粉反应制备多胺基淀粉的方法此后并未得到进一步的发展。多胺基淀粉是一类重要的淀粉衍生物，但至今为止还没有关于用多胺、交联剂和淀粉通过一步干法制备多胺基淀粉的报道。 There are not many reports about the preparation of polyamine-based starch, and almost all methods are wet methods. Qu Rongjun et al. prepared polyamine-based starch resin by one-step reaction method of soluble starch, epichlorohydrin and diethylenetriamine in alkaline aqueous solution [Qu Rongjun, Sun Yanzhi, Wang Chunhua, Synthesis of New Spherical Amino-based Starch Resin and properties, Journal of Materials Research, 2009, 15, 473-478]; Xiangbo et al. prepared cross-linked amino starch in aqueous solution by a three-step method, and first reacted starch with epichlorohydrin in alkaline medium to prepare cross-linked starch Starch, and then use perchloric acid as an initiator to introduce 3-chloro-hydroxypropenyl on the cross-linked starch, and finally the above-mentioned intermediate product is mixed with diethylenetriamine, triethylenetetramine, tetraethylenepentylamine respectively in alkaline aqueous solution Reaction to obtain the corresponding cross-linked amino starch Synergy Research, Industrial Water Treatment, 2003, 23, 26-28; Xiangbo, Li Yijiu, Ni Yaming, Preparation of cross-linked amino starch and its adsorption performance on copper ions, Shanghai Environmental Science, 2003, 22, 828-831]. The polyamine-based starch prepared by Xiangbo et al. only reacted with one amine group on the polyamine. The above two methods are all wet methods for preparing polyamine-based starch, and the process is relatively complicated. The method of preparing polyamine-based starch by direct reaction of cross-linking agent and polyamine with starch has not been further developed since then. Polyamine-based starch is an important class of starch derivatives, but so far there is no report on the preparation of polyamine-based starch by a one-step dry method using polyamines, cross-linking agents and starch.
发明内容 Contents of the invention
本发明的目的在于提供一种多胺基淀粉及其制备方法。本发明中的多胺基淀粉是由淀粉、交联剂与含两个端伯胺基的有机化合物通过干法反应制备而成的；该发明所涉及的多胺基淀粉的制备方法具备工艺简单、环境友好、反应条件温和等特点，所生产的多胺基淀粉具有成本低、吸附性与稳定性可调等特点，可应用于纯化分离、废水处理、填充剂等领域。 The object of the present invention is to provide a polyamine-based starch and a preparation method thereof. The polyamine-based starch in the present invention is prepared by dry reaction of starch, a cross-linking agent and an organic compound containing two terminal primary amino groups; the preparation method of the polyamine-based starch involved in the present invention has a simple process , environmental friendliness, mild reaction conditions, etc. The polyamine-based starch produced has the characteristics of low cost, adjustable adsorption and stability, and can be used in purification and separation, wastewater treatment, fillers and other fields.
本次发明所提出的技术方案是：通过含两个端伯胺基的有机化合物、交联剂直接与淀粉反应制备多胺基淀粉，交联剂一端与淀粉羟基反应，另一端与胺基反应；本发明中的多胺基淀粉具有如下化学分子结构通式： The technical solution proposed in this invention is to prepare polyamine-based starch by reacting an organic compound containing two terminal primary amino groups and a cross-linking agent directly with starch. One end of the cross-linking agent reacts with the starch hydroxyl group, and the other end reacts with the amine group. ; Polyamine-based starch in the present invention has following chemical molecular structure general formula:
(St-R)nNHmR'NHm(R-St)n (St-R) n NH m R'NH m (R-St) n
式中：St为淀粉分子；R为乙二醇二缩水甘油醚、甲醛、戊二醛、环氧氯丙烷、三偏磷酸钠中的1～3种；NH2R'NH2为尿素、三聚氰胺、硫脲、乙二胺、1,3-丙二胺、1,6-己二胺、苯二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺中的1～4种；1≤n≤2，0≤m≤1，m+n=2。 In the formula: St is starch molecule; R is ethylene glycol diglycidyl ether, formaldehyde, glutaraldehyde, epichlorohydrin, sodium trimetaphosphate 1 to 3 kinds; NH 2 R'NH 2 is urea, melamine , thiourea, ethylenediamine, 1,3-propylenediamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine ~4 types; 1≤n≤2, 0≤m≤1, m+n=2.
分碱化、交联两步制备多胺基淀粉：(1)碱化过程选用碱性催化剂为KOH、NaOH、Na2CO3、K2CO3、CH3COOK、CH3COONa中的1～3种。将浓度为1～100%，更优为30～70%的碱液在搅拌下加入到淀粉中，然后用高速搅拌机搅拌混合1～30min，再将混合物置于温度为20～60℃的环境中碱化0.1～5h，得到碱化淀粉。碱摩尔用量为淀粉按葡萄糖单元摩尔数计算量的0.01～3倍。碱化温度优选为40～50℃，碱化时间优选为0.5～3h。 The polyamine-based starch is prepared in two steps of alkalization and crosslinking: (1) The alkalinity catalyst is selected as KOH, NaOH, Na 2 CO 3 , K 2 CO 3 , CH 3 COOK, CH 3 COONa in 1~ 3 types. Add the lye with a concentration of 1 to 100%, more preferably 30 to 70%, into the starch under stirring, then stir and mix with a high-speed mixer for 1 to 30 minutes, and then place the mixture in an environment with a temperature of 20 to 60°C Alkalinize for 0.1-5 hours to obtain alkalized starch. The molar amount of alkali used is 0.01 to 3 times the amount of starch calculated on the basis of glucose unit moles. The alkalization temperature is preferably 40-50°C, and the alkalization time is preferably 0.5-3h.
(2)交联反应是将碱化淀粉、含两个端伯胺基的有机化合物以及交联剂初步混合后用高速搅拌机搅拌混合1～30min，再将混合物置于温度为20～80℃的环境中交联反应1～10h。反应完毕将产物用甲醇、乙醇、水、丙酮中的1～3种溶剂反复洗涤，然后过滤、干燥、粉碎得到多胺基淀粉。含两个端伯胺基的有机化合物的摩尔用量为淀粉按葡萄糖单元摩尔数计算量的0.01～3倍，交联剂摩尔用量为含两个端伯胺基的有机化合物的摩尔用量的2～8倍。交联温度优选为40～70℃，交联反应时间优选为3～8h。 (2) The cross-linking reaction is to preliminarily mix the alkalized starch, the organic compound containing two terminal primary amino groups, and the cross-linking agent, then stir and mix with a high-speed mixer for 1 to 30 minutes, and then place the mixture in a room with a temperature of 20 to 80 ° C. The cross-linking reaction in the environment takes 1-10 hours. After the reaction is completed, the product is repeatedly washed with 1 to 3 kinds of solvents among methanol, ethanol, water and acetone, then filtered, dried and pulverized to obtain the polyamine starch. The molar dosage of the organic compound containing two terminal primary amino groups is 0.01 to 3 times the amount of starch calculated by the number of moles of glucose units, and the molar dosage of the crosslinking agent is 2 to 3 times the molar dosage of the organic compound containing two terminal primary amino groups. 8 times. The crosslinking temperature is preferably 40-70° C., and the crosslinking reaction time is preferably 3-8 hours.
制备多胺基淀粉所用交联剂为乙二醇二缩水甘油醚、甲醛、戊二醛、环氧氯丙烷、三偏磷酸钠的1～3种；所用的含两个端伯胺基的有机化合物包括尿素、硫脲、乙二胺、1,3-丙二胺、1,6-己二胺、苯二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺中的1～4种。 The cross-linking agents used in the preparation of polyamine-based starch are 1 to 3 kinds of ethylene glycol diglycidyl ether, formaldehyde, glutaraldehyde, epichlorohydrin, and sodium trimetaphosphate; Compounds include urea, thiourea, ethylenediamine, 1,3-propylenediamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine 1 to 4 of them.
本发明中碱化步骤主要是提高淀粉与交联剂的反应效率，当直接把淀粉、碱催化剂、交联剂与含两个端伯胺基的有机化合物混合均匀后也可以反应。当选用反应活性高的含两个端伯胺基的有机化合物如乙二胺、1,3-丙二胺、1,6-己二胺、苯二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺等，采用湿法制备多胺基淀粉时，反应非常剧烈，难以控制甚至无法反应，采用本发明中的半干法固相反应方法可以使反应温和进行，而且还有副产物少、产率高等优点。 The alkalization step in the present invention is mainly to improve the reaction efficiency of the starch and the cross-linking agent, and the reaction can also be performed after directly mixing the starch, the alkali catalyst, the cross-linking agent and the organic compound containing two terminal primary amino groups. When using highly reactive organic compounds containing two terminal primary amino groups such as ethylenediamine, 1,3-propylenediamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylenetetramine , tetraethylenepentamine, pentaethylenehexamine, etc., when the polyamine-based starch is prepared by a wet method, the reaction is very violent, difficult to control or even unable to react, and the semi-dry solid-phase reaction method in the present invention can make the reaction mild. It also has the advantages of less by-products and high yield.
本发明的有益效果是直接用含两个端伯胺基的有机化合物、交联剂与淀粉通过干法反应制备多胺基淀粉，代替传统的用湿法反应制备多胺基淀粉的路线。该多胺基淀粉由于胺基的引入而具有一些新的性质；通过调整多胺、交联剂与淀粉的比例可以调整多胺基淀粉的氮含量、吸附性、稳定性等。该发明所涉及的多胺基淀粉的制备方法具备工艺简单、环境友好、反应条件温和等特点，所生产的多胺基淀粉具有成本低、吸附性与稳定性可调等特点，可应用于纯化分离、废水处理、填充剂等领域。 The beneficial effect of the present invention is that the polyamine-based starch is directly prepared by dry reaction with an organic compound containing two terminal primary amino groups, a cross-linking agent and starch, instead of the traditional method of preparing polyamine-based starch by wet reaction. The polyamine-based starch has some new properties due to the introduction of amine groups; the nitrogen content, adsorption and stability of the polyamine-based starch can be adjusted by adjusting the ratio of polyamine, cross-linking agent and starch. The preparation method of polyamine-based starch involved in this invention has the characteristics of simple process, environment-friendly, mild reaction conditions, etc. The produced polyamine-based starch has the characteristics of low cost, adjustable adsorption and stability, etc., and can be applied to purification Separation, wastewater treatment, fillers and other fields.
具体实施方式：下面结合实施例对本发明作进一步的说明。 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS: The present invention will be further described below in conjunction with the examples.
实施例1：取干燥的玉米淀粉100g，另取0.01～3倍淀粉摩尔数（按葡萄糖单元摩尔数计算）的NaOH配成1～100%的碱液，将碱液在搅拌下加入到淀粉中，然后用高速搅拌机搅拌混合1～30min，再将混合物置于温度为20～60℃的环境中碱化0.1～5h，得到碱化淀粉。 Example 1: Take 100g of dry cornstarch, and take 0.01 to 3 times the molar number of starch (calculated by the molar number of glucose units) of NaOH to prepare 1 to 100% lye, and add the lye to the starch under stirring , and then use a high-speed mixer to stir and mix for 1 to 30 minutes, and then place the mixture in an environment with a temperature of 20 to 60° C. for 0.1 to 5 hours of alkalization to obtain alkalized starch.
将的0.01～3倍淀粉摩尔数（按葡萄糖单元摩尔数计算）的乙二胺、2～8倍乙二胺摩尔数的环氧氯丙烷混合均匀后在搅拌下加入到碱化淀粉中，经初步混合后用高速搅拌机搅拌混合1～30min，再将混合物置于温度为20～80℃的环境中交联反应1～10h。反应完毕将产物用体积比5:5的乙醇水溶液反复洗涤，然后过滤、干燥、粉碎得到多胺基淀粉。 Mix ethylenediamine with 0.01-3 times the moles of starch (calculated on the basis of moles of glucose units) and epichlorohydrin with 2-8 times the moles of ethylenediamine, and add them to the alkalized starch under stirring. After preliminary mixing, use a high-speed mixer to stir and mix for 1-30 minutes, and then place the mixture in an environment with a temperature of 20-80° C. for 1-10 hours for cross-linking reaction. After the reaction is completed, the product is repeatedly washed with an aqueous ethanol solution with a volume ratio of 5:5, then filtered, dried, and pulverized to obtain polyamine-based starch.
实施例2-5：方法同实施例1，即利用乙二醇二缩水甘油醚、甲醛、戊二醛、三偏磷酸钠替代实施例1中的环氧氯丙烷，分别得到相应的多胺基淀粉。 Embodiment 2-5: method is the same as embodiment 1, promptly utilizes ethylene glycol diglycidyl ether, formaldehyde, glutaraldehyde, sodium trimetaphosphate to replace epichlorohydrin in embodiment 1, obtains corresponding polyamine group respectively starch.
实施例6-14：用尿素、硫脲、1,3-丙二胺、1,6-己二胺、苯二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺分别代替实施例1中的乙二胺，其他条件同实施例1，得到相应的多胺基淀粉。 Example 6-14: Using urea, thiourea, 1,3-propylenediamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexa Amines were used to replace ethylenediamine in Example 1, and other conditions were the same as in Example 1 to obtain the corresponding polyamine-based starch.
实施例15-23：用尿素、硫脲、1,3-丙二胺、1,6-己二胺、苯二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺分别代替实施例2中的乙二胺，其他条件同实施例2，得到相应的多胺基淀粉。 Example 15-23: Using urea, thiourea, 1,3-propylenediamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexa Amines were used to replace ethylenediamine in Example 2, and other conditions were the same as in Example 2 to obtain the corresponding polyamine-based starch.
实施例24-32：用尿素、硫脲、1,3-丙二胺、1,6-己二胺、苯二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺分别代替实施例3中的乙二胺，其他条件同实施例3，得到相应的多胺基淀粉。 Example 24-32: Using urea, thiourea, 1,3-propylenediamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexa Amines were used to replace ethylenediamine in Example 3, and other conditions were the same as in Example 3 to obtain the corresponding polyamine-based starch.
实施例33-41：用尿素、硫脲、1,3-丙二胺、1,6-己二胺、苯二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺分别代替实施例4中的乙二胺，其他条件同实施例4，得到相应的多胺基淀粉。 Example 33-41: Using urea, thiourea, 1,3-propylenediamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexa Amines were used to replace ethylenediamine in Example 4, and other conditions were the same as in Example 4 to obtain the corresponding polyamine-based starch.
实施例42-50：用尿素、硫脲、1,3-丙二胺、1,6-己二胺、苯二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺分别代替实施例5中的乙二胺，其他条件同实施例5，得到相应的多胺基淀粉。 Example 42-50: Using urea, thiourea, 1,3-propylenediamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexa Amines were used to replace ethylenediamine in Example 5, and other conditions were the same as in Example 5 to obtain the corresponding polyamine-based starch.
实施例51-60：用乙二醇二缩水甘油醚、环氧氯丙烷、甲醛、戊二醛、三偏磷酸钠中的二种、三种替代实施例1中的环氧氯丙烷，用尿素、硫脲、乙二胺、1,3-丙二胺、1,6-己二胺、苯二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、五乙烯六胺中的二种、三种、四种分别代替实施例5中的乙二胺，其他条件同实施例1，得到相应的多胺基淀粉。 Embodiment 51-60: replace the epichlorohydrin in Example 1 with two or three kinds of ethylene glycol diglycidyl ether, epichlorohydrin, formaldehyde, glutaraldehyde, and sodium trimetaphosphate, and use urea , thiourea, ethylenediamine, 1,3-propylenediamine, 1,6-hexanediamine, phenylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine One kind, three kinds, four kinds replace the ethylenediamine in embodiment 5 respectively, other conditions are the same as embodiment 1, obtain corresponding polyamine base starch.
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